CN104204105B

CN104204105B - Triarylmethane compounds, colored resin composition, light filter, liquid crystal indicator and organic EL display

Info

Publication number: CN104204105B
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: 2016-12-07
Anticipated expiration: 2033-03-28
Also published as: JPWO2013147099A1; TWI588212B; CN104204105A; JP6168048B2; TW201348341A; KR20140142262A; WO2013147099A1

Abstract

The problem of the present invention is to provide the colored resin composition of a kind of pixel obtaining and having both brightness and voltage retention.The problem of the present invention also resides in and provides a kind of and comprise the light filter of pixel and the liquid crystal indicator of high-quality and organic EL display that brightness is high and voltage retention is the highest.The colored resin composition that the present invention relates to contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that, should (A) dyestuff contain compound that below formula (I) represents (in formula, R¹～R⁸、M⁺, n represent the meaning described in claim 1).

Description

Triarylmethane compounds, colored resin composition, light filter, liquid crystal display fill Put and organic EL display

Technical field

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

Background technology

The flat faced display as representative with liquid crystal indicator and organic EL (Electroluminescence) display device It is widely used, these display employ light filter.

Along with the trend in energy-saving such epoch, as light filter, it is desirable to more high brightness and high-contrast.

Light filter mainly employs colored resin composition, this colored resin composition employs pigment, but in order to Obtain high brightness and high-contrast, such as, disclose in non-patent literature 1 and the particle diameter differential of pigment particles is dissipated to its color development The method of less than the 1/2 of wavelength.

On the other hand, as coloring agent, also carried out the exploitation of dyestuff.

For example, Patent Document 1 discloses use triarylmethane derivatives as dyestuff.It addition, patent documentation 2 and 3 In, disclose the technology making anion be ad hoc structure further in triarylmethane salt.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2008-304766 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2011-132492 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2011-133844 publication

Non-patent literature

Non-patent literature 1: bridge pawl is clear " Se Cai association will " (" color material meeting "), in December, 1967, p608

Summary of the invention

The problem that invention is to be solved

But, about the method disclosed in non-patent literature 1, particularly blue pigment, due to other redness, green Pigment is compared, and its color development wavelength is shorter, in this case, needs further differential to dissipate, the stability after cost raising and dispersion Become problem.

It addition, in the patent documentation 1～3 that triarylmethane salt is improved, find that pixel to be obtained is difficult to Have both brightness and voltage retention.

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

Additionally, the problem of the present invention is to provide a kind of novel pigmentary resin group containing triarylmethane compounds Compound, it can form the pixel that brightness is high and voltage retention is the highest.

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

The method of solution problem

That the present inventor etc. conduct in-depth research it was found that had the novel triaryl of ad hoc structure by use Methane compound, can solve above-mentioned problem, thus complete the present invention.

That is, the present invention relates to triarylmethane compounds (following, sometimes referred to simply as " compound (I) "), containing chemical combination Colored resin composition, light filter, liquid crystal indicator and the organic EL display of thing (I), described triarylmethane class Compound is characterised by, it is represented by following formula (I).

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

[chemical formula 1]

(in above-mentioned formula (I), R¹～R⁶Represent hydrogen atom independently of one another, optionally there is the carbon number 1～10 of substituent group Alkyl or optionally there is the aromatic ring group of substituent group, adjacent R¹～R⁶Can be connected to each other and form ring, this ring optionally has Substituted base,

R⁷And R⁸Represent hydrogen atom or arbitrary substituent group independently of one another,

Wherein, R⁷And R⁸In at least one be halogen atom or the alkyl of the carbon number optionally with substituent group 1～10,

M⁺Represent cation,

N represents the integer of 0～4.)

[2] the triarylmethane compounds described in above-mentioned [1], wherein, in above-mentioned formula (I), R⁷For hydrogen atom, R⁸For Halogen atom or optionally there is the alkyl of carbon number 1～10 of substituent group.

[3] above-mentioned [1] or [2] described in triarylmethane compounds, 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⁺、R¹～R⁵、R⁷And R⁸With the definition synonym in above-mentioned formula (I),

R¹¹And R¹²Represent hydrogen atom or arbitrary substituent group independently of one another,

M represents the integer of 1～8.)

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

(A) dyestuff is the triarylmethane compounds according to any one of above-mentioned [1]～[3].

[5] colored resin composition described in above-mentioned [4], wherein, possibly together with (D) polymerizable monomer.

[6] above-mentioned [4] or [5] described in colored resin composition, wherein, cause composition and heat possibly together with (E) photopolymerization Polymerization causes at least one in composition.

[7] a kind of light filter, it has the colored resin composition formation used according to any one of above-mentioned [4]～[6] Pixel.

[8] a kind of liquid crystal indicator, it has the light filter described in above-mentioned [7].

[9] a kind of organic EL display, it has the light filter described in above-mentioned [7].The effect of invention

According to the present invention, it is provided that a kind of novel triarylmethane compounds, it can obtain having both brightness and electricity The pixel of pressure conservation rate.

Additionally, according to the present invention, it is provided that a kind of novel pigmentary resin group containing triarylmethane compounds Compound, it can form the pixel that brightness is high and voltage retention is the highest.

