CN104204105A

CN104204105A - Triarylmethane compound, colored resin composiiton, color filter, liquid crystal display device, and organic EL display device

Info

Publication number: CN104204105A
Application number: CN201380017411.5A
Authority: CN
Inventors: 西村政昭; 志贺靖; 藤原宗贤; 高桥裕子; 铃木夕起
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Rayon Co Ltd
Priority date: 2012-03-29
Filing date: 2013-03-28
Publication date: 2014-12-10
Anticipated expiration: 2033-03-28
Also published as: KR20140142262A; CN104204105B; JPWO2013147099A1; TWI588212B; TW201348341A; JP6168048B2; WO2013147099A1

Abstract

The present invention addresses the problem of providing a colored resin composition which is capable of providing a pixel that has a good balance between luminance and voltage holding ratio. The present invention also addresses the problem of providing: a color filter which comprises a pixel that has high luminance and high voltage holding ratio; a high-quality liquid crystal display device; and an organic EL display device. The present invention relates to a colored resin composition which is characterized by containing (A) a dye, (B) a solvent and (C) a binder resin, and which is also characterized in that the dye (A) contains a compound that is represented by formula (I). (In the formula, R1-R8, M+ and n are as defined in claim 1.)

Description

Triarylmethane compounds, colored resin composition, colour filter, liquid crystal indicator and organic EL display

Technical field

The present invention relates to triarylmethane compounds, colored resin composition, colour filter, liquid crystal indicator and organic EL display.

Background technology

The flat-panel monitor that liquid crystal indicator and organic EL (Electroluminescence) display unit be representative of take is widely used, and in these indicating meters, has used colour filter.

Be accompanied by the energy-saving trend in such epoch, as colour filter, require more high brightness and high-contrast.

In colour filter, mainly used colored resin composition, in this colored resin composition, used pigment, but in order to obtain high brightness and high-contrast, for example, the method below 1/2 that the particle diameter differential of pigment particles is dissipated to its color development wavelength is disclosed in non-patent literature 1.

On the other hand, as tinting material, also carried out the exploitation of dyestuff.

For example, use triarylmethane derivatives is disclosed as dyestuff in patent documentation 1.In addition, in patent documentation 2 and 3, disclosing and in triarylmethane salt, further having made negatively charged ion is the technology of ad hoc structure.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2008-304766 communique

Patent documentation 2: TOHKEMY 2011-132492 communique

Patent documentation 3: TOHKEMY 2011-133844 communique

Non-patent literature

Non-patent literature 1: the clear < < of the bridge pawl Se Cai will > > of association (< < look material Association meeting Chi > >), in December, 1967, p608

Summary of the invention

The problem that invention will solve

But about disclosed method, particularly blue pigments in non-patent literature 1, because the redness with other, veridian are compared, its color development wavelength is shorter, in this case, need further differential loose, the stability after cost raising and dispersion becomes problem.

In addition, in triarylmethane salt having been carried out to the patent documentation 1～3 of improvement, the pixel that discovery will obtain is difficult to have both brightness and voltage retention.

Therefore, problem of the present invention is, a kind of novel triarylmethane compounds is provided, and it can obtain the pixel that has both brightness and voltage retention.

In addition, problem of the present invention is to provide a kind of novel colored resin composition that contains triarylmethane compounds, and it can form also high pixel of the high and voltage retention of brightness.

In addition, problem of the present invention is to provide a kind of high and voltage retention of the brightness also colour filter of high pixel and high-quality liquid crystal indicator and organic EL display of comprising.

The method of dealing with problems

What the inventor etc. conducted in-depth research found that, has the novel triarylmethane compounds of ad hoc structure by use, can solve above-mentioned problem, thereby complete the present invention.

; the present invention relates to triarylmethane compounds (following; sometimes referred to as " compound (I) "), the colored resin composition, colour filter, liquid crystal indicator and the organic EL display that contain compound (I); described triarylmethane compounds is characterised in that, it is represented by following formula (I).

[1] the triarylmethane compounds that following formula (I) represents,

[Chemical formula 1]

(in above-mentioned formula (I), R ¹～R ⁶represent independently of one another hydrogen atom, optionally there is the alkyl of substituent carbonatoms 1～10 or optionally there is substituent aromatic ring group, adjacent R ¹～R ⁶can be connected to each other and form ring, this ring optionally has substituting group,

R ⁷and R ⁸represent independently of one another hydrogen atom or substituting group arbitrarily,

Wherein, R ⁷and R ⁸in at least one for halogen atom or optionally there is the alkyl of substituent carbonatoms 1～10,

M ⁺represent positively charged ion,

N represents 0～4 integer.)

[2] above-mentioned [1] described triarylmethane compounds, wherein, in above-mentioned formula (I), R ⁷for hydrogen atom, R ⁸for halogen atom or optionally there is the alkyl of substituent carbonatoms 1～10.

[3] the described triarylmethane compounds in above-mentioned [1] or [2], wherein, the compound that above-mentioned formula (I) represents is the compound that following formula (II) represents.

[Chemical formula 2]

(in above-mentioned formula (II), n, M ⁺, R ¹～R ⁵, R ⁷and R ⁸with the definition synonym in above-mentioned formula (I),

R ¹¹and R ¹²represent independently of one another hydrogen atom or substituting group arbitrarily,

M represents 1～8 integer.)

[4] colored resin composition, it contains (A) dyestuff, (B) solvent and (C) adhesive resin, wherein,

(A) dyestuff is the triarylmethane compounds described in any one in above-mentioned [1]～[3].

[5] above-mentioned [4] described colored resin composition, wherein, also contains (D) polymerizable monomer.

[6] the described colored resin composition in above-mentioned [4] or [5], wherein, also contains (E) photopolymerization and causes composition and thermopolymerization and cause at least one in composition.

[7] colour filter, it has the pixel of using the formation of the colored resin composition described in any one in above-mentioned [4]～[6].

[8] liquid crystal indicator, it has above-mentioned [7] described colour filter.

[9] organic EL display, it has above-mentioned [7] described colour filter.The effect of invention

According to the present invention, a kind of novel triarylmethane compounds can be provided, it can obtain having both the pixel of brightness and voltage retention.

In addition, according to the present invention, can provide a kind of novel colored resin composition that contains triarylmethane compounds, it can form also high pixel of the high and voltage retention of brightness.

In addition, the present invention can provide and contain the high and voltage retention of the brightness also colour filter of high pixel and high-quality liquid crystal indicator and organic EL display.

Accompanying drawing explanation

[Fig. 1] Fig. 1 is the constructed profile that an example of the organic EL with colour filter of the present invention is shown.

[Fig. 2] Fig. 2 is direct peak (direct peak) figure occurring due to liquid crystal aligning in embodiment.

Nomenclature

100 organic ELs

10 transparent support substrates

20 pixels

30 organic protection layers

40 inorganic oxide films

50 transparent anodes

500 organic luminophors

51 hole injection layers

52 hole transmission layers

53 luminescent layers

54 electron injecting layers

55 negative electrodes

A impurity peaks

B impurity peaks

C maximum ion density

The direct peak current of d liquid crystal (polarity of impurity peaks)

E impurity peaks electric current (selecting peak maximum in impurity peaks)

The direct peak of f liquid crystal

Embodiment

Below, for embodiments of the present invention, be elaborated, but following record is only an example of embodiment of the present invention, the present invention is not limited to these contents.

It should be noted that, in the present invention, " (methyl) acryloyl ", " (methyl) acrylate " etc. refer to " at least one in acryloyl and methacryloyl ", " at least one in acrylate and methacrylic ester " etc., and for example " (methyl) vinylformic acid " refers to " at least one in vinylformic acid and methacrylic acid ".

In addition, " total solids composition " refers to total composition of solvent composition described later colored resin composition of the present invention in addition.

In addition, " aromatic ring " refer to " aromatic hydrocarbons ring " and " heteroaromatic " both.

In addition, the term such as " C.I. Pigment green " refers to pigment call number (C.I.).

First, for the compound in the present invention (I), be described in detail.

[about compound (I)]

Triarylmethane compounds of the present invention is represented by following formula (I).

[chemical formula 3]

M ⁺represent positively charged ion,

N represents 0～4 integer.)

It should be noted that, in above-mentioned formula (I), outside [], illustrate-SO ₃ ^-base and-(SO ₃ ^-m ⁺) _nbasis representation be aromatic ring, the R in [] ¹～R ⁸, or R ¹～R ⁸the substituting group having is respectively by-SO ₃ ^-base or-(SO ₃ ^-m ⁺) _nbase replaces.

(about R ¹～R ⁶)

R ¹～R ⁶represent independently of one another hydrogen atom, optionally there is the alkyl of substituent carbonatoms 1～10 or optionally there is substituent aromatic ring group.

As R ¹～R ⁶in alkyl, can enumerate the alkyl that carbonatoms is generally more than 1 and is generally straight chain shape below 10, a chain or ring-type.As concrete example, can enumerate methyl, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, the tertiary butyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, styroyl etc.

As R ¹～R ⁶in aromatic ring group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group.

As aromatic cyclic hydrocarbon group group, it can be monocycle, also can be condensed ring, be 5～18 to be just not particularly limited so long as form the carbonatoms of ring, for example can enumerate: have 1 free valency phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, the group of ring, benzo phenanthrene ring, acenaphthene ring, benzo acenaphthene ring, fluorenes ring etc.

In addition, as aromatic heterocyclic group, it can be monocycle, also can be condensed ring, as long as form the carbonatoms of ring and be 3～10, be just not particularly limited, for example can enumerate: have 1 free valency furan nucleus, cumarone ring, thiphene ring, thionaphthene ring, pyrrole ring, pyrazole ring, imidazole ring, diazole ring, indole ring, carbazole ring, pyrrolo-imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole ring, Thienopyrroles ring, thienothiophene ring, furo pyrrole ring, furo furan nucleus, thienofuran ring, benzisoxa azoles ring, benzisothiazole ring, benzoglyoxaline ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline 99.9 ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzoglyoxaline ring, the group of pyridine ring, quinazoline ring, quinazolinone ring, Azulene ring etc.

Adjacent R ¹～R ⁶(be specially R ¹and R ², R ³and R ⁴, R ⁵and R ⁶) also can be connected to each other and form ring, and this ring optionally has substituting group.

In addition, this ring can be also the ring forming by heteroatoms bridging, as its concrete example, can enumerate for example following structure.

[chemical formula 4]

From the viewpoint of chemical stability, as R ¹～R ⁶, be preferably hydrogen atom independently of one another, optionally there is the alkyl of substituent carbonatoms 1～10 or optionally there is substituent phenyl, or adjacent R ¹～R ⁶mutually link and the situation of formation ring.These substituting groups are also preferred aspect brightness.From the viewpoint of improving the thermotolerance of compound (I), the excellent in light-resistance of gained colour filter, more preferably hydrogen atom, optionally there is the alkyl of substituent carbonatoms 1～10 or optionally there is substituent phenyl.

R ¹～R ⁶for optionally having in the situation of alkyl of substituent carbonatoms 1～10, can infer, under the effect of hyperconjugation, the electric charge in positively charged ion disperses, and positively charged ion is able to stabilization.

More specifically, for R ¹～R ⁴in the carbonatoms of alkyl, from difficult structure (impact on brightness is little) and the substituting group N that affects triarylmethane skeleton, be difficult for aspect, disengaging aspect (compound (I) is stable), be preferably below 8, more preferably below 4, and be preferably more than 2.

In addition, for R ⁵and R ⁶, the viewpoint that is difficult for decomposition and tone (brightness is high) from compound (I) is considered, preferred R ⁵for hydrogen atom, R ⁶for alkyl.R ⁶in the carbonatoms of alkyl more preferably below 8, more preferably below 5.

In addition, adjacent R ¹～R ⁶mutually link and form in the situation of ring, the substituting group on N is difficult for departing from, therefore stable.

R ¹～R ⁶for optionally having in the situation of substituent phenyl, because conjugated system extends, the electric charge in positively charged ion disperses, cationic stabilized.So, can think that the result of cationic stabilized can make the thermotolerance of resulting colour filter more excellent.

As R ¹～R ⁶in alkyl, aromatic ring group and mutually link and substituting group that the ring that forms optionally has, can enumerate the group in for example following (substituting group group W).

(substituting group group W)

The alkoxyl group of the alkyl of fluorine atom, chlorine atom, carbonatoms 1～8, the thiazolinyl of carbonatoms 2～8, carbonatoms 1～8, phenyl, the alkylsulfamoyl group of the alkyl carbonyl oxy of base, tolyl, naphthyl, cyano group, acetoxyl group, carbonatoms 2～9, sulfamyl, carbonatoms 2～9, the alkyl-carbonyl of carbonatoms 2～9, styroyl, hydroxyethyl, acetamido, bonding have trialkylsilkl, the nitro of dialkyl amido ethyl that the alkyl of carbonatoms 1～4 forms, trifluoromethyl, carbonatoms 1～8, the alkylthio of carbonatoms 1～8.

Wherein, as R ¹～R ⁶in alkyl, aromatic ring group and mutually link and substituting group that the ring that forms optionally has, be preferably the alkyl of carbonatoms 1～10, alkylsulfamoyl group and the fluorine atom of the alkyl carboxyl of the alkoxyl group of carbonatoms 2～8, cyano group, acetoxyl group, carbonatoms 2～8, sulfamyl, carbonatoms 2～9.

(about R ⁷and R ⁸)

R ⁷and R ⁸expression hydrogen atom or arbitrarily substituting group.

As above-mentioned substituting group arbitrarily, can enumerate such as halogen atom, optionally have the alkyl of substituent carbonatoms 1～10, optionally there is substituent aromatic ring group etc.

Wherein, R ⁷and R ⁸in at least one for halogen atom or optionally there is the alkyl of substituent carbonatoms 1～10.

; in phenyl ring in formula (I), with respect to the bonding with being positioned at the carbon atom of triarylmethane structure central authorities, if in ortho position bonding bulky group; from space, near triarylmethane structure central authorities, protected, thereby the thermotolerance of compound (I) improves.

In addition the brightness decline that causes absorption spectrum to change and cause therefrom resulting pixel from the viewpoint of the difficult molecule structure change because of compound (I), R, ⁷and R ⁸in the carbonatoms of alkyl be preferably below 8, more preferably below 6, be particularly preferably below 4, and be generally more than 1.

As R ⁷and R ⁸in preferred mode, preferably R ⁷for hydrogen atom, R ⁸for alkyl, R particularly preferably ⁷for hydrogen atom, R ⁸for methyl.

In addition, R ⁷and R ⁸can mutually link and form ring, this ring optionally has substituting group.As this substituting group, can enumerate the group of recording in for example above-mentioned (substituting group group W).

R ⁷and R ⁸in alkyl have in substituent situation, be preferably halogen atom.That is, can preferably enumerate the fluoro methyl such as trifluoromethyl etc.

(about M ⁺and n)

M ⁺represent positively charged ion, for example can enumerate: hydrogen ion, alkali metal cation, alkaline earth metal cation, tertiary amine positively charged ion or quaternary ammonium cation.

As the basic metal of alkali metal cation, can enumerate lithium, sodium, potassium etc.In addition, as the alkaline-earth metal of alkaline earth metal cation, can enumerate magnesium, calcium, barium etc.

Tertiary amine positively charged ion N ⁺hR ₃(R represents hydrogen atom, optionally has substituent alkyl or optionally have substituent aromatic ring group, it should be noted that, a plurality of R that contain can be the same or different) represents.

The substituent example that in above-mentioned R, the preferred carbonatoms of this alkyl and this alkyl optionally have and above-mentioned R ¹～R ⁶the situation of alkyl under cited carbonatoms, substituting group identical.Substituent example and above-mentioned R that the preferred carbonatoms of this aromatic ring group and this aromatic ring group optionally have ¹～R ⁶the situation of aromatic ring group under cited carbonatoms, substituting group identical.Specifically can enumerate: the low alkyl group ammonium cation of carbonatoms 1～6 (ammonium methyl positively charged ion for example, ethyl ammonium positively charged ion, diethyl ammonium positively charged ion, triethyl ammonium positively charged ion etc.), alkyl ammonium cation (the ethanol ammonium cation for example that replaces the carbonatoms 1～6 there is hydroxyl, di-alcohol ammonium cation, triethanol ammonium positively charged ion etc.), the alkyl ammonium cation of the carbonatoms 1～6 of carboxyl substituted (carboxymethyl ammonium cation for example, propyloic ammonium cation, carboxylic propyl ammonium positively charged ion, dicarboxyl ammonium methyl positively charged ion etc.), replace and to have the ammonium cation of aromatic ring group and alkyl (N for example, N-diethyl phenyl ammonium cation etc.) etc.

Quaternary ammonium cation N ⁺r ₄represent, R represents optionally to have substituent alkyl or optionally has substituent aromatic ring group.It should be noted that, a plurality of R that contain can be the same or different.The substituent example and the above-mentioned R that as preferred carbonatoms and this alkyl of this alkyl, optionally have ¹～R ⁶the situation of alkyl under cited carbonatoms, substituting group identical.Substituent example and above-mentioned R that the preferred carbonatoms of this aromatic ring group and this aromatic ring group optionally have ¹～R ⁶the situation of aromatic ring group under cited carbonatoms, substituting group identical.

Specifically, can enumerate the quaternary alkyl ammonium positively charged ion (for example, tetramethylammonium cation, tetraethylammonium cation, TBuA positively charged ion etc.) etc. of carbonatoms 1～6.

It should be noted that M ⁺cationic kind be not limited to a kind, also can mix multiple.In addition, M ⁺positively charged ion can in a part of compound, mix exist multiple, also can in colored resin composition, mix exist multiple.As M ⁺preferred example, from the deliquescent viewpoint of the organic solvent for using colored resin composition, consider, preferred hydrogen ion, alkali metal cation, tertiary amine positively charged ion, quaternary ammonium cation, more preferably lithium cation, sodium cation, unsubstituted ammonium cation, TBuA positively charged ion.

N represents 0～4 integer.

N is larger, compound (I) is replaced by the sulfo group of hydrophilic radical manyly, its thermotolerance, photostabilization improve, the solvability of compound (I) in hydrophobic liquid crystal also declines, therefore voltage retention improves, but the high viewpoint of solvability from the organic solvent using colored resin composition is considered, is preferably 0～2.

(about-SO ₃ ^-the position of substitution of base)

In compound (I), outside []-SO ₃ ^-basis representation is substituted in [] interior aromatic ring, R ¹～R ⁸, or R ¹～R ⁸on the substituting group having.-SO ₃ ^-preferred the position of substitution of base is hydrogen atom or the R forming on the naphthalene nucleus of triarylmethane skeleton ⁶on substituent hydrogen atom.

Preferably-SO ₃ ^-base is substituted in the reasons are as follows on the naphthalene nucleus that forms triarylmethane skeleton.-SO ₃ ^-base is substituted in compound (I) on naphthalene nucleus in the situation that of intermolecular salify, forms ionic linkage with nitrogen-atoms or the central carbon atom of another molecule, now, due to compound (I)-SO ₃ ^-base is positioned on naphthalene nucleus, and it is near that the distance between the aromatic ring that the naphthalene nucleus of compound (I) and another molecule have becomes.Therefore, 2 is intermolecular except ionic linkage, and also produce π-π and interact, so intermolecular forces enhancing, thermotolerance and electric reliability uprise.In addition, due to-SO ₃ ^-base is positioned on naphthalene nucleus, with the center carbon of a part and-SO ₃ ^-it is near that the position of base becomes, and can also expect in intramolecular firmly salify effect.In addition, particularly-SO ₃ ^-in situation on the ring that the nitrogen-atoms that base is substituted in naphthalene nucleus does not occur to replace, triarylmethane skeleton is little on the contribution of conjugated system, little on the impact of color development, from the viewpoint of brightness, is preferred.

Then, preferably-SO ₃ ^-base is replaced in R ⁶on substituting group on the reasons are as follows.With general-SO ₃ ^-base imports to R ¹～R ⁴substituting group on situation compare, general-SO ₃ ^-base imports to R ⁶on substituting group on restriction on synthetic little, than being easier to, R simultaneously ⁶substituting group on-SO ₃ ^-base, in molecule or during intermolecular formation ionic linkage, can be got position more freely, is easily configured in and can forms the firmly position of ionic linkage.Particularly, R ⁶in situation for alkyl, because substituent degree of freedom is high ,-SO ₃ ^-base is easily positioned at for the ideal position that forms molecule and intermolecular ionic linkage, thereby forms firmly ionic linkage, therefore, from the viewpoint of thermotolerance and electric reliability, is preferred.In addition, brightness little on the contribution of conjugated system, little on the impact of color development from the viewpoint of triarylmethane skeleton, resulting pixel is also preferred.

It should be noted that, in formula (I) ,-SO ₃ ^-base ,-SO ₃ ^-m ⁺the covalent linkage of base is labeled as and refers to being connected in [], has a plurality of the position of substitution, what obtain on synthetic is the meanings such as mixture of the different compound of the position of substitution.

[compound that formula (II) represents]

Excellent from the viewpoint of brightness and the voltage retention of resulting pixel, compound (I) is preferably the represented compound of following formula (II) (following, to be called " compound (II) ").

[chemical formula 5]

(in above-mentioned formula (II), n, M ⁺, R ¹～R ⁵, R ⁷and R ⁸with n, the M in above-mentioned formula (I) ⁺, R ¹～R ⁵, R ⁷and R ⁸synonym.

R ¹¹and R ¹²represent independently of one another hydrogen atom or substituting group arbitrarily.

M represents 1～8 integer.)

(about R ¹¹and R ¹²)

As R ¹¹and R ¹²in substituting group arbitrarily, can enumerate the group of recording in above-mentioned (substituting group group W), from the viewpoint of synthetic easy, be preferably hydrogen atom.

In addition, a plurality of R that contain in a part ¹¹each other and R ¹²each other can be identical or different respectively, from the viewpoint of synthetic easy, preferably identical.

In addition R, ¹¹and R ¹²can be identical or different, from the viewpoint of synthetic easy, preferably identical.

(about m)

M is generally more than 1, is preferably more than 2, and is generally below 8, is preferably below 5.

If in above-mentioned scope ,-(CR ¹¹r ¹²) _mthe SO that-Ji end has ₃ ^-degree of freedom uprise, easily form intermolecular ionic linkage and easily form ionic linkage with intramolecular central carbon atom, thereby thermotolerance and voltage retention are become well, it is preferred from this, putting.

[molecular weight]

The molecular weight of the compound in the present invention (I) is generally more than 450, is preferably more than 500, and is generally below 5000, is preferably below 2000.

In above-mentioned scope, from the viewpoint of synthesizing easy, be preferred if.

[concrete example]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

< is about the synthetic method > of compound (I)

Compound (I) can synthesize based on the theoretical method of manufacturing record in dyestuff chemistry > > (thin Tian Fengzhu, skill report hall, nineteen fifty-seven) of for example < < synthetic dyestuff summary (Gross is said synthetic dyestuff) > > (the rich work of hole mouth, three is publication, nineteen sixty-eight altogether), < <, but is not limited to the method.

Specifically, there is following method: (i) by method, (ii) with the compound structure triarylmethane skeleton of sulfo group, after building triarylmethane skeleton, import the method for sulfo group.

(i) in situation, there is following method: utilize usual method, by forming directly to replace on the phenyl ring of triarylmethane skeleton or naphthalene nucleus, have the raw material of sulfo group or have the raw material of sulfo group to build triarylmethane skeleton forming replacement on the phenyl ring of triarylmethane skeleton or substituting group that naphthalene nucleus has.

(ii) in situation, there is following method: utilize usual method to build triarylmethane skeleton, with sulfuric acid, chlorsulfonic acid, oleum etc., carry out sulfonation, thereby import the method for sulfo group; And the compound with triarylmethane skeleton is reacted with sodium hydroxymethane sulfonate, PS, Isosorbide-5-Nitrae-butane sultone etc., thereby import the substituent method with sulfo group.

The purposes > of < compound (I)

The purposes of compound of the present invention (I) is not particularly limited, can be for various uses.Wherein, from the viewpoint of the brightness of resulting pixel and voltage retention is high and the thermotolerance of compound (I) is high, compound of the present invention (I) is preferred for colour filter.

That is, compound of the present invention (I) is preferably used with dyestuff as colour filter.

Below, for describing as being used for the colored resin composition of the inclusion compound in the situation of dyestuff (I) for colour filter.

< colored resin composition >

Colored resin composition of the present invention contains (A) dyestuff, (B) solvent and (C) adhesive resin, wherein, (A) dyestuff contains compound (1), colored resin composition of the present invention more preferably further contains at least one in (D) polymerizable monomer, (E) photopolymerization initiation composition and thermopolymerization initiation composition, also contains as required other composition.

First, (A) dyestuff is elaborated.

[about (A) dyestuff]

For colored resin composition of the present invention, (A) dyestuff inclusion compound (I), but only otherwise damage effect of the present invention, also can contain compound (I) other dyestuff in addition.

As other dyestuff, can preferably enumerate such as azo dyes, anthraquinone dyes, phthalocyanines dye, quinone imides dyestuff, quinoline dyestuff, nitro class dyestuff, carbonyl class dyestuff, methine class dyestuff, cyanine class dyestuff, triarylmethane class dyestuff, methyne two pyroles dyestuffs, xanthene class dyestuff etc.

As azo dyes, for example can enumerate: C.I. acid yellow 11, C.I. acid orange 7, C.I. Xylene Red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. directly yellow 12, C.I. direct orange 26, C.I. sun green 28, C.I. sun green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. DISPERSE ORANGE 30 200 5, C.I. Disperse Red 58, C.I. EX-SF DISPERSE BLUE EX-SF 300 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. medium Huang 5, C.I. Mordant Black 7 etc.

As anthraquinone dyes, can enumerate such as C.I. Vat blue 4, C.I. acid blue 25, C.I. Acid Blue 40, C.I. acid blue 80, C.I. ACID GREEN 25, C.I. Reactive Blue 19 100, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. Disperse Blue-60 etc.