It addition, the present invention can provide light filter and the Gao Pin of the pixel containing brightness is high and voltage retention is the highest The liquid crystal indicator of matter and organic EL display.

Accompanying drawing explanation

[Fig. 1] Fig. 1 is the constructed profile of an example of the organic EL element illustrating the light filter with the present invention.

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

Symbol description

100 organic EL element

10 transparent support substrates

20 pixels

30 organic protection layers

40 inorganic oxide films

50 transparent anodes

500 organic luminorphors

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 (polarity of impurity peaks) of d liquid crystal

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

The direct peak of f liquid crystal

Detailed description of the invention

Hereinafter, it is described in detail for embodiments of the present invention, but following record is only embodiment of the present invention One example, 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 " acryloyl With at least one in methacryl ", " at least one in acrylate and methacrylate " etc., such as " (methyl) Acrylic acid " refer to " at least one in acrylic acid and methacrylic acid ".

It addition, " total solid composition " refers to the assembly of the colored resin composition of the present invention beyond solvent composition described later Point.

Additionally, " aromatic ring " refers to both " aromatic series hydrocarbon ring " and " heteroaromatic ".

It addition, terms such as " C.I. naphthol greens " refers to pigment call number (C.I.).

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

[about compound (I)]

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

[chemical formula 3]

M⁺Represent cation,

N represents the integer of 0～4.)

It should be noted that in above-mentioned formula (I) ,-SO illustrated outside []₃ ^-Base and-(SO₃ ^-M⁺)_nBasis representation be [] in Aromatic ring, R¹～R⁸, or R¹～R⁸The substituent group being had is respectively by-SO₃ ^-Base or-(SO₃ ^-M⁺)_nBase replaces.

(about R¹～R⁶)

R¹～R⁶Represent hydrogen atom independently of one another, optionally there is the alkyl of the carbon number 1～10 of substituent group or optionally have The aromatic ring group of substituted base.

As R¹～R⁶In alkyl, can enumerate carbon number be usually more than 1 and the straight-chain of usually less than 10, Chain or ring-type alkyl.As concrete example, methyl, ethyl, n-pro-pyl, 2-propyl group, normal-butyl, isobutyl group, tertiary fourth can be enumerated Base, cyclohexyl, cyclohexyl methyl, cyclohexyl-ethyl, phenethyl etc..

As R¹～R⁶In aromatic ring group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group.

As aromatic cyclic hydrocarbon group group, can be monocycle, it is also possible to for condensed ring, as long as the looped carbon number of shape is 5 ～18 be just not particularly limited, can enumerate such as: there is the phenyl ring of 1 free valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene Ring, pyrene ring, benzopyrene ring,The group of ring, benzo phenanthrene ring, acenaphthene ring, benzo acenaphthene ring, fluorenes ring etc..

It addition, as aromatic heterocyclic group, can be monocycle, it is also possible to be condensed ring, as long as the looped carbon number of shape It is 3～10 to be just not particularly limited, can enumerate such as: there is the furan nucleus of 1 free valency, benzofuran ring, thiphene ring, benzo Thiphene 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, benzisoxaAzoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline Quinoline ring, isoquinolin ring, cinnolines (cinnoline) ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Pyridine ring, quinazoline ring, quinoline The group of oxazoline ketone ring, ring etc..

Adjacent R¹～R⁶(specially R¹And R²、R³And R⁴、R⁵And R⁶) can also be connected to each other and form ring, and, this ring Optionally there is substituent group.

It addition, this ring can also be the ring by hetero atom bridging, as its concrete example, can enumerate below such as Structure.

[chemical formula 4]

Chemically from the standpoint of stability, as R¹～R⁶, preferably it is each independently hydrogen atom, optionally there is substituent group The alkyl of carbon number 1～10 or optionally there is the phenyl of substituent group, or adjacent R¹～R⁶Interconnected and shape is looped Situation.These substituent groups are also preferred in terms of brightness.From improve compound (I) thermostability, gained light filter fast light From the standpoint of property excellence, more preferably hydrogen atom, optionally there is the alkyl of the carbon number 1～10 of substituent group or optionally have take The phenyl of Dai Ji.

R¹～R⁶In the case of optionally there is the alkyl of carbon number 1～10 of substituent group, it may be speculated that in hyperconjugation Effect under, the dispersion of electric charge in cation, being stabilized of cation.

More specifically, for R¹～R⁴In alkyl carbon number for, from being difficult to affect the structure of triarylmethane skeleton Make from the point of view of the substituent group on (impact on brightness is little) and N is not easily disconnected from aspect (compound (I) stable) aspect, preferably 8 with Under, more preferably less than 4, and preferably more than 2.

Additionally, for R⁵And R⁶For, it is not easily decomposed and from the viewpoint of tone (brightness is high) from compound (I), preferably R⁵ For hydrogen atom, R⁶For alkyl.R⁶In the carbon number of alkyl be more preferably less than 8, more preferably less than 5.

It addition, adjacent R¹～R⁶Interconnected and in the case of forming ring, the substituent group on N is not easily disconnected from, the most surely Fixed.

R¹～R⁶In the case of optionally having the phenyl of substituent group, owing to conjugated system extends, the electric charge in cation divides Dissipate, cation stabilization.So, it is believed that the result of cation stabilization, the heat-resisting of obtained light filter can be made Property is more excellent.

As R¹～R⁶In the substituent group that optionally has of alkyl, aromatic ring group and ring that is interconnected and that formed, permissible Enumerate the group in the most following (replacing basis set W).

(replacing basis set W)

Fluorine atom, chlorine atom, the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkane of carbon number 1～8 Epoxide, phenyl,Base, tolyl, naphthyl, cyano group, acetoxyl group, the alkyl carbonyl oxy of carbon number 2～9, sulfamoyl, carbon The alkylsulfamoyl group of atomic number 2～9, the alkyl-carbonyl of carbon number 2～9, phenethyl, ethoxy, acetamido, it is bonded with The di-alkyaminoethyl group of alkyl of carbon number 1～4, trifluoromethyl, the trialkylsilkl of carbon number 1～8, Nitro, the alkylthio group of carbon number 1～8.

Wherein, as R¹～R⁶In the replacement that optionally has of alkyl, aromatic ring group and ring that is interconnected and that formed Base, the preferably alkyl of carbon number 1～10, the alkoxyl of carbon number 2～8, cyano group, acetoxyl group, carbon number 2～8 Alkyl carboxyl, sulfamoyl, the alkylsulfamoyl group of carbon number 2～9 and fluorine atom.

(about R⁷And R⁸)

R⁷And R⁸Represent hydrogen atom or arbitrary substituent group.

As above-mentioned arbitrary substituent group, such as halogen atom can be enumerated, optionally there is the carbon number 1～10 of substituent group Alkyl, optionally there is the aromatic ring group etc. of substituent group.

Wherein, R⁷And R⁸In at least one be halogen atom or the alkyl of the carbon number optionally with substituent group 1～10.

That is, in the phenyl ring in formula (I), being bonded of the carbon atom central relative to being positioned at triarylmethane structure, if It is bonded bulky group at ortho position, is then protected near triarylmethane structure central authorities from space, thus compound (I) thermostability improves.

Additionally, from being difficult to cause because of the molecule structure change of compound (I) absorption spectrum change and causing therefrom From the standpoint of the brightness of obtained pixel declines, R⁷And R⁸In the carbon number of alkyl be preferably less than 8, more preferably 6 with Under, particularly preferably less than 4, and usually more than 1.

As R⁷And R⁸In preferably mode, preferably R⁷For hydrogen atom, R⁸For alkyl, particularly preferred R⁷For hydrogen atom, R⁸For Methyl.

It addition, R⁷And R⁸Can be interconnected and form ring, this ring optionally has substituent group.As this substituent group, Ke Yiju Go out the group described in the most above-mentioned (replacing basis set W) item.

R⁷And R⁸In alkyl there is substituent group in the case of, preferably halogen atom.I.e., preferably enumerate trifluoromethyl etc. Fluoromethyl etc..

(about M⁺And n)

M⁺Represent cation, can enumerate such as: hydrion, alkali metal cation, alkaline earth metal cation, tertiary amine sun from Son or quaternary ammonium cation.

As the alkali metal of alkali metal cation, lithium, sodium, potassium etc. can be enumerated.It addition, as alkaline earth metal cation Alkaline-earth metal, can enumerate magnesium, calcium, barium etc..

Tertiary ammonium cation N⁺HR₃(R represents hydrogen atom, the alkyl optionally with substituent group or optionally has the virtue of substituent group Cyclic group, it should be noted that the multiple R contained can be the same or different) represent.

In above-mentioned R, the example of the substituent group that the preferred carbon number of this alkyl and this alkyl optionally have is with above-mentioned R¹～R⁶Alkyl in the case of cited carbon number, substituent group identical.The preferred carbon number of this aromatic ring group and The example of the substituent group that this aromatic ring group optionally has and above-mentioned R¹～R⁶Aromatic ring group in the case of cited carbon atom Number, substituent group are identical.Specifically can enumerate: low alkyl group ammonium cation (the such as methyl ammonium cation, second of carbon number 1～6 Base ammonium cation, diethyl ammonium cation, triethyl ammonium cation etc.), replace the alkylammonium of carbon number 1～6 having hydroxyl Cation (such as ethanolammonium cation, diethanol ammonium cation, triethanolammonium cations etc.), the substituted carbon number of carboxyl 1 ～alkyl ammonium cation (such as carboxymethyl ammonium cation, carboxyethyl ammonium cation, carboxylic propyl ammonium cation, the dicarboxy-methyl of 6 Ammonium cation etc.), replace and have the ammonium cation (such as N, N-diethyl phenyl ammonium cation etc.) etc. of aromatic ring group and alkyl.

Quaternary ammonium cation N⁺R₄Representing, R represents the alkyl optionally with substituent group or the aromatic ring optionally with substituent group Group.It should be noted that the multiple R contained can be the same or different.As this alkyl preferred carbon number and The example of the substituent group that this alkyl optionally has and above-mentioned R¹～R⁶Alkyl in the case of cited carbon number, replacement Base is identical.The example of the substituent group that the preferred carbon number of this aromatic ring group and this aromatic ring group optionally have is with above-mentioned R¹～R⁶Aromatic ring group in the case of cited carbon number, substituent group identical.