In addition, as phthalocyanines dye, can enumerate such as: the C.I. phthalocyanines dye that directly blue 86, C.I. directly records in blue 199, C.I. vat blue 5, TOHKEMY 2002-14222 communique, TOHKEMY 2005-134759 communique, TOHKEMY 2010-191358 communique, TOHKEMY 2011-148950 communique etc.; As quinone imides dyestuff, can enumerate such as C.I. Basic Blue 3, C.I. alkali blue 9 etc., as quinoline dyestuff, can enumerate such as C.I. solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64 etc., as nitro class dyestuff, can enumerate such as C.I. turmeric yellow 1, C.I. von Muller's indicator 3, C.I. Disperse Yellow 42 etc.

In addition, as triarylmethane class dyestuff, can enumerate such as the triarylmethane class dyestuff recorded in C.I. acid blue 86, C.I. acid blue 88, C.I. Blue VRS 08, No. 2009/107734th, International Publication, No. 2011/162217th, International Publication etc.

In addition, as flower cyanine type dye, can enumerate the colored cyanine type dye of recording in No. 2011/162217th, International Publication for example, preferably mode is also identical.

As methyne two pyroles dyestuffs, can enumerate such as the methyne two pyroles dyestuffs recorded in TOHKEMY 2008-292970 communique, TOHKEMY 2010-84009 communique, TOHKEMY 2010-84141 communique, TOHKEMY 2010-85454 communique, TOHKEMY 2011-158654 communique, TOHKEMY 2012-158739 communique, TOHKEMY 2012-224852 communique, TOHKEMY 2012-224849 communique, TOHKEMY 2012-224847 communique, TOHKEMY 2012-224846 communique etc.

As xanthene class dyestuff, for example can enumerate: the xanthene class dyestuff of recording in the 326th page～348 pages of C.I. Xylene Red 50, C.I. Xylene Red 52, C.I. Xylene Red 289, No. 3387541 communique of Japan's patent, TOHKEMY 2010-32999 communique, No. 4492760 communique of Japan's patent, < < synthetic dyestuff summary (Gross is said synthetic dyestuff) > > (the rich work of hole mouth, three is published altogether, nineteen sixty-eight).

Particularly when forming blue pixel, preferably xanthene class dyestuff, triarylmethane class dyestuff, anthraquinone dyes, azo dyes, methyne two pyroles dyestuffs, flower cyanine type dye, phthalocyanines dye.

In colored resin composition of the present invention, as (A) dyestuff, can only contain a kind of compound (I), also can contain two or more.

In addition, can also contain compound (I) one kind or two or more other dyestuff in addition.

(content)

For the whole content of (A) dyestuff in colored resin composition of the present invention, in total solids composition, more than being preferably 0.01 % by weight, or be preferably below 50 % by weight.

In addition, for content for compound (I) in colored resin composition, in total solids composition, be generally 0.01 % by weight above, be preferably 0.1 % by weight above, more preferably more than 1 % by weight, and be generally 50 % by weight following, be preferably 40 % by weight following, more preferably below 30 % by weight.

Below the above-mentioned upper limit, the solidified nature of filming is difficult for reducing if, and film toughness is abundant, therefore preferably.In addition, more than above-mentioned lower limit, tinting strength is abundant if, and the therefore easy colourity that obtains desired concentration, and thickness is difficult for thickening, therefore preferably.

It should be noted that, in colored resin composition of the present invention, more than the content of compound (I) is preferably 30 % by weight in the solids component of whole (A) dyestuffs.

[(B) solvent]

(B) solvent containing in colored resin composition of the present invention has the function that makes each composition dissolving contained in colored resin composition or dispersion, adjusting viscosity.

As (B) solvent, so long as can make to form each composition dissolving of colored resin composition or the solvent disperseing, preferably select boiling point at the solvent of 100～200 ℃ of scopes.The solvent more preferably with 120～170 ℃ of boiling points.

As such solvent, can enumerate for example following solvents.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the tertiary butyl ether of propylene glycol list, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethyl amylalcohol, dihydroxypropane single-ether, DPE, 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 monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxy butyl acetate, acetic acid 3-methoxyl group butyl ester, acetic acid methoxyl group pentyl ester, diethylene glycol monoethyl ether acetic ester, butyl carbitol acetate, dipropylene glycol monomethyl ether acetic ester, the such glycol alkyl ether acetate esters of acetic acid 3-methyl-3-methoxyl group butyl ester;

Ether, dipropyl ether, Di Iso Propyl Ether, diamyl ether, ethyl isobutyl ether, the such ethers of hexyl ether;

Acetone, methylethylketone, Methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, the such ketone of methyl nonyl ketone;

Ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, 1 yuan such or polyalcohols of glycerine;

Skellysolve A, octane, diisobutylene, normal hexane, hexene, isoprene, limonene, the such aliphatic hydrocarbon of dodecane;

Hexanaphthene, methylcyclohexane, tetrahydrotoluene, the so alicyclic hydro carbons of bicyclohexyl;

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

Pentyl formate, ethyl formate, ethyl acetate, butylacetate, propyl acetate, pentyl acetate, hexalin acetate, methyl isobutyrate, ethylene glycol ethyl ethers acid esters, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octylate, butyl stearate, ethyl benzoate, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the chain that gamma-butyrolactone is such or cyclic ester class,

3-methoxypropionic acid, the such alkoxyl group carboxylic-acid of 3-ethoxy-propionic acid;

Chloro-butane, the such halogenated hydrocarbon of chloro-pentane;

The ether ketone that methoxymethyl pentanone is such;

Acetonitrile, the such nitrile of benzonitrile.

These solvents can be used singly or in combination of two or more.

In above-mentioned solvent, from the viewpoint of the solvability of (A) of the present invention dyestuff, preferred diol monoalkyl ethers.Wherein, particularly the solvability aspect of the various moietys from colored resin composition is considered, especially preferably propylene glycol monomethyl ether.

In addition, in the situation that for example comprising (F) described later pigment as any composition, because the solubleness of the moiety in further mixing the well balanced and colored resin composition that can obtain coating, surface tension etc. while using glycol alkyl ether acetate esters as solvent is higher, therefore more preferred.It should be noted that, in comprising the colored resin composition of pigment, because the polarity of glycol monoalkyl ethers is high, to there is the tendency that makes pigment cohesion, thereby may occur the situation that the viscosity rise etc. of colored resin composition reduces storage stability.Therefore, the usage quantity of preferred diol monoalkyl ethers is exceeded, and (B) ratio of the glycol monoalkyl ethers in solvent is preferably 5～50 % by weight, 5～30 % by weight more preferably.

In addition, consider that also preferably combination use boiling point is 150 ℃ of solvents above for the adaptability of recently corresponding with large substrate etc. slot coated (slit coat) mode.Now, with respect to (B) solvent total amount, the content of above-mentioned high boiling solvent be preferably 3～50 % by weight, more preferably 5～40 % by weight, be especially preferably 5～30 % by weight.If the amount of high boiling solvent is very few, what for example may occur to occur at slit spray nozzle front end that dyestuff becomes to grade separates out, solidifies, and then causes foreign matter defect; In addition, if the amount of high boiling solvent is too much, can cause the rate of drying of composition slack-off, and then may cause in the drying under reduced pressure technique in colour filter described later manufacturing process and occur that rhythm of production (tact) is bad, the problems such as pin-and-hole vestige of prebake (pre-bake).

It should be noted that, boiling point is that 150 ℃ of above solvents can be glycol alkyl ether acetate esters, also can be glycol alkyl ether classes, and now, can also make it not contain in addition boiling point is 150 ℃ of above solvents.

Colored resin composition of the present invention can be supplied to the colour filter manufacture that adopts ink jet method, in the colour filter that adopts ink jet method is manufactured, the ink being sprayed by nozzle is very small, for a few pL～tens pL, therefore, before in being sprayed onto jet hole periphery or pixel basin, solvent evaporation, ink has concentrated, solid trend.For fear of this situation, the boiling point of preferred solvent is higher, and specifically, (B) solvent preferably comprises 180 ℃ of above solvents of boiling point.Particularly preferably containing boiling point is that 200 ℃ above, especially boiling point is 220 ℃ of above solvents.In addition, preferably 180 ℃ of above high boiling solvents of boiling point are more than 50 % by weight in (B) solvent.In the situation of the ratio of such high boiling solvent lower than 50 % by weight, likely can not give full play to the effect that prevents that solvent from evaporating from droplet of ink.

In colored resin composition of the present invention, (B) content of solvent is not particularly limited, and its upper limit is made as 99 % by weight conventionally.When the content of (B) solvent in composition surpasses 99 % by weight, the concentration of each composition except (B) solvent becomes too small, is sometimes difficult to form coated film.On the other hand, consider the viscosity etc. that is suitable for coating, (B) lower value of the content of solvent be generally 75 % by weight, be preferably 80 % by weight, 82 % by weight more preferably.

[(C) adhesive resin]

For (C) adhesive resin, preferred resin is because of the curing difference of colored resin composition.

Colored resin composition of the present invention is in the situation of optical polymerism resin combination, as (C) adhesive resin, can use the middle macromolecular compounds of recording such as each communiques such as Japanese kokai publication hei 7-207211 communique, Japanese kokai publication hei 8-259876 communique, Japanese kokai publication hei 10-300922 communique, Japanese kokai publication hei 11-140144 communique, Japanese kokai publication hei 11-174224 communique, TOHKEMY 2000-56118 communique, TOHKEMY 2003-233179 communique, wherein, preferably enumerate the resin etc. of following (C-1)～(C-5).

(C-1): for (methyl) acrylate that contains epoxy group(ing) and the multipolymer of other free radical polymerization monomer, at least a portion of the hydroxyl that the resin that makes at least a portion of the epoxy group(ing) that this multipolymer has and unsaturated monoprotic acid addition and obtain or make generates by this addition reaction and the alkali soluble resin (following, to be sometimes referred to as " resin (C-1) ") that multi-anhydride addition obtains

(C-2): the straight chain shape alkali soluble resin (C-2) that contains carboxyl (following, to be sometimes referred to as " resin (C-2) ")

(C-3): the unsaturated compound that addition contains epoxy group(ing) on the carboxy moiety of above-mentioned resin (C-2) and the resin that obtains (following, to be sometimes referred to as " resin (C-3) ")

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

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

Wherein, particularly preferably enumerate resin (C-1), below for this resin, describe.

It should be noted that, resin (C-2)～(C-5) being so long as can be dissolved by alkaline-based developer and have a deliquescent resin that can make the development treatment of target be accomplished degree, its respectively with TOHKEMY 2009-025813 communique in the resin-phase recorded as identical items with.Preferred implementation is also identical.

(C-1): for (methyl) acrylate that contains epoxy group(ing) and the multipolymer of other free radical polymerization monomer, make at least a portion of the epoxy group(ing) that this multipolymer has and unsaturated monoprotic acid addition and at least a portion of the hydroxyl that the resin that obtains or make generates by this addition reaction and the alkali soluble resin that multi-anhydride addition obtains

As one of particularly preferred resin of resin (C-1), can enumerate: the multipolymer forming for other free radical polymerization monomers of (methyl) acrylate that contains epoxy group(ing) by 5～90 % by mole and 10～95 % by mole, makes 10～100 % by mole of resins that obtain with unsaturated monoprotic acid addition of the epoxy group(ing) that this multipolymer has or 10～100 % by mole of alkali soluble resins that obtain with multi-anhydride addition of the hydroxyl that makes to generate by this addition reaction.

As described (methyl) acrylate that contains epoxy group(ing), for example can enumerate: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) butyl ester, (methyl) vinylformic acid (3,4-epoxycyclohexyl) methyl esters, (methyl) vinylformic acid 4-hydroxyl butyl ester glycidyl ether etc.Wherein, preferred (methyl) glycidyl acrylate.Above-mentioned (methyl) acrylate that contains epoxy group(ing) can be used separately a kind, also two or more can be used in combination.

As other free radical polymerization monomer that carries out copolymerization with above-mentioned (methyl) acrylate that contains epoxy group(ing), in the scope of not damaging effect of the present invention, there is no particular determination, 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., particularly preferably there is list (methyl) acrylate of structure shown in following formula (7).

In the repeating unit from " other free radical polymerization monomer ", from have structure shown in following formula (7) list (methyl) acrylate repeating unit containing proportional be preferably 5～90 % by mole, more preferably 10～70 % by mole, be particularly preferably 15～50 % by mole.

[Chemical formula 1 0]

In above-mentioned formula (7), R ⁸⁹represent hydrogen atom or methyl, R ⁹⁰represent the structure shown in following formula (8).

[Chemical formula 1 1]

In above-mentioned formula (8), R ⁹¹～R ⁹⁸the alkyl that represents independently of one another hydrogen atom or carbonatoms 1～3.It should be noted that R ⁹⁶and R ⁹⁸optionally mutually link and formation ring.

R ⁹⁶and R ⁹⁸the ring that links and form is preferably aliphatics ring, can be any situation in saturated rings or unsaturated ring, and in addition, carbonatoms is preferably 5～6.