Specifically, can enumerate carbon number 1～6 quaternary alkyl ammonium cation (such as, tetramethylammonium cation, Tetraethylammonium cation, tetrabutyl ammonium cation etc.) etc..

It should be noted that M⁺The kind of cation be not limited to a kind, it is also possible to mix multiple.It addition, M⁺Cation Can be mixed multiple in a part of compound, it is also possible to be mixed multiple in colored resin composition.As M⁺Preferred example, from the viewpoint of the dissolubility for the organic solvent used in colored resin composition, preferably hydrogen from Son, alkali metal cation, tertiary ammonium cation, quaternary ammonium cation, more preferably lithium cation, sodium cation, unsubstituted ammonium sun from Son, tetrabutyl ammonium cation.

N represents the integer of 0～4.

N is the biggest, then compound (I) is replaced by the sulfo group of hydrophilic radical manyly, and its thermostability, light resistance improve, and changes The compound (I) dissolubility in hydrophobic liquid crystal also declines, and therefore voltage retention improves, but from colored resin composition Used in organic solvent in dissolubility height from the viewpoint of, preferably 0～2.

(about-SO₃ ^-The position of substitution of base)

In compound (I), []-SO outward₃ ^-Aromatic ring that basis representation is substituted in [], R¹～R⁸, or R¹～R⁸Had Substituent group on.-SO₃ ^-Preferred the position of substitution of base is to form the hydrogen atom on the naphthalene nucleus of triarylmethane skeleton or R⁶On take The hydrogen atom of Dai Ji.

Preferably-SO₃ ^-The reason that base is substituted on the naphthalene nucleus forming triarylmethane skeleton is as follows.-SO₃ ^-Base is substituted in naphthalene Compound (I) on ring, in the case of intermolecular one-tenth salt, forms ionic bond with nitrogen-atoms or the central carbon atom of another molecule, Now, due to-the SO of compound (I)₃ ^-Base is positioned on naphthalene nucleus, the aromatic ring that the naphthalene nucleus of compound (I) and another molecule are had it Between distance become near.Therefore, 2 is intermolecular in addition to ionic bond, also produces π-π and interacts, and therefore molecular separating force strengthens, resistance to Hot and electric reliability uprises.Further, since-SO₃ ^-Base is positioned on naphthalene nucleus, with center carbon and the-SO of a part₃ ^-The position of base Become near, it is also possible to expect in intramolecular firm one-tenth salt effect.Additionally, particularly-SO₃ ^-Base is substituted in the nitrogen-atoms of naphthalene nucleus not In the case of occurring on substituted ring, triarylmethane skeleton is little, little, from brightness on the impact of color development on the contribution of conjugated system From the standpoint of be preferred.

Then, preferably-SO₃ ^-Base is replaced in R⁶On substituent group on reason as follows.With by-SO₃ ^-Base imports to R¹～R⁴ Substituent group on situation compare, by-SO₃ ^-Base imports to R⁶On substituent group on synthesis on restriction little, be easier, with Time R⁶Substituent group on-SO₃ ^-Base, when intramolecular or intermolecular formation ionic bond, can take and compare position freely, easily It is arranged in the position that can form firm ionic bond.Particularly, R⁶In the case of alkyl, due to the degree of freedom of substituent group Height ,-SO₃ ^-Base is easily positioned at for forming intramolecular and the ideal position of intermolecular ionic bond, thus forms firm ion Key, therefore, is preferred from the standpoint of thermostability and electricity reliability.It addition, from triarylmethane skeleton to conjugated system Also it is preferred from the standpoint of contributing the brightness of little, little, obtained on the impact of color development pixel.

It should be noted that in formula (I) ,-SO₃ ^-Base ,-SO₃ ^-M⁺The covalent bond of base is labeled as referring to being connected in [], exists Multiple the position of substitution, obtain in synthesis is the meaning such as mixture of the different compound of the position of substitution.

[compound that formula (II) represents]

From the standpoint of the brightness and voltage retention excellence of obtained pixel, compound (I) is preferably following formula (II) compound (hereinafter referred to as " compound (II) ") represented by.

[chemical formula 5]

(in above-mentioned formula (II), n, M⁺、R¹～R⁵、R⁷And R⁸With n, the M in above-mentioned formula (I)⁺、R¹～R⁵、R⁷And R⁸Synonym.

R¹¹And R¹²Represent hydrogen atom or arbitrary substituent group independently of one another.

M represents the integer of 1～8.)

(about R¹¹And R¹²)

As R¹¹And R¹²In arbitrary substituent group, the group described in above-mentioned (replacing basis set W) item can be enumerated, from From the standpoint of synthesis easily, preferably hydrogen atom.

It addition, the multiple R contained in a part¹¹Each other and R¹²Each other can be the most identical or different, from conjunction From the standpoint of becoming easily, the most identical.

Additionally, R¹¹And R¹²Can be identical or different, from the standpoint of synthesis easily, the most identical.

(about m)

M is usually more than 1, is preferably more than 2, and usually less than 8, be preferably less than 5.

If in above-mentioned scope, then-(CR¹¹R¹²)_mThe SO that-base end is had₃ ^-Degree of freedom uprise, easily formed Intermolecular ionic bond and easy and intramolecular central carbon atom formation ionic bond, so that thermostability and voltage keep Rate becomes good, is preferred from this point of view.

[molecular weight]

The molecular weight of the compound (I) in the present invention is usually more than 450, is preferably more than 500, and usually 5000 with Under, be preferably less than 2000.

If in above-mentioned scope, then it is preferred from the standpoint of synthesis easily.

[concrete example]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

＜ is about synthetic method ＞ of compound (I)

Compound (I) can based on such as " synthetic dyestuffs summary (synthetic dyestuffs) " (hole mouth is rich to be write, three publish altogether, Nineteen sixty-eight), method described in " theoretical manufacture dyestuff chemistry " (thin Tian Fengzhu, skill report hall, nineteen fifty-seven) synthesizes, but do not limits Due to the method.

Specifically, have following method: (i) by have sulfo group compound build triarylmethane skeleton method, (ii) method importing sulfo group after building triarylmethane skeleton.

In the case of (i), there is following method: utilize usual way, by the phenyl ring or the naphthalene that form triarylmethane skeleton Take in the substituent group that on ring, the direct substitution raw material having sulfo group or phenyl ring or naphthalene nucleus at formation triarylmethane skeleton are had , there is the raw material of sulfo group in generation to build triarylmethane skeleton.

(ii), in the case of, have a following method: utilize usual way to build triarylmethane skeleton, use sulphuric acid, Chlorosulfonic acid, oleum etc. carry out sulfonation, thus the method importing sulfo group；And will there is the chemical combination of triarylmethane skeleton Thing reacts with sodium hydroxymethane sulfonate, PS, Isosorbide-5-Nitrae-butane sultone etc., thus imports the substituent group with sulfo group Method.

Purposes ＞ of ＜ compound (I)

The purposes of the compound (I) of the present invention is not particularly limited, and may be used for various uses.Wherein, from obtained The brightness of pixel and voltage retention are high and from the standpoint of the thermostability height of compound (I), the compound (I) of the present invention is excellent It is selected to light filter.

That is, the compound (I) of the present invention uses preferably as light filter dyestuff.

Hereinafter, for the colored resin composition as the inclusion compound (I) in the case of light filter dyestuff Illustrate.

＜ colored resin composition ＞

The colored resin composition of the present invention contains (A) dyestuff, (B) solvent and (C) adhesive resin, wherein, (A) dyestuff Containing compound (1), the colored resin composition of the present invention contains (D) polymerizable monomer the most further, (E) photopolymerization is drawn Send out composition and thermal polymerization causes at least one in composition, as required possibly together with other composition.

First, (A) dyestuff is described in detail.

[about (A) dyestuff]

For the colored resin composition of the present invention, (A) dyestuff inclusion compound (I), but as long as not damaging this Bright effect, it is also possible to containing other dyestuff beyond compound (I).

As other dyestuff, it may be preferred to enumerate such as: azo dyes, anthraquinone dyes, phthalocyanines dye, quinone are sub- Amine dyestuff, quinolines dyestuff, nitro class dyestuff, carbonyl class dyestuff, methine class dyestuff, cyanine class dyestuff, triarylmethane class Dyestuff, methine two pyroles dyestuff, ton class dyestuff etc..

As azo dyes, can enumerate such as: 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. be the reddest 28, C.I. is the reddest 83, C.I. directly yellow 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. active red 17, C.I. active red 120, C.I. activity Black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 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. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. disperse blue 56, C.I. disperse blue 60 etc..

Additionally, as phthalocyanines dye, can enumerate such as: C.I. sun blue 86, C.I. sun blue 199, C.I. reduce Indigo plant 5, Japanese Unexamined Patent Publication 2002-14222 publication, Japanese Unexamined Patent Publication 2005-134759 publication, Japanese Unexamined Patent Publication 2010-191358 Phthalocyanines dye etc. described in publication, Japanese Unexamined Patent Publication 2011-148950 publication；As quinone imides dyestuff, can enumerate Such as: C.I. alkali blue 3, C.I. alkali blue 9 etc., as quinolines 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. Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42 etc..

It addition, as triarylmethane class dyestuff, can enumerate such as: C.I. acid blue 86, C.I. acid blue 88, C.I. Triarylmethane described in Blue VRS 08, International Publication No. 2009/107734th number, International Publication the 2011/162217th etc. Class dyestuff.

Additionally, as flower cyanine type dye, the colored cyanines class such as described in International Publication the 2011/162217th can be enumerated Dyestuff, preferred mode is the most identical.