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

[Chemical formula 1 2]

It should be noted that, list (methyl) acrylate with structure shown in above-mentioned formula (8) can be used separately a kind, also two or more can be used in combination.

As " other free radical polymerization monomer " except thering is list (methyl) acrylate of structure shown in above-mentioned formula (8), from the viewpoint of improving excellent thermotolerance and the intensity of colored resin composition, can enumerate: vinylbenzene, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, N-phenylmaleimide, N-N-cyclohexylmaleimide.

From the content that is selected from least a kind of repeating unit in above-mentioned set of monomers, be preferably 1～70 % by mole, more preferably 3～50 % by mole.

It should be noted that, for above-mentioned (methyl) acrylate that contains epoxy group(ing) and the copolyreaction of above-mentioned other free radical polymerization monomer, can adopt known solution polymerization process.

In the present invention, multipolymer as above-mentioned (methyl) acrylate that contains epoxy group(ing) and above-mentioned other free radical polymerization monomer formation, preferably by 5～90 % by mole of the repeating units of (methyl) acrylate from containing epoxy group(ing) with from 10～95 % by mole of multipolymers that form of repeating unit of other free radical polymerization monomer, more preferably by the former 20～80 % by mole and 80～20 % by mole of multipolymers that form of the latter, particularly preferably by the former 30～70 % by mole and 70～30 % by mole of multipolymers that form of the latter.

In the time of in above-mentioned scope, the addition amount of aftermentioned polymerizability composition and alkali-soluble composition is abundant, and thermotolerance, film strength are abundant, therefore preferably.

The epoxy group(ing) part of the above-mentioned synthetic multipolymer that contains epoxy group(ing) is reacted with unsaturated monoprotic acid (polymerizability composition) and multi-anhydride (alkali-soluble composition).

Here, the unsaturated monoprotic acid as with epoxy group(ing) addition, can be used known compound, for example, can enumerate the unsaturated carboxylic acid with ethylenical unsaturated double bonds.

As concrete example, can enumerate: (methyl) vinylformic acid, β-crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to vinyl benzoic acid, the monocarboxylic acids such as (methyl) vinylformic acid that alpha-position is replaced by haloalkyl, alkoxyl group, halogen atom, nitro or cyano group etc. etc.Wherein, preferred (methyl) vinylformic acid.These unsaturated carboxylic acids can be used alone a kind, also two or more can be used in combination.

By addition mentioned component, can give polymerizability for the adhesive resin using in the present invention.

Conventionally, these unsaturated monoprotic acid of addition on 10～100 % by mole of the epoxy group(ing) having at above-mentioned multipolymer, preferably 30～100 % by mole of additions, more preferably 50～100 % by mole of additions.In the time of in above-mentioned scope, the ageing stability of colored resin composition is excellent, therefore preferably.Wherein, as the unsaturated monacid method of addition in the epoxy group(ing) of multipolymer, can adopt known method.

In addition, the multi-anhydride of the hydroxyl addition producing when with the unsaturated monoprotic acid of addition in the epoxy group(ing) of multipolymer, can be used known multi-anhydride.

For example, can enumerate the dibasic acid anhydrides such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, chlorendic acid acid anhydride; The sour acid anhydrides more than ternary such as trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Wherein, preferred succinyl oxide and Tetra Hydro Phthalic Anhydride.These multi-anhydrides can be used alone a kind, also two or more can be used in combination.

By addition mentioned component, can give alkali-soluble for the adhesive resin using in the present invention.

Conventionally, the unsaturated monoprotic acid of addition in the epoxy group(ing) that makes to have at above-mentioned multipolymer and the hydroxyl that generates 10～100 % by mole with above-mentioned multi-anhydride addition, preferably make 20～90 % by mole of additions, more preferably make 30～80 % by mole of additions.

In the time of in above-mentioned scope, residual film ratio and solvability during development are abundant, therefore preferably.

It should be noted that, the method as making this hydroxyl and multi-anhydride addition, can adopt known method.

In addition, for luminous sensitivity is improved, also can be after the above-mentioned multi-anhydride of addition, a part that makes the carboxyl that generates and (methyl) glycidyl acrylate or there is the glycidyl ether compound addition of polymerizability unsaturated group.Relevant this resinoid structure, is for example documented in Japanese kokai publication hei 8-297366 communique, TOHKEMY 2001-89533 communique.

Utilize the weight-average molecular weight that is converted into polystyrene (Mw) of the above-mentioned adhesive resin (C-1) of GPC (gel permeation chromatography) mensuration to be preferably 3000～100000, to be particularly preferably 5000～50000.In above-mentioned scope, thermotolerance, film toughness and the favorable solubility in developing solution are preferred from this aspect if.

In addition, as the roughly standard of molecular weight distribution, the ratio of weight-average molecular weight (Mw)/number-average molecular weight (Mn) is preferably 2.0～5.0.

It should be noted that, the acid number of adhesive resin (C-1) is generally 10～200mg-KOH/g, is preferably 15～150mg-KOH/g, 25～100mg-KOH/g more preferably.If acid number is too low, may cause the solvability in developing solution to reduce.On the contrary, if acid number is too high, there is sometimes film cracking.

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

In above-mentioned scope, good to the adaptation of substrate if, in addition, developing solution is suitable to the impregnability of exposure portion, and surface smoothness and the sensitivity of pixel are good, from the viewpoint of these, is preferred.

[(D) polymerizable monomer]

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

(D) polymerizable monomer so long as low molecular compound that can polymerization be just not particularly limited, preferably have at least one olefinic double bond can addition polymerization compound (following, to be sometimes referred to as " olefinic compounds ").

Olefinic compounds is when colored resin composition of the present invention is subject to the irradiation of active ray, can under the effect of aftermentioned photopolymerization initiation composition, addition polymerization occur and the curing compound with olefinic double bond.It should be noted that, (D) polymerizable monomer in the present invention is the concept relative with so-called polymer substance, except the monomer of narrow sense, also comprises dimer, tripolymer, oligopolymer.

As the olefinic compounds in (D) polymerizable monomer, can enumerate such as unsaturated carboxylic acids such as (methyl) vinylformic acid; The ester that monohydroxy compound and unsaturated carboxylic acid form; The ester that aliphatic polyhydroxy compound and unsaturated carboxylic acid form; The ester that aromatic polyhydroxy compounds and unsaturated carboxylic acid form; The ester that the multi-hydroxy compounds such as unsaturated carboxylic acid and polycarboxylic acid and above-mentioned aliphatic polyhydroxy compound, aromatic polyhydroxy compounds obtain by esterification; By polyisocyanate compound, react with the oxy-compound that contains (methyl) acryl the olefinic compounds with carbamate skeleton obtaining; Etc..

Ester as aliphatic polyhydroxy compound and unsaturated carboxylic acid formation, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, (methyl) acrylate such as glycerol (methyl) acrylate.In addition, (methyl) acrylate moiety of these (methyl) acrylate is replaced with to itaconic ester that methylene-succinic acid partly forms, (methyl) acrylate moiety of these (methyl) acrylate is replaced with to crotonate that β-crotonic acid partly forms or (methyl) acrylate moiety of these (methyl) acrylate replaced with to maleic acid ester that toxilic acid partly forms etc.

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

The ester obtaining by esterification as unsaturated carboxylic acid and polycarboxylic acid and multi-hydroxy compound, can be single thing, can be also mixture.As typical example, can enumerate: the condenses of (methyl) vinylformic acid, phthalic acid and ethylene glycol; The condenses of (methyl) vinylformic acid, toxilic acid and Diethylene Glycol; The condenses of (methyl) vinylformic acid, terephthalic acid and tetramethylolmethane; The condenses of (methyl) vinylformic acid, hexanodioic acid, butyleneglycol and glycerine etc.

As reacting with the oxy-compound that contains (methyl) acryl the olefinic compounds with carbamate skeleton obtaining by polyisocyanate compound, can enumerate: the aliphatic diisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate; The alicyclic diisocyanate such as cyclohexyl diisocyanate, isophorone diisocyanate; The aromatic diisocyanate such as tolylene diisocyanate, diphenylmethanediisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate, 3-hydroxyl [1; 1,1-tri-(methyl) acryloyl-oxy ylmethyl] reaction product of the oxy-compound that contains (methyl) acryl such as propane.

In addition, as the example of the olefinic compounds using in the present invention, can enumerate: (methyl) acrylic amides such as ethylenebis (methyl) acrylamide; The allyl ester classes such as Phthalic acid, diallyl ester; The compound that phthalic acid divinyl ester etc. contains vinyl etc.

In above-mentioned, the ester that preferred aliphat polyol and unsaturated carboxylic acid form, more preferably (methyl) acrylate of tetramethylolmethane or Dipentaerythritol, particularly preferably Dipentaerythritol six (methyl) acrylate.

In addition, olefinic compounds can also be the monomer with acid number.As the monomer with acid number, it is for example the ester that aliphatic polyhydroxy compound and unsaturated carboxylic acid form, be preferably the polyfunctional monomer with acidic group that the unreacted hydroxyl of aliphatic polyhydroxy compound is reacted with non-aromatic carboxylic acid anhydride and obtain, be particularly preferably aliphatic polyhydroxy compound in this ester and be at least one in tetramethylolmethane and Dipentaerythritol.

Above-mentioned monomer can be used separately a kind, but owing to being difficult to obtain single compound with regard to manufacture view, therefore also can use mixture of more than two kinds.

In addition, can also as required the polyfunctional monomer without acidic group be used in combination with the polyfunctional monomer with acidic group, be used as (D) polymerizable monomer.

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

In above-mentioned scope, the dissolution characteristics that develops is difficult for reducing, and manufacture and processing ease if.In addition, photopolymerization performance is difficult for declining, and the solidified nature such as the surface smoothness of pixel are good, therefore preferably.

In the present invention, the preferred polyfunctional monomer with acidic group is for example to take the mixture that the succinate of dipentaerythritol acrylate, Dipentaerythritol five acrylate, Dipentaerythritol five acrylate is principal constituent.Also this polyfunctional monomer and other polyfunctional monomer can be used in combination.

In colored resin composition of the present invention, the content of above-mentioned (D) polymerizable monomer is as follows: be generally 1 % by weight in total solids composition more than, be preferably 5 % by weight more than, more preferably more than 10 % by weight, and be generally 80 % by weight following, be preferably 70 % by weight following, more preferably 50 % by weight following, be particularly preferably below 40 % by weight.

In addition, for (D) polymerizable monomer for the ratio of above-mentioned (A) dyestuff, in weight ratio, be generally 1 % by weight above, be preferably 5 % by weight above, more preferably 10 % by weight above, be particularly preferably 20 % by weight more than, and be generally 200 % by weight following, be preferably 100 % by weight following, more preferably below 80 % by weight.

In the time of in above-mentioned scope, photocuring appropriateness, is difficult for causing when developing closely sealed bad, and the cross section after development is difficult for becoming inverted cone shape, and it is bad etc. to be difficult for occurring the peeling, the molding that by decreased solubility, are caused, therefore preferably.

[(E) photopolymerization causes composition, thermopolymerization causes composition]

In order to reach the object that makes curing of coating, colored resin composition of the present invention preferably comprises (E) photopolymerization and causes at least one in composition and thermopolymerization initiation composition.Wherein, curing method can be also the method for not using these initiators.

Particularly, for comprising situation as the resin with olefinic double bond of (C) composition in colored resin composition of the present invention, comprise as for the situation of the olefinic compounds of (D) composition, thereby preferably contain, there is direct absorb light or photosensitization occurs and cause that photopolymerization that decomposition reaction or dehydrogenation reaction produce the function of polymerization activity free radical causes composition and under heat effect, produces at least one in the thermopolymerization initiation composition of polymerization activity free radical.It should be noted that, in the present invention, (E) composition as photopolymerization initiation composition refers to: the mixture that has been used in combination the additives such as polymerization accelerator (being called arbitrarily below (E2) composition), enhanced sensitivity pigment (being called arbitrarily below (E3) composition) in Photoepolymerizationinitiater initiater (being called arbitrarily below (E1) composition).

[(E) photopolymerization causes composition]

(E) photopolymerization in the present invention cause composition conventionally with (E1) Photoepolymerizationinitiater initiater and (E2) polymerization accelerator adding as required and (E3) form of the mixture of the additives such as enhanced sensitivity pigment use, thereby there is direct absorb light or photosensitization occurs and cause the composition of the function of decomposition reaction or dehydrogenation reaction generation polymerization activity free radical.

As (E1) Photoepolymerizationinitiater initiater that forms photopolymerization and cause composition, can enumerate such as the two luxuriant titanium derivative classes of recording in Japanese kokai publication sho 59-152396 communique, Japanese kokai publication sho 61-151197 communique etc.; The Hexaarylbiimidazole derivatives class of recording in Japanese kokai publication hei 10-300922 communique, Japanese kokai publication hei 11-174224 communique, TOHKEMY 2000-56118 communique etc.; The halomethylation of recording in Japanese kokai publication hei 10-39503 communique etc. free radical activity agent, the alpha-aminoalkyl benzophenone derivatives classes such as N-aryl-alpha-amino group acids such as oxadiazole derivative class, monochloromethyl s-triazine derivative class, N-phenylglycine, N-aryl-a-amino acid salt, N-aryl-α-aminoacidesters class; The oxime ester of recording in TOHKEMY 2000-80068 communique etc. is derivatives class etc.

Specifically can enumerate such as Photoepolymerizationinitiater initiater of recording in No. 2009/107734 grade of International Publication etc.

In these Photoepolymerizationinitiater initiaters, more preferably alpha-aminoalkyl benzophenone derivatives class, oxime ester are derivatives class, di-imdazole derivatives class, acetophenone derivs class and thioxanthone derivates class.

In addition; as oxime ester, it is derivatives class; can enumerate: 1-[4-(thiophenyl) phenyl]-1,2-octane diketone 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] compound that represents of-ketene-1-(O-ethanoyl oxime) and following formula (XI) etc.

[Chemical formula 1 3]

(in formula (XI), R ¹⁰¹represent hydrogen atom, the alkyl of carbonatoms 1～20, the heteroaryl of the thiazolinyl of carbonatoms 2～25, carbonatoms 3～20 or the heteroarylalkyl of carbonatoms 4～25, these groups all optionally have substituting group.Or, R ¹⁰¹also can be with X or Z bonding and form ring.

R ¹⁰²represent the alkyloyl of carbonatoms 2～20, the cycloalkanes acyl group of the enoyl-of carbonatoms 3～25, carbonatoms 4～8, the carbalkoxy of the aroyl of carbonatoms 7～20, carbonatoms 2～10, the heteroaryl of the aryloxy carbonyl of carbonatoms 7～20, carbonatoms 2～20, the alkyl amino-carbonyl of the 4-hetaroylpyrazol of carbonatoms 3～20 or carbonatoms 2～20, these groups all optionally have substituting group.

X represents optionally to have the substituent divalent aromatic cyclic hydrocarbon group group being formed by 2 above cyclic condensations and at least one in aromatic heterocyclic group.

Z represents optionally to have substituent aromatic ring group.)

It should be noted that, in the compound that above-mentioned formula (XI) represents, preferably X, for optionally to have the compound of substituent carbazole ring, specifically can enumerate the compound of following formula (XII) expression etc., wherein, the compound that particularly preferably following formula (XIII) represents.

[Chemical formula 1 4]

(in formula, R ¹⁰¹, R ¹⁰²and the definition synonym in Z and above-mentioned formula (XI).R ¹⁰³～R ¹⁰⁹represent independently of one another hydrogen atom or substituting group arbitrarily.)

[Chemical formula 1 5]

(in formula, R ^101arepresent the alkyl of carbonatoms 1～3 or the group that following formula (XIIIa) represents.

[Chemical formula 1 6]

(in formula, R ¹⁰³and R ¹⁰⁴represent that independently of one another hydrogen atom, phenyl or N-ethanoyl-N-acetoxyl group are amino.

* represent bonding position.)

R ^102athe alkyloyl that represents carbonatoms 2～4, X ^arepresent that nitrogen-atoms optionally replaces by 1～4 alkyl 3,6-carbazyl.Z ^arepresent the phenyl optionally being replaced by alkyl or the naphthyl optionally being replaced by morpholinyl.)

As oximes initiator, can use commercially available product.Example as commercially available product, can enumerate OXE-01, OXE-02 (BASF AG's manufacture), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305 (Changzhou Tronly New Electronic Materials Co., Ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) manufacture).

As Photoepolymerizationinitiater initiater, can enumerate in addition: benzoin alkylether class, anthraquinone derivative class; Acetophenone derivs class, the 2-ethyl thioxanthone, 2 such as 2-methyl-(4 '-methylthio group phenyl)-2-morpholinyl-1-acetone, the thioxanthone derivates classes such as 4-diethyl thioxanthone, benzoate derivatives class, acridine derivatives class, azophenlyene derivatives class, anthracyclinone derivatives class etc.These initiators also can be used commercially available product.

As commercially available product, can enumerate such as IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784 (being BASF AG manufactures) etc.

In above-mentioned Photoepolymerizationinitiater initiater, more preferably alpha-aminoalkyl benzophenone derivatives class, thioxanthone derivates class, oxime ester are derivatives class.Particularly preferably oxime ester is derivatives class.

As (E2) polymerization accelerator using as required, for example can enumerate: N, the N such as N-dimethylaminobenzoic acid ethyl ester, N-dialkyl amido phenylformic acid alkyl ester class; 2-mercaptobenzothiazole, 2-sulfydryl benzo azoles, 2-mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle; The sulfhydryl compound classes such as the multifunctional sulfhydryl compound of aliphatics etc.

Above-mentioned (E1) Photoepolymerizationinitiater initiater and (E2) polymerization accelerator can be used separately respectively a kind, also two or more can be used in combination.

In addition,, in order to improve induction sensitivity, can use as required (E3) enhanced sensitivity pigment.As enhanced sensitivity pigment, can adopt suitable enhanced sensitivity pigment according to the wavelength of image exposure light source, can enumerate such as the xanthene class pigment recorded in Japanese kokai publication hei 4-221958 communique, Japanese kokai publication hei 4-219756 communique etc., the coumarins pigment with heterocycle of recording in Japanese kokai publication hei 3-239703 communique, Japanese kokai publication hei 5-289335 communique etc., the 3-oxo coumarins pigment of recording in Japanese kokai publication hei 3-239703 communique, Japanese kokai publication hei 5-289335 communique etc., the methylene pyrrole class pigment of recording in Japanese kokai publication hei 6-19240 communique etc., Japanese kokai publication sho 47-2528 communique, Japanese kokai publication sho 54-155292 communique, Japanese Patent Publication 45-37377 communique, Japanese kokai publication sho 48-84183 communique, Japanese kokai publication sho 52-112681 communique, Japanese kokai publication sho 58-15503 communique, Japanese kokai publication sho 60-88005 communique, Japanese kokai publication sho 59-56403 communique, Japanese kokai publication hei 2-69 communique, Japanese kokai publication sho 57-168088 communique, Japanese kokai publication hei 5-107761 communique, Japanese kokai publication hei 5-210240 communique, the pigment with dialkyl amido benzene skeleton of recording in Japanese kokai publication hei 4-288818 communique etc. etc.

(E3) enhanced sensitivity pigment also can be used separately a kind, also two or more can be used in combination.

In colored resin composition of the present invention, for the content that causes composition for above-mentioned (E) photopolymerization, be generally 0.1 % by weight in total solids composition more than, be preferably 0.2 % by weight more than, more preferably more than 0.5 % by weight, and be generally 40 % by weight following, be preferably that 30 % by weight are following, the scope below 20 % by weight more preferably.

In the time of in above-mentioned scope, good to the sensitivity of exposure light, and the favorable solubility of unexposed portion in developing solution, be difficult for occurring poor visualization etc., therefore preferably.

[(E) thermopolymerization causes composition]

As colored resin composition of the present invention, contained (E) thermopolymerization causes the concrete example of composition, can enumerate azo compound, organo-peroxide and hydrogen peroxide etc.In the middle of these, preferably use azo compound.More specifically, can use such as the thermopolymerization of recording in No. 2009/107734 grade of International Publication and cause composition.

Above-mentioned thermopolymerization causes composition can use separately a kind, also two or more can be used in combination.

[other any composition]

Except above-mentioned each composition, in colored resin composition of the present invention, can also contain: at least one in tensio-active agent, organic carboxyl acid and organic carboxyl acid acid anhydride, heat-curable compounds, softening agent, thermopolymerization preventing agent, preserving stabilizer, surface protectant, closely sealed rising agent, development modifying agent etc.As above-mentioned any composition, can use the various compounds that for example TOHKEMY 2007-113000 communique is recorded.In addition, in the situation that containing (F) described later pigment, can also contain dispersion agent, dispersing auxiliary.

[(F) pigment]

In order to improve thermotolerance of resulting colour filter etc., colored resin composition of the present invention can also contain (F) pigment in the scope of not damaging effect of the present invention.

As (F) pigment, such as in the situation that form the pixel etc. of colour filter, can use the versicolor pigment such as blueness, purple.In addition, as its chemical structure, can enumerate for example phthalocyanines, quinacridine ketone, benzoglyoxaline ketone, two the pigment dyestuffs such as piperazine class, indanthrone kinds, perylene kinds.In addition, can also use various mineral dyes etc.The concrete example of the pigment that can use is shown by pigment call number below.

As blue pigments, 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.

In the middle of these, preferably blue copper phthalocyanine, as this copper phthalocyanine, can enumerate C.I. pigment Blue 15,15:1,15:2,15:3,15:4,15:6 etc., more preferably C.I. pigment Blue 15: 6.

Therefore, in the situation that colored resin composition of the present invention contains blue pigments, preferably with respect to the total content of blue pigments, C.I. pigment Blue 15: 6 be 80 % by weight above, be particularly preferably 90 % by weight above, be especially preferably 95～100 % by weight.

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.

In the middle of these, two of preferred purple piperazine pigment, as this two piperazine pigment, can preferably enumerate C.I. pigment violet 19,23 etc., more preferably C.I. pigment Violet 23.

Therefore, in the situation that colored resin composition of the present invention contains violet pigment, with respect to the total content of violet pigment, preferably C.I. pigment Violet 23 be 80 % by weight above, be particularly preferably 90 % by weight above, be especially preferably 95～100 % by weight.

They can use separately a kind, also can be to combine arbitrarily and ratio mixes two or more use.

From the viewpoint of forming the pixel of high-contrast, the little person of (F) pigment optimization average primary particle diameter who uses in colored resin composition of the present invention, specifically, preferably average primary particle diameter is below 40nm, more preferably below 35nm.

Particularly, for blue copper phthalocyanine, same preferably average primary particle diameter is below 40nm, more preferably below 35nm, and 20～30nm more preferably.

In addition, for two piperazine pigment, average primary particle diameter is preferably below 40nm, more preferably 25～35nm.From pigment, be difficult for aspect cohesion, considering colored resin composition, preferably average primary particle diameter is too not little.

It should be noted that, here, (F) average primary particle diameter of pigment is the value of measuring, calculating according to following method.

First, (F) pigment is carried out to ultrasonic wave dispersion in chloroform, be added drop-wise on the screen cloth that is fitted with collodion membrane, make it dry, and by transmission electron microscope (TEM), observe the primary particle image that obtains pigment.By this image, the particle diameter of each pigment particles is converted into equal area circular diameter, as area equivalent circular diameter, and the pigment particles of a plurality of (being generally 200～300 left and right) is obtained respectively to particle diameter.

The value of using resulting primary particle diameter calculates number mean value according to calculating formula below, obtains median size.

The particle diameter of each pigment particles: X ₁, X ₂, X ₃, X ₄,, X _i, X _m(number that m is particle)

[mathematical expression 1]

{ use level }

In the present invention, in the situation that containing (F) pigment, for the content of the pigment in colored resin composition, in total solids composition, be generally below 80 % by weight, be preferably below 50 % by weight.

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

By being in above-mentioned scope, can on transmissivity, not bring large impact due to dyestuff (I), it is better that the thermotolerance of the pixel obtaining easily becomes, and it is preferred from this, putting.

[dispersion agent]

In the situation that colored resin composition of the present invention comprises (F) pigment, preferably further contain dispersion agent.

As long as dispersion agent of the present invention can make colo(u)rant dispersion and keep stable, to its kind indefinite.

Can use the dispersion agent such as cationic, anionic property, nonionic or both sexes etc., but preferred polymers dispersion agent.Specifically can enumerate: the alkylammonium salt of segmented copolymer, urethane, polyester, high-molecular copolymer or phosphate ester salt, cationic comb shape graftomer etc.In these dispersion agents, preferred block copolymer, urethane, cationic comb shape graftomer.Segmented copolymer particularly preferably, wherein, preferably by thering is the A block of solvophilic and thering is the segmented copolymer that the B block of the functional group that comprises nitrogen-atoms forms.

Particularly, as the B block with the functional group of nitrogen atom, can enumerate the modular construction that side chain has at least one group in quaternary ammonium salt base and amino; On the other hand, as the A block of solvophilic, can enumerate and not there is quaternary ammonium salt base and amino modular construction.

The B block of described formation acrylic block copolymer has the modular construction that comprises at least one group in quaternary ammonium salt base and amino, is the position with pigment adsorption function.

In addition, as described B block, in the situation that thering is quaternary ammonium salt base, this quaternary ammonium salt base can Direct Bonding on main chain, also can link group by divalent and be bonded on main chain.

As such segmented copolymer, can enumerate the multipolymer of recording in TOHKEMY 2009-025813 communique for example.

In addition, in colored resin composition of the present invention, also can comprise above-mentioned dispersion agent in addition.As other dispersion agent, can enumerate the dispersion agent of recording in TOHKEMY 2006-343648 communique for example.

In the situation that colored resin composition of the present invention contains (F) pigment, preferably make the content of used dispersion agent in total solids composition for 2～1000 % by weight of (F) pigment total content, be particularly preferably 5～500 % by weight, especially preferably in the scope of 10～250 % by weight.