As methine two pyroles dyestuff, can enumerate such as: Japanese Unexamined Patent Publication 2008-292970 publication, Japan spy Open 2010-84009 publication, Japanese Unexamined Patent Publication 2010-84141 publication, Japanese Unexamined Patent Publication 2010-85454 publication, Japanese Unexamined Patent Publication 2011-158654 publication, Japanese Unexamined Patent Publication 2012-158739 publication, Japanese Unexamined Patent Publication 2012-224852 publication, Japan spy Open note in 2012-224849 publication, Japanese Unexamined Patent Publication 2012-224847 publication, Japanese Unexamined Patent Publication 2012-224846 publication etc. The methine two pyroles dyestuff carried.

As ton class dyestuff, can enumerate such as: C.I. Xylene Red 50, C.I. Xylene Red 52, C.I. Xylene Red 289, No. 3387541 publication of Japan's patent, Japanese Unexamined Patent Publication 2010-32999 publication, No. 4492760 publication of Japan's patent, Described in " synthetic dyestuffs summary (synthetic dyestuffs) " (hole mouth is rich to be write, three publish altogether, nineteen sixty-eight) page 326～page 348 Ton class dyestuff.

Particularly when forming blue pixel, preferably ton class dyestuff, triarylmethane class dyestuff, anthraquinone dyes, idol Nitrogen class dyestuff, methine two pyroles dyestuff, flower cyanine type dye, phthalocyanines dye.

In the colored resin composition of the present invention, as (A) dyestuff, a kind of compound (I) can be contained only, it is also possible to Containing two or more.

Further, it is also possible to containing other dyestuff one kind or two or more beyond compound (I).

(content)

For all (A) dyestuff content in the colored resin composition of the present invention, in total solid composition, excellent Elect below more than 0.01 weight %, or preferably 50 weight % as.

It addition, for the compound (I) content in colored resin composition, in total solid composition, usually More than 0.01 weight %, it is preferably more than 0.1 weight %, more than more preferably 1 weight %, and usually below 50 weight %, It is preferably below below 40 weight %, more preferably 30 weight %.

Below the above-mentioned upper limit, then the curable of film is difficult to reduce, and film-strength is abundant, the most preferably.It addition, such as Fruit is more than above-mentioned lower limit, then tinting strength, tinting power is abundant, is therefore readily available the colourity of desired concentration, and thickness is difficult to thickening, therefore Preferably.

It should be noted that in the colored resin composition of the present invention, the content of compound (I) is at all (A) dyestuffs Solid constituent in be preferably more than 30 weight %.

[(B) solvent]

(B) solvent contained in the colored resin composition of the present invention has makes each one-tenth contained in colored resin composition Divide and dissolve or dispersion, the function of regulation viscosity.

As (B) solvent, as long as each composition of composition colored resin composition can be made to dissolve or scattered solvent i.e. Can, preferably select the boiling point solvent 100～200 DEG C of scopes.More preferably there is the solvent of 120～170 DEG C of boiling points.

As such solvent, such as following solvents can be enumerated.

Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the third two The tertiary butyl ether of alcohol list, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxy amylalcohol, dihydroxypropane single-ether, dipropylene glycol Single ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, Tripropylene glycol monomethyl Ether such glycol monoalkyl ethers；

Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, dibutyl ethylene glycol ether such glycol dialkyl ether class；

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate, dihydroxypropane single-ether Acetas, propylene glycol monopropyl ether acetas, methoxy butyl acetate, acetic acid 3-methoxybutyl, acetic acid methoxyl group pentyl ester, diethyl 2-ethoxyethanol acetas, butyl carbitol acetate, dipropylene glycol monomethyl ether acetas, acetic acid 3-methyl-3-methoxy Base butyl ester such glycol alkyl ether acetate esters；

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

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

Ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol are such 1 yuan or polyalcohols；

The such aliphatic of pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene, dodecane Hydro carbons；

The such alicyclic hydro carbons of hexamethylene, hexahydrotoluene, methylcyclohexene, bicyclohexyl；

Benzene,toluene,xylene, isopropylbenzene are such aromatic hydrocarbon；

Amyl formate, Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, cyclohexyl acetate, isobutyl Acid methyl ester, Ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, octanoic acid second Ester, butyl stearate, ethyl benzoate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, gamma-butyrolacton such chain or ring-type Esters；

3-methoxypropionic acid, 3-ethoxy-propionic acid such alkoxyl carboxylic acids；

The such halogenated hydrocarbon of chloro-butane, chloro-pentane；

Methoxy pentanone such ether ketone；

The such nitrile of acetonitrile, benzonitrile.

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

In above-mentioned solvent, from the standpoint of the dissolubility of (A) dyestuff of the present invention, preferred diol monoalkyl ethers.Wherein, Particularly from the standpoint of the dissolubility of the various constituents from colored resin composition, particularly preferred propylene glycol monomethyl ether.

Additionally, such as comprise (F) described later pigment as any composition in the case of, owing to being used in mixed way further Glycol alkyl ether acetate esters is as obtaining the well balanced of coating, surface tension etc. and pigmentary resin combination during solvent The dissolubility of the constituent in thing is higher, is therefore more highly preferred to.It should be noted that combine at the pigmentary resin comprising pigment In thing, owing to the polarity of glycol monoalkyl ethers is high, there is the tendency making pigment agglomeration, thus be likely to occur pigmentary resin combination The viscosity rising etc. of thing makes the situation that storage stability reduces.It is therefore preferable that the usage amount of glycol monoalkyl ethers is not too much, (B) ratio of the glycol monoalkyl ethers in solvent is preferably 5～50 weight %, more preferably 5～30 weight %.

In addition, it is contemplated that for the adaptability of recently corresponding with large substrate etc. slot coated (slit coat) mode, Further preferably it is applied in combination the solvent that boiling point is more than 150 DEG C.Now, relative to (B) solvent total amount, containing of above-mentioned high boiling solvent Amount is preferably 3～50 weight %, more preferably 5～40 weight %, especially preferably 5～30 weight %.If high boiling solvent Amount very few, then it may happen that such as the precipitation of dye component etc., solidification occur at slit spray nozzle front end, and then cause foreign body Defect；It addition, if the amount of high boiling solvent is too much, then the rate of drying that can cause compositions is slack-off, and then may cause Drying under reduced pressure technique in light filter manufacturing process described later occurring, rhythm of production (tact) is bad, prebake (pre-bake) The problem such as pin-and-hole vestige.

It should be noted that the solvent that boiling point is more than 150 DEG C can be glycol alkyl ether acetate esters, can also be two Alcohol alkyl ether, now, it is also possible to make it the most additionally contain solvent that boiling point is more than 150 DEG C.

The colored resin composition of the present invention can be supplied to use the light filter manufacture of ink-jet method, is using ink-jet method During light filter manufactures, nozzle the ink sprayed is the most small, for several pL～tens pL, therefore, be sprayed onto jet hole periphery or Before in pixel basin, solvent evaporates, and ink has concentration, solid trend.In order to avoid this situation, the boiling point of preferred solvent is relatively Height, specifically, (B) solvent preferably comprises the solvent of boiling point more than 180 DEG C.Particularly preferably containing boiling point be more than 200 DEG C, especially It is boiling point be the solvent of more than 220 DEG C.Additionally, it is preferred that the high boiling solvent of boiling point more than 180 DEG C is 50 weights in (B) solvent Amount more than %.The ratio of such high boiling solvent is less than in the case of 50 weight %, it is possible to can not give full play to prevent molten The effect that agent is evaporated from droplet of ink.

In the colored resin composition of the present invention, the content of (B) solvent is not particularly limited, and its upper limit is typically set to 99 Weight %.When the content of (B) solvent in compositions is more than 99 weight %, the concentration of each composition in addition to (B) solvent becomes Obtain too small, be sometimes difficult to form coated film.On the other hand, it is contemplated that be suitable to the viscosity etc. of coating, under the content of (B) solvent Limit value is usually 75 weight %, is preferably 80 weight %, more preferably 82 weight %.

[(C) adhesive resin]

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

In the case of the colored resin composition of the present invention is optical polymerism resin combination, as (C) adhesive resin, Such as Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-can be used No. 300922 publications, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publications Macromolecular compound described in each publications such as 2000-56118 publication, Japanese Unexamined Patent Publication 2003-233179 publication etc., its In, preferably enumerate following (C-1)～the resin etc. of (C-5).

(C-1): for the copolymer of (methyl) acrylate containing epoxy radicals Yu other free radical polymerization monomer, make At least some of and the unsaturation monoacid addition of the epoxy radicals that this copolymer is had and the resin that obtains or make to be added by this Become reaction and at least some of and multi-anhydride addition of the hydroxyl that generates and obtain alkali soluble resin (following, be sometimes referred to as For " resin (C-1) ")

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

(C-3): addition contains epoxy radicals on the carboxy moiety of above-mentioned resin (C-2) unsaturated compound and obtain Resin (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): there is the Epocryl (following, be sometimes referred to as " resin (C-5)) of carboxyl

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

It should be noted that resin (C-2)～(C-5) are as long as can be dissolved by alkaline-based developer and have and can make mesh Target development treatment is accomplished the deliquescent resin of degree, its respectively with Japanese Unexamined Patent Publication 2009-025813 publication The middle resin-phase as identical items record is same.Preferred implementation is the most identical.

(C-1): for the copolymer of (methyl) acrylate containing epoxy radicals Yu other free radical polymerization monomer, make At least some of and the unsaturation monoacid addition of the epoxy radicals that this copolymer is had and the resin that obtains or make to be added by this Become reaction and at least some of and multi-anhydride addition of the hydroxyl that generates and the alkali soluble resin that obtains

One of particularly preferred resin as resin (C-1), can enumerate: for by 5～90 moles of % containing epoxy The copolymer that other free radical polymerization monomer of (methyl) acrylate of base and 10～95 moles of % is formed, makes this copolymer 10～100 moles of % of the epoxy radicals being had and unsaturated monoacid addition and the resin that obtains or make by this addition anti- Should and 10～100 moles of % of hydroxyl of generating and multi-anhydride addition and the alkali soluble resin that obtains.

As described (methyl) acrylate containing epoxy radicals, can enumerate such as: (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid (3,4-epoxycyclohexyl) methyl ester, (methyl) acrylic acid 4-hydroxyl Base butyl ester glycidyl ether etc..Wherein, preferably (methyl) glycidyl acrylate.Above-mentioned (methyl) propylene containing epoxy radicals Acid esters can be used alone a kind, it is also possible to two or more is applied in combination.