In the time of in above-mentioned scope, can not impact the thermotolerance of dyestuff (I), can guarantee good pigment-dispersing, and can obtain better colo(u)rant dispersion stability, therefore preferably.

[dispersing auxiliary]

In colored resin composition of the present invention, can also contain dispersing auxiliary.The described dispersing auxiliary here can be pigment derivative, as pigment derivative, can use such as the various compounds of recording in TOHKEMY 2001-220520 communique, TOHKEMY 2001-271004 communique, TOHKEMY 2002-179976 communique, TOHKEMY 2007-113000 communique and TOHKEMY 2007-186681 communique etc. etc.

It should be noted that, total solids with respect to pigment becomes component, more than the content of the dispersing auxiliary in colored resin composition of the present invention is generally 0.1 % by weight, in addition, be generally 30 % by weight following, be preferably 20 % by weight following, more preferably 10 % by weight following, more preferably below 5 % by weight.By addition being controlled to above-mentioned scope, can give play to the effect as dispersing auxiliary, and can obtain more good dispersiveness and dispersion stabilization, therefore preferably.

[dispersion resin]

In colored resin composition of the present invention, can contain the part or all of resin that is selected from above-mentioned (C) adhesive resin or other adhesive resin as following dispersion resin.

Particularly, in [preparation method of colored resin composition] described later, by contain (C) adhesive resin when containing the compositions such as above-mentioned dispersion agent, can be conducive to by being somebody's turn to do the synergy of (C) adhesive resin and dispersion agent the dispersion stabilization of (F) pigment.Thus, likely make the addition of dispersion agent reduce, therefore preferably.In addition, also play raising developability, improving pixel can be in the effect of the residual not solute of non-pixel portions of substrate, therefore preferred with the adaptation of substrate.

Like this, also (C) adhesive resin for dispersion treatment operation is called to dispersion resin.With respect to the pigment total amount in colored resin composition, the consumption of dispersion resin is preferably in 0～200 % by weight left and right, more preferably in 10～100 % by weight left and right.

[preparation method of colored resin composition]

In the present invention, colored resin composition can be prepared by suitable method, for example, can be by by (A) dye well (C) adhesive resin of inclusion compound (I) and (B) solvent and mix to prepare together with any composition of use as required.

In addition, as the preparation method in the situation that comprises (F) pigment, can enumerate following method: in the solvent that comprises (F) pigment, under the existence of dispersion agent and the dispersing auxiliary that adds as required, in some situation with together with the part of (C) adhesive resin, use for example coating vibrator, sand mill, ball mill, roller mill, burrstone mill, airflow milling, when pulverizing, mix by homogenizer etc., disperse, thereby prepare dispersible pigment dispersion, to (A) dyestuff that adds inclusion compound (I) in this dispersible pigment dispersion, (C) adhesive resin, (D) polymerizable monomer as required, (E) at least one in Photoepolymerizationinitiater initiater and thermal polymerization etc., and mix, prepare thus colored resin composition.

[application of colored resin composition]

Colored resin composition of the present invention is all dissolved or dispersed in the state in solvent in repertoire conventionally.Such colored resin composition is fed on substrate, forms the component parts such as colour filter, liquid crystal indicator, organic EL display.

Below, as the application examples of colored resin composition of the present invention, for it as the application of the pixel of colour filter and used their liquid crystal indicator (panel) and organic EL display to describe.

< colour filter >

Colour filter of the present invention has the pixel being formed by colored resin composition of the present invention.

For the method that forms colour filter of the present invention, describe below.

The pixel of colour filter can utilize the whole bag of tricks to form.Here, so that be that example describes with the colored resin composition of optical polymerism the situation of utilizing photolithography to form pixel, but manufacture method is not limited to the method.

First, on the surface of substrate, the mode that forms as required the part of pixel to mark off wish forms black matrix", and is coated with colored resin composition of the present invention on this substrate, then, carries out prebake so that solvent evaporation is filmed thereby form.Then, across mask, this is filmed and is exposed, then use alkaline developer to develop, dissolve and remove the unexposed portion of filming, after then carrying out, cure, form thus each red, green, blue pattern of pixels, thereby can be made into colour filter.

In the present invention, the pixel of particularly preferably using colored resin composition of the present invention to form is blue pixel.

The substrate using during as formation pixel, so long as transparent and there is the substrate of suitable intensity, there is no particular determination, can enumerate such as polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin film-making material, epoxy resin, thermosetting resin, various glass etc.

In addition, for these substrates, can also implement as required following suitable pre-treatment: utilize surface treatments such as film formation processing that silane coupling agent, polyurethanes resin etc. carry out, Corona discharge Treatment, ozonize etc.

When colored resin composition is coated on substrate, can enumerate spin-coating method, line rod (Wire bar) method, flow coat method, slit spin-coating method (Slit and Spin Coating) method, mould painting method, rolling method, spraying method etc.Wherein, preferably slit spin-coating method and mould are coated with method.

The thickness of coated film is generally 0.2～20 μ m, is preferably 0.5～10 μ m, is particularly preferably 0.8～5.0 μ m with dried film thickness gauge.

In the time of in above-mentioned scope, easily in pattern development and liquid crystal cells chemical industry order, carry out gap adjustment, and easily demonstrate desired color, therefore preferably.

The radioactive rays that use during as exposure, can be used such as visible ray, ultraviolet ray, far ultraviolet rays yue, electron beam, X ray etc., the radioactive rays of optimal wavelength within the scope of 190～450nm.

For can be used for image exposure for obtaining the light source of the radioactive rays of wavelength 190～450nm, there is no particular determination, can enumerate such as lamp source such as xenon lamp, halogen lamp, tungsten lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp, carbon arc, luminescent lamps; The LASER Light Source such as argon laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser etc.When the light of use specific wavelength irradiates, also can utilize optical filter.

The exposure of radioactive rays is preferably 10～10000J/m ².

In addition, as above-mentioned alkaline developer, preference is as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, water glass, potassium silicate, Starso, sodium phosphate, potassiumphosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, ammonium hydroxide; The aqueous solution of the organic basic compounds such as monoethanolamine, diethanolamine, trolamine, monomethyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, ethyleneimine, ethene diimine (ethylene diimine), Tetramethylammonium hydroxide (TMAH), choline etc.

Can also in above-mentioned alkaline developer, add appropriate water-miscible organic solvents such as Virahol, benzylalcohol, ethyl cellosolve, ethylene glycol butyl ether, phenyl cellosolve, propylene glycol, diacetone alcohol, tensio-active agent etc.It should be noted that, alkali is washed after developing conventionally.

As development treatment method, can adopt any means in immersion development method, spray development method, brushing development method, ultrasonic wave development method etc.Development conditions is preferably under room temperature (23 ℃) 5～300 seconds.

The condition of development treatment there is no particular determination, development temperature be generally 10 ℃ above, be preferably 15 ℃ above, more preferably more than 20 ℃, and be generally 50 ℃ following, be preferably 45 ℃ of following, 40 ℃ of following scopes more preferably.

Developing method can adopt any means in immersion development method, spray development method, brushing development method, ultrasonic wave development method etc.

When the colour filter of making is thus used for to liquid crystal indicator, can directly with the state after making, on image, form the transparency electrodes such as ITO, and used as the parts of the parts such as color monitor, liquid crystal indicator, but in order to improve surface smoothness and weather resistance, the top coats such as polymeric amide, polyimide can also be set on image as required.In addition,, in the purposes such as part planar orientation type type of drive (IPS pattern), sometimes do not form transparency electrode yet.In addition, in vertical orientating type type of drive (MVA pattern), sometimes also form rib (rib).In addition, sometimes also utilize photolithography to form rod structure (light sensitive spacer) and replace pearl decentralized spacer.

< liquid crystal indicator >

Liquid crystal indicator of the present invention is the liquid crystal indicator that has used the colour filter of the invention described above.Pattern and the structure of liquid crystal indicator of the present invention there is no particular restriction, can utilize ordinary method to assemble with colour filter of the present invention.

For example, can utilize the method for recording in " liquid crystal apparatus handbook " (daily magazine industry newspaper office (daily magazine industry XinWen society), distribution on September 29th, 1989, JSPS 142 council work), form liquid crystal indicator of the present invention.

< organic EL display >

In making, comprise colour filter of the present invention organic EL display time; can adopt following method: for example; as illustrated in fig. 1; on transparent support substrate 10, utilize colored resin composition of the present invention to form pixel 20 and obtain blue color filter; and on this blue color filter across organic protection layer 30 and inorganic oxide film 40 lamination organic luminophors 500, make thus the organic EL of polychrome.

As the laminating method of organic luminophor 500, can enumerate: the method that forms successively transparent anode 50, hole injection layer 51, hole transmission layer 52, luminescent layer 53, electron injecting layer 54 and negative electrode 55 at colour filter upper surface; The organic luminophor 500 that makes to be formed on another substrate is fitted in method on inorganic oxide film 40 etc.The organic EL 100 of making is thus applicable to the organic EL display of passive matrix mode, also applicable to the organic EL display of active drive mode.

Embodiment

Then, enumerate synthesis example, embodiment and comparative example and be described more specifically the present invention, but within not exceeding the scope of main points of the present invention, the present invention is not subject to the restriction of following embodiment.

The synthetic > of < dyestuff

(synthesis example 1: dyestuff A's is synthetic)

[Chemical formula 1 7]

(synthesizing of compound 2)

1-amino naphthalenes (14.3g) is dissolved in 1-propyl alcohol (300ml), adds methyl alcohol (20ml) solution of PS (12.2g), reflux 2 hours.Filter out generated precipitation, with 1-propyl alcohol, clean, obtained compound 2 (12.3g).

(dyestuff A's is synthetic)

At compound 1 (record according to TOHKEMY 2011-70171 communique method synthetic), (8.05g) and in the mixture of 2-propyl alcohol (100ml) add sodium borohydride (1.0g), reflux 18.5 hours.Append sodium borohydride (1.0g), further reflux 1.5 hours.Carry out concentrating under reduced pressure, add tetrahydrofuran (THF) (50ml), reflux 2 hours.Carry out concentrating under reduced pressure, add 1N aqueous sodium hydroxide solution, with toluene extraction, with saturated aqueous common salt, clean, carry out anhydrous sodium sulfate drying, obtained oily matter.

In resulting oily matter (total amount), add compound 2 (3.71g) and 2N hydrochloric acid (40ml), reflux 2 hours.Add aqueous sodium hydroxide solution to become after alkalescence, generated tarry insolubles.By decant, removed supernatant liquor, then carried out concentrating under reduced pressure, added water to stir, then by decant, removed and anhydrate, by resulting solid drying.

In resulting solid (total amount), add methyl alcohol (100ml) and chloranil (3.44g), at 50 ℃, stirred 2 hours.Carry out concentrating under reduced pressure, add chloroform and water, isolate chloroform layer, with silica gel chromatography (eluting solvent: chloroform～chloroform/methanol=10/1) carry out purifying, obtained dyestuff A (1.30g).

Compound identification method: mass spectroscopy

Ionization mode: LDI

Posi?m/z＝586[M+H] ⁺

Neg?m/z＝585[M] ^-

The very big absorbing wavelength (λ max) of this compound in 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=4/6 solution is that 639nm, gram specific absorbance are 125.

(synthesis example 2: dyestuff B's is synthetic)

(synthesizing of compound 11)

[Chemical formula 1 8]

By 1,7-Ke Liewei acid (2.23g, Tokyo change into industry manufacture), 1,1, the fluoro-4-butyl iodide of 1-tri-(2.98g, Tokyo change into industry manufacture), salt of wormwood (the pure pharmaceutical worker's industry of 2.76g and light is manufactured) and N-Methyl pyrrolidone (22mL) mix, and under nitrogen atmosphere, in 80 ℃, have stirred 10 hours.Reaction solution is cooled to room temperature, then mixes with water (150mL), with concentrated hydrochloric acid, be adjusted to pH=5.3, then by ethyl acetate, extract.By organic layer anhydrous sodium sulfate drying, then filter out siccative, solvent has been removed in distillation.With Di Iso Propyl Ether, to the cleaning that suspends of gained crystal, by filtration under diminished pressure and separated from solvent, and then resulting solid is under reduced pressure removed to residual solvent in 50 ℃, obtained the compound 11 (2.79g) of white solid.

The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?334(M+H ⁺,C ₁₄H ₁₅F ₃NO ₃S)

(dyestuff B's is synthetic)

[Chemical formula 1 9]

Compound 1 (8.46g) is dissolved in THF (68mL), adds lithium borohydride (3mol/L, THF solution, 9.2mL), under nitrogen atmosphere, in 50 ℃, stirred 3 hours.Be cooled to after room temperature, add aqueous sodium hydroxide solution (1mol/L, 10mL) and stir, then mix with water (300mL), by ethyl acetate, extract.Organic layer water, saturated aqueous common salt are cleaned, by anhydrous sodium sulphate, be dried.Filter out siccative, distillation, except desolventizing, has obtained oily matter (7.96g) thus.

The resulting oily matter of above-mentioned reaction (2.04g) and compound 11 (2.06g) are dissolved in acetic acid (26mL), have at room temperature stirred 5 hours.Reaction solution is mixed with water (150mL), is 6.5 with aqueous sodium hydroxide solution (20 % by weight) by pH regulator, and solid is separated out.Filter out resulting solid, under reduced pressure in 50 ℃ dry, obtained light blue solid (3.16g).By (the eluting solvent: chloroform/methanol=93/7～78/22) carry out purifying, obtained light blue solid (1.66g) of silica gel chromatography for 2.5g wherein.The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?656(M+H ⁺,C ₃₆H ₄₅F ₃N ₃O ₃S)

The light blue solid (1.64g) that above-mentioned reaction is obtained, chloranil (0.61g) and methyl alcohol (33mL) mix, at room temperature stir 4 hours, at 45 ℃, stirred 8 hours.Reaction solution is cooled to after room temperature, and solvent has been removed in distillation.By this silica gel chromatography (eluting solvent: chloroform/methanol=95/5～82/18) carry out purifying, obtained the dyestuff B (0.82g) of mazarine solid for crude product.

The very big absorbing wavelength (λ max) of this compound in 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is that 633nm, gram specific absorbance are 126.The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?654(M+H ⁺,C ₃₆H ₄₃F ₃N ₃O ₃S)

(synthesis example 3: dyestuff C's is synthetic)

(synthesizing of compound 12)

[Chemical formula 2 0]

By 1,6-Ke Liewei acid (3.35g, Tokyo change into industry manufacture), 1,1, the fluoro-4-butyl iodide of 1-tri-(3.57g, Tokyo change into industry manufacture), salt of wormwood (the pure pharmaceutical worker's industry of 2.07g and light is manufactured) and N-Methyl pyrrolidone (27mL) mix, and under nitrogen atmosphere, in 80 ℃, have stirred 8 hours.Then, add the fluoro-4-butyl iodide of 1,1,1-tri-(0.71g), further at 80 ℃, heated 2 hours.

Reaction solution is cooled to after room temperature, mixes with water (150ml), with concentrated hydrochloric acid, be adjusted to pH=4, then by ethyl acetate, extract.With rotatory evaporator distillation, remove the solvent in extract layer, by the Di Iso Propyl Ether cleaning that suspends for the crystal of separating out, by filtration under diminished pressure and separated from solvent, and then resulting solid is under reduced pressure removed to residual solvent in 50 ℃, obtained the compound 12 (2.43g) of white solid.

The result of the LC-MS analysis of this compound is as follows.LCMS(ESI,posi)m/z334(M+H ⁺,C ₁₄H ₁₅F ₃NO ₃S)

(dyestuff C's is synthetic)

[Chemical formula 2 1]

Compound 1 (2.71g) is dissolved in THF (22mL), adds lithium borohydride (3mol/L, THF solution, 2.9mL), under nitrogen atmosphere, in 50 ℃, stirred 2 hours.Be cooled to after room temperature, add aqueous sodium hydroxide solution (1mol/L, 6mL) and stir, then mix with water (150mL), by ethyl acetate, extract.Organic layer water, saturated aqueous common salt are cleaned, by anhydrous sodium sulphate, be dried.Filter out siccative, distillation, except desolventizing, has obtained oily matter (2.74g) thus.

The oily matter that above-mentioned reaction is obtained (2.38g) and compound 12 (2.31g) are dissolved in acetic acid (19mL), at room temperature stir 1 hour, then place a night.Second day, mixes reaction solution with water (200mL), with aqueous sodium hydroxide solution (20 % by weight), by pH regulator to 4.1, solid is separated out.Filter out resulting solid, under reduced pressure in 50 ℃ dry, obtained light blue solid (3.77g).The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?656(M+H ⁺,C ₃₆H ₄₅F ₃N ₃O ₃S)

The light blue solid (1.44g) that above-mentioned reaction is obtained, chloranil (0.54g) and methyl alcohol (29mL) mix, at room temperature stir 4 hours, at 55 ℃, stirred 4.5 hours.Then, add chloranil (0.27g), further heated 10.75 hours.Reaction solution is cooled to after room temperature, and filtering reacting liquid, has removed insolubles, and then distillation is except desolventizing.By this silica gel chromatography (eluting solvent: chloroform/methanol=95/5～85/15) carry out purifying, obtained the dyestuff C (0.31g) of mazarine solid for crude product.

The very big absorbing wavelength (λ max) of this compound in 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is that 639nm, gram specific absorbance are 111.The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?654(M+H ⁺,C ₃₆H ₄₃F ₃N ₃O ₃S)

(synthesis example 4: dyestuff D's is synthetic)

(synthesizing of compound 13)

[Chemical formula 2 2]

By 1,8-Ke Liewei acid (3.35g, Tokyo change into industry manufacture), 1,1, the fluoro-4-butyl iodide of 1-tri-(3.57g, Tokyo change into industry manufacture), salt of wormwood (the pure pharmaceutical worker's industry of 2.07g and light is manufactured) and N-Methyl pyrrolidone (27mL) mix, and under nitrogen atmosphere, in 80 ℃, have stirred 7.5 hours.Then, add the fluoro-4-butyl iodide of 1,1,1-tri-(0.89g), further heated 3.75 hours.Reaction solution is cooled to after room temperature, mixes with water (150mL), with concentrated hydrochloric acid, be adjusted to pH=1.3, filter out the solid of separating out, under reduced pressure in 50 ℃ dry, obtained the compound 13 (4.23g) of white solid.

(dyestuff D's is synthetic)

[Chemical formula 2 3]

Compound 1 (1.69g) is dissolved in THF (14mL), adds lithium borohydride (3mol/L, THF solution, 1.8mL), under nitrogen atmosphere, in 50 ℃, stirring 2 hours.Be cooled to after room temperature, add aqueous sodium hydroxide solution (1mol/L, 6mL) and stir, then mix with water (100mL), by ethyl acetate, extract.Organic layer water, saturated aqueous common salt are cleaned, by anhydrous sodium sulphate, be dried.Filter out siccative, distillation, except desolventizing, has obtained oily matter (1.76g) thus.

The oily matter that above-mentioned reaction is obtained (1.57g) and compound 13 (1.53g) are dissolved in acetic acid (23mL), at room temperature stir 1.5 hours, have placed a night.Second day, mixes reaction solution with water (150mL), with aqueous sodium hydroxide solution (20 % by weight), by pH regulator, be 3.83, and solid is separated out.Filter out resulting solid, under reduced pressure in 50 ℃ dry, obtained light blue solid (2.5g).

This crude product (2.5g) is merged with utilizing the synthetic crude product of same synthesis method (0.8g), with silica gel chromatography (eluting solvent: chloroform/methanol=98/2～90/10) carry out purifying, obtained light blue solid (1.89g).The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?656(M+H ⁺,C ₃₆H ₄₅F ₃N ₃O ₃S)

The light blue solid (1.89g) that above-mentioned reaction is obtained, chloranil (0.71g) and methyl alcohol (30mL) mix, and have stirred 4 hours at 45 ℃.Reaction solution is cooled to after room temperature, removes by filter insolubles, and solvent has been removed in distillation.By this silica gel chromatography (eluting solvent: chloroform/methanol=98/2～92/8) carry out purifying, obtained the dyestuff D (0.75g) of mazarine solid for crude product.

The very big absorbing wavelength (λ max) of this compound in 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 solution is that 648nm, gram specific absorbance are 104.The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z?654(M+H ⁺,C ₃₆H ₄₃F ₃N ₃O ₃S)

(with reference to synthesis example 1: relatively dyestuff 1)

[Chemical formula 2 4]

By the mixture of compound 21 (6.0g, 25mmol, synthetic according to the method for recording in No. 2008/003604th, International Publication), compound 22 (6.4ml, 50mmol, change into and buy from Tokyo), salt of wormwood (6.9g, 50mmol), METHYLPYRROLIDONE (25ml) 110～125 ℃ heated and stirred 4 hours.Be cooled to after room temperature, add water, with toluene, extract, toluene layer is cleaned with dilute hydrochloric acid and saturated aqueous common salt, by anhydrous sodium sulphate, be dried.Carry out concentrating under reduced pressure, obtained shallow dark brown oil (9.2g).This shallow dark brown oil is dissolved in ethanol (40ml), adds water (25ml) solution of sodium hydroxide (2g, 52.3mmol), at 85 ℃, stirred 1 hour.After naturally cooling, with toluene, extract, toluene layer is cleaned with saturated aqueous common salt, by anhydrous sodium sulphate, be dried.Carry out concentrating under reduced pressure, with silica gel chromatography (hexane/ethyl acetate=3/1), carry out purifying, obtained the white powder of compound 23 (5.95g, yield 94%).

[Chemical formula 2 5]

By the mixture reflux of compound 1 (1.47g, 4.34mmol, synthetic according to the method for recording in No. 2009/107734th, International Publication), compound 23 (1.1g, 4.34mmol), toluene (30ml), phosphoryl chloride (0.6ml) after 4 hours, be cooled to room temperature, add water, with chloroform, extract, by chloroform layer concentrating under reduced pressure, with silica gel chromatography (eluting solvent: chloroform/methanol=15/1～10/1) carry out purifying, with hexane, resulting solid is cleaned, obtained compound 25 (1.32g, yield 50%).

[Chemical formula 2 6]

The mixture of compound 25 (8.9g, 14.6mmol), compound 26 (4.2g, 14.6mmol, change into and buy from Tokyo), methyl alcohol (50ml) is stirred after 1.5 hours 50 ℃, concentrating under reduced pressure, methanol/water=1/2 for solid obtaining is cleaned, obtained relatively dyestuff 1 (11.5g, yield 92.3%).

(with reference to synthesis example 2: relatively dyestuff 2)

[Chemical formula 2 7]

By compound 25 (1.95g), C.I. acid blue 80, (Aldrich company manufactures: 1.36g), the mixture of methyl alcohol (25mL) stirred 30 minutes at 50 ℃, then carry out concentrating under reduced pressure, the mixed solvent of solid water/methyl alcohol=2/1 obtaining is cleaned, obtained relatively dyestuff 2 (2.22g).

The synthetic > of < resin

(with reference to synthesis example 3: Resin A synthetic)

Propylene glycol methyl ether acetate 145 weight parts are carried out to nitrogen displacement on one side and stir on one side, be warming up to 120 ℃.With within 3 hours, dripping wherein vinylbenzene 10 weight parts, glycidyl methacrylate 85.2 weight parts, there are mono acrylic ester FA-513M (Hitachi changes into Co., Ltd. and manufactures) 66 weight parts and 2 of tricyclodecane skeleton, 2 '-azo is two-and the mixed solution of 2-methylbutyronitrile 8.47 weight parts further continues to have stirred 2 hours at 90 ℃.Then, will in reaction vessel, become air displacement, in vinylformic acid 43.2 weight parts, drop into three (dimethylaminomethyl) phenol 0.7 weight part and quinhydrones 0.12 weight part, at 100 ℃, continue reaction 12 hours.Then, add Tetra Hydro Phthalic Anhydride (THPA) 56.2 weight parts, triethylamine 0.7 weight part, at 100 ℃, reacted 3.5 hours.The weight-average molecular weight Mw of the resin solution obtained above of measuring by GPC is about 8400, acid number is 80mg-KOH/g.In this resin solution, add propylene glycol methyl ether acetate, making solids component is 44 % by weight, as Resin A, uses.

(with reference to synthesis example 4: resin B synthetic)

Propylene glycol methyl ether acetate 145 weight parts are carried out to nitrogen displacement on one side and stir on one side, be warming up to 120 ℃.With within 3 hours, dripping wherein vinylbenzene 5.2 weight parts, glycidyl methacrylate 132 weight parts, there are mono acrylic ester FA-513M (Hitachi changes into Co., Ltd. and manufactures) 4.4 weight parts and 2 of tricyclodecane skeleton, 2 '-azo is two-and the mixed solution of 2-methylbutyronitrile 8.47 weight parts further continues to stir 2 hours at 90 ℃.Then, will in reaction vessel, become air displacement, in vinylformic acid 67.0 weight parts, drop into three (dimethylaminomethyl) phenol 1.1 weight parts and quinhydrones 0.19 weight part, at 100 ℃, continue to have reacted 12 hours.Then, add Tetra Hydro Phthalic Anhydride (THPA) 15.2 weight parts, triethylamine 0.2 weight part, at 100 ℃, reacted 3.5 hours.The weight-average molecular weight Mw that the resin solution obtained above of measuring by GPC is converted into polystyrene is about 9000, acid number is 25mg-KOH/g.In this resin solution, add propylene glycol methyl ether acetate, making solids component is 40 % by weight, as resin B, uses.

(with reference to synthesis example 5: resin C's is synthetic)

In reaction vessel, pack " NC3000H " (Nippon Kayaku K. K's manufacture) (69 ℃ of epoxy equivalent (weight) 288, softening temperatures) 400 weight parts, vinylformic acid 102 weight parts, p methoxy phenol 0.3 weight part, triphenylphosphine 5 weight parts and propylene glycol methyl ether acetate 264 weight parts into, at 95 ℃, stir, until acid number reaches below 3mg-KOH/g.Acid number reaches target value needs 9 hours (acid number 2.2mg-KOH/g).Then, further add Tetra Hydro Phthalic Anhydride 151 weight parts, at 95 ℃, react 4 hours, the resin solution that the weight-average molecular weight that is converted into polystyrene (Mw) that to have obtained acid number be 102mg-KOH/g, measure by GPC is 3900.In this resin solution, add propylene glycol methyl ether acetate, making solids component is 44 % by weight, as resin C, uses.

The preparation > of < colored resin composition

By dyestuff A, the B, C and the D that obtain in above-mentioned synthesis example 1～4, with reference to the comparison dyestuff 1 and 2 obtaining in synthesis example 1 and 2, with reference to the Resin A obtaining in synthesis example 3 and the mixing of other composition, making them is the composition of recording in following table 1, has prepared colored resin composition.

The numerical value of table 1 all represents the weight part of each added composition.

During mixing, stir 1 hour above until each composition fully mixes, finally utilize the canopy-type strainer (Horse type Off ィルター of 5 μ m) filter, removed foreign matter.

By dyestuff A, the B, C and the D that obtain in above-mentioned synthesis example 1～4, with reference to the comparison dyestuff 1 and 2 obtaining in synthesis example 1 and 2, with reference to the resin B obtaining in synthesis example 4 and 5 and C and the mixing of other composition, making them is the composition of recording in following table 1, has prepared colored resin composition.

The numerical value of table 2 all represents the weight part of each added composition.

During mixing, stir 1 hour above until each composition fully mixes, finally utilize the canopy-type strainer of 5 μ m to filter, removed foreign matter.

Each compound in table 1 is as follows respectively.

PBG-305:TRONLYTR-PBG-305 Changzhou Tronly New Electronic Materials Co., Ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) manufactures

DPHA: dipentaerythritol acrylate

PGMEA: propylene glycol methyl ether acetate

PGME: propylene glycol monomethyl ether

F475 DIC company manufactures: the oligopolymer that contains perfluoroalkyl

Irganox1010 BASF AG manufactures: tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester]

JPP-100 Johoku Chemical Co., Ltd. manufactures: tetraphenyl dipropylene glycol diphosphites [table 2]

It should be noted that, each compound in table 2 is as follows respectively.

DPHA: dipentaerythritol acrylate

PET-P: tetramethylolmethane four (3-mercaptopropionic acid ester)

IRGACURE 907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone

EABF:4,4 '-bis-(diethylamino) benzophenone

Compounds X: 3-(2-acetoxyl group imino--1,5-dioxy-5-methoxyl group amyl group)-9-ethyl-6-(toluoyl base)-9H-carbazole

F475 DIC company manufactures: the oligopolymer that contains perfluoroalkyl

JPP-100 Johoku Chemical Co., Ltd. manufactures: tetraphenyl dipropylene glycol diphosphites

PGMEA: propylene glycol methyl ether acetate

PGME: propylene glycol monomethyl ether

< evaluates >

The brightness of the film of [1] being made by colored resin composition and stable on heating evaluation (embodiment 1～4 and comparative example 1 and 2)

Utilize spin-coating method at the colored resin composition that is cutting on the square glass substrate of 5cm coating as the preparation of above-mentioned table 1, making dried sy value is 0.120, after drying under reduced pressure, on hot plate in 80 ℃ of prebake (pre-bake) of having carried out 3 minutes.Then, with 60mJ/cm ²exposure whole face is exposed, then, with dustless baking oven, fire 30 minutes in 200 ℃, use spectrophotometer U-3310 (Hitachi's manufactures) mensuration spectral transmission, and calculate its colourity (illuminant-C) in XYZ colour system.

Result is summarized in table 3.

[table 3]

?	Colored resin composition	sx	sy	Brightness
					Embodiment 1	A-1	0.139	0.120	17.0
Embodiment 2	B-1	0.138	0.120	16.9
					Embodiment 3	C-1	0.139	0.120	16.5
Embodiment 4	D-1	0.141	0.120	16.5
					Comparative example 1	Compare 1	0.138	0.120	17.0
Comparative example 2	Compare 2	0.139	0.120	16.4

[2] mensuration of the voltage retention based on liquid crystal and ion density (embodiment 5～16 and comparative example 3～6)

Use spinner and set rotating speed (300rpm～700rpm) and at whole evaporation, have the upper coating colored resin composition of glass substrate (the full version of glass ITO (beta) MN-1392 for EHC evaluation processed) of ITO (indium doped stannum oxide alloy) electrode, the thickness that makes coated film is 2～3 μ m (thickness after thermofixation is about 2 μ m), the dyestuff that described colored resin composition comprises embodiment and comparative example and making with above-mentioned ratio and composition, by the hot plate prebake of 80 ℃ 3 minutes, then at vacuum chamber inner drying 1 minute.

Then, use high pressure mercury vapour lamp, the periphery as electrode is implemented to photomask, with 62mJ/cm ²the exposure radioactive rays 30mW of each wavelength that the exposure of filming is comprised to 303nm, 313nm, 334nm, 365nm, 405nm and 436nm, and then at 200 ℃, carry out 60 minutes after fixing (below, also referred to as " solidification value "), make curing of coating, obtained blue pixel substrate for liquid crystal evaluation (following, also referred to as " resist film ").

After the warm water of water and 45 ℃ cleans the electrode base board that has formed the substrate of blue pixel and be only given shape by ITO electrode evaporation (EHC is glass SZ-B11MIN (B) MN11396 for evaluation processed), dry in the baking oven of 105 ℃, after fitting with the sealing agent that is mixed with the granulated glass sphere of 5 μ m (gap is 5 μ m), the baking close annealings of 180 ℃ 2 hours, in the box obtaining, inject liquid crystal MLC-7021-000 (manufacture of Merck company), having made electrode area is 1cm ²liquid crystal cell.

Then, utilize liquid crystal evaluation of physical property system 6254 types (TOYO Corporation manufacture), at 25 ℃, measured the voltage retention of liquid crystal cell.Now to apply rectangular wave, the mensuration frequency that voltage is 5.0V be 60Hz, 2Hz and 0.6Hz.Here said voltage retention is conventionally known Area Ratio and 2 kinds of method for expressing of voltage ratio, has adopted in this application the value (ratio of the area that the area surrounding to voltage trace and the voltage zero level of 16.7 milliseconds (examples of 60Hz) after 0 millisecond obtains with respect to the voltage of 0 millisecond being kept to 16.7 milliseconds of observation times (situation about measuring at 60Hz), observation time 0.5 second (in the situation of 2Hz mensuration) or 1.67 seconds (situation of 0.6Hz)) of Area Ratio.

Ion density is used the device identical with voltage retention to measure.Apply the choppy sea of frequency 0.1Hz, ± 10V, to calculate the form of the waveform hour changing of electric current, be output.In waveform, the direct peak of liquid crystal only utilizes in advance as the above-mentioned box of liquid crystal is measured, and then, each routine liquid crystal cell is measured.The method of asking about the direct peak of the liquid crystal that occurs in ion waveform and foreign ion peak and foreign ion density, is shown in Fig. 2.

For voltage retention, at 60Hz, be preferably more than 85%, at 2Hz, be preferably more than 25%, more preferably more than 30%, more preferably more than 60%, be particularly preferably more than 80%, desirable voltage retention is more than 90%.

In addition, the voltage retention below 2Hz is the characteristic very responsive to ionic impurity.This voltage retention below 2Hz wants voltage retention under intervention of coupled ion etc. and ion density measurement result (ion density, the direct peak current/foreign ion of liquid crystal peak current), 60Hz and the performance of liquid crystal to observe to consider its preferred scope.

In addition it is more remarkable that, the voltage retention under 0.6Hz is subject to the impact of ionic impurity.This be due to, the in the situation that of 0.6Hz, the movement of the foreign ion on resist film surface in liquid crystal is more abundant, the time that measuring voltage changes is longer.

By measuring ion density, can learn the impact of the ionic impurity that derives from resist film.That is, positive ion side and negative ion side are executed in alive situation, being illustrated in any side is all that ion density is higher, in liquid crystal, comprises ionic impurity, comprises the factor that liquid crystal cell is applied to the voltage maintenance of voltage and obstruction liquid crystal cell that hinders.That is, ion density is less, and electrical characteristic are better.It should be noted that, be only in the situation of liquid crystal, and ion density is 0nC.

Liquid crystal evaluation result is summarized in to table 4 (colored resin composition of table 1) and table 5 (coloured composition of table 2).

It should be noted that, in table, voltage retention refers to for " because current leakage cannot quantize ", in the time shorter than the response speed of liquid crystal, namely apply voltage after in time below 1 millisecond, voltage drop is extremely lower than 2V, therefore, voltage during liquid crystal cell work is not applied to the phenomenon on liquid crystal cell, and electrical characteristic are obviously lower.

In addition, ion density is that " because current leakage cannot be measured " refers to, in the box that is " cannot measure because of current leakage " in voltage retention, electrical characteristic are obviously lower, therefore can not measure exactly ion density.

" ion density too high and cannot measure " refers to, owing to there being current leakage, liquid crystal does not respond, therefore the direct peak of liquid crystal does not embody in ion density, and because the electric current producing is excessive, quasi-molecular ions is capped and cannot distinguishes, the ion density determination limit that has exceeded device, represents that electrical characteristic are low.

As shown in table 3, use the brightness of the pixel that colored resin composition of the present invention forms high, be good blue pixel.In addition, as shown in table 4 and table 5, the voltage retention of this liquid crystal cell being formed by the blue pixel substrate (resist film) that has used colored resin composition of the present invention is also high, and ion density is little, has good electrical characteristic.Particularly 200 ℃ of such temperature are slightly low as the solidification value of resin combination, and ionic composition, in liquid crystal or in the stripping of the interface of liquid crystal and resist film, is evaluated characteristic for liquid crystal and had disadvantageous tendency.Even if adopt 200 ℃ of so slightly low solidification values, also low by the ion density of the film formed liquid crystal cell of resist with embodiment compound, compare with comparative example, there is the repressed tendency of stripping of ionic impurity.Its result, voltage retention is high, is good.Particularly, for the colored resin composition (embodiment 6,8,10,14) of the compound that comprises dyestuff B, its ion density is the highest also lower than 1nC, and the voltage retention under 0.2Hz has surpassed 85%.That is, known its electrical characteristic are good and voltage retention is also high.

As previously discussed, it is high-quality having the colour filter of the pixel of using colored resin composition formation of the present invention and the liquid crystal indicator that comprises this colour filter and organic EL display.

With reference to specific embodiment, the present invention is had been described in detail, but it will be understood by those skilled in the art that without prejudice to the spirit and scope of the invention in the situation that, can carry out various changes or correction.The Japanese patent application (Patent 2012-077457) of the application based on proposing on March 29th, 2012 and completing, its content is introduced in the application as a reference.

Industrial applicibility

According to the present invention, a kind of novel triarylmethane compounds can be provided, by this triarylmethane compounds, can be obtained having realized the pixel of brightness and voltage retention simultaneously.In addition, according to the present invention, a kind of novel colored resin composition can be provided, by this colored resin composition, also high pixel of the high and voltage retention of brightness can be obtained.In addition, the present invention can provide and comprise the high and voltage retention of the brightness also colour filter of high pixel and high-quality liquid crystal indicator and organic EL display.Therefore, the present invention is useful in the application aspect for colour filter and liquid crystal indicator and organic EL display etc.

Claims

1. the triarylmethane compounds that following formula (I) represents,

In above-mentioned formula (I), R ¹～R ⁶represent independently of one another hydrogen atom, optionally there is the alkyl of substituent carbonatoms 1～10 or optionally there is substituent aromatic ring group, adjacent R ¹～R ⁶can be connected to each other and form ring, this ring optionally has substituting group,

M ⁺represent positively charged ion,

N represents 0～4 integer.

2. triarylmethane compounds according to claim 1, wherein, in above-mentioned formula (I), R ⁷for hydrogen atom, R ⁸for halogen atom or optionally there is the alkyl of substituent carbonatoms 1～10.

3. triarylmethane compounds according to claim 1 and 2, wherein, the compound that above-mentioned formula (I) represents is the compound that following formula (II) represents,

In above-mentioned formula (II), n, M ⁺, R ¹～R ⁵, R ⁷and R ⁸with the definition synonym in above-mentioned formula (I),

M represents 1～8 integer.

4. a colored resin composition, it contains (A) dyestuff, (B) solvent and (C) adhesive resin, wherein,

(A) dyestuff is the triarylmethane compounds described in any one in claim 1～3.

5. colored resin composition according to claim 4, wherein, also contains (D) polymerizable monomer.

6. according to the colored resin composition described in claim 4 or 5, wherein, also contain (E) photopolymerization and cause composition and thermopolymerization and cause at least one in composition.

7. a colour filter, it has right to use and requires the pixel that in 4～6, the colored resin composition described in any one forms.

8. a liquid crystal indicator, it has colour filter claimed in claim 7.

9. an organic EL display, it has colour filter claimed in claim 7.