As carrying out other free radical polymerization monomer of copolymerization with above-mentioned (methyl) acrylate containing epoxy radicals, Do not damage and there is no particular determination in the range of effect of the present invention, can enumerate such as: the vinyl aromatic same clan, dienes, (methyl) Esters of acrylic acid, (methyl) acrylic amide, vinyl compound class, unsaturated dicarboxylic two esters, single maleimide Deng, particularly preferably there is list (methyl) acrylate of structure shown in following formula (7).

In the repetitive from " other free radical polymerization monomer ", from having structure shown in following formula (7) Preferably 5～90 moles % of content ratio of the repetitive of single (methyl) acrylate, more preferably 10～70 rub You are %, particularly preferably 15～50 moles of %.

[chemical formula 10]

In above-mentioned formula (7), R⁸⁹Represent hydrogen atom or methyl, R⁹⁰Represent the structure shown in following formula (8).

[chemical formula 11]

In above-mentioned formula (8), R⁹¹～R⁹⁸Represent hydrogen atom or the alkyl of carbon number 1～3 independently of one another.Need explanation , R⁹⁶And R⁹⁸Optionally mutually link and form ring.

R⁹⁶And R⁹⁸The ring linked and formed is preferably aliphatic ring, can be any one in saturated rings or unsaturated ring Situation, additionally, carbon number is preferably 5～6.

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

[chemical formula 12]

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

As " other radical polymerization in addition to list (methyl) acrylate with structure shown in above-mentioned formula (8) Property monomer ", from the standpoint of the excellent thermostability that can improve colored resin composition and intensity, can enumerate: styrene, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobomyl acrylate Ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, N-phenyl maleoyl Imines, N-N-cyclohexylmaleimide.

Content from least one repetitive in above-mentioned monomer group is preferably 1～70 mole of %, more preferably 3～50 moles of %.

It should be noted that for above-mentioned (methyl) acrylate containing epoxy radicals with above-mentioned other is free-radical polymerised The copolyreaction of monomer, can use known solution polymerization process.

In the present invention, as above-mentioned (methyl) acrylate containing epoxy radicals and other free-radical polymerised list above-mentioned The copolymer that body is formed, preferably by from repetitive 5～90 moles of % of (methyl) acrylate containing epoxy radicals with come The copolymer formed from the repetitive 10 of other free radical polymerization monomer～95 moles of %, more preferably 20～80 is rubbed by the former The copolymer that your % and the latter 80～20 moles of % are formed, is particularly preferably rubbed by the former 30～70 moles of % and the latter 70～30 The copolymer that you % is formed.

Time within the above range, the addition amount of aftermentioned polymerizable component and alkali-soluble composition is abundant, and thermostability, film Intensity abundant, therefore preferably.

Make the epoxy radicals part of the copolymer containing epoxy radicals of above-mentioned synthesis and unsaturated monoacid (polymerizable component) And multi-anhydride (alkali-soluble composition) reaction.

Here, as the unsaturated monoacid with epoxy radicals addition, known compound can be used, such as, tool can be enumerated There is the unsaturated carboxylic acid of ethylenical unsaturated double bonds.

As concrete example, can enumerate: (methyl) acrylic acid .beta.-methylacrylic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, To vinyl benzoic acid, (methyl) acrylic acid etc. that alpha-position is replaced by haloalkyl, alkoxyl, halogen atom, nitro or cyano group etc. Monocarboxylic acid etc..Wherein, preferably (methyl) acrylic acid.These unsaturated carboxylic acids can be used alone a kind, it is also possible to by two or more group Close and use.

By addition mentioned component, can be that the adhesive resin used in the present invention gives polymerism.

Generally, these unsaturated monoacid of addition on 10～100 moles of % of the epoxy radicals being had at above-mentioned copolymer, Preferably addition 30～100 moles of %, more preferably addition 50～100 moles of %.Time within the above range, colored resin composition Ageing stability is excellent, therefore preferably.Wherein, as the unsaturated monacid method of addition in the epoxy radicals of copolymer, can adopt Use known method.

Additionally, as the polyprotic acid with the hydroxyl addition produced during addition unsaturation monoacid in the epoxy radicals of copolymer Acid anhydride, can use known multi-anhydride.

Such as, can enumerate maleic anhydride, succinic anhydrides, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, The dibasic acid anhydrides such as hexahydrophthalic anhydride, chlorendic acid acid anhydride；Trimellitic anhydride, pyromellitic acid dianhydride, hexichol first The anhydride of the acid more than ternarys such as ketone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Wherein, preferably succinic anhydrides and tetrahydrophthalic acid Acid anhydride.These multi-anhydrides can be used alone a kind, it is also possible to two or more is applied in combination.

By addition mentioned component, can be that the adhesive resin used in the present invention gives alkali-soluble.

Generally, the hydroxyl making addition unsaturation monoacid in the epoxy radicals that above-mentioned copolymer is had and generate 10～ 100 moles of % and above-mentioned multi-anhydride addition, preferably make 20～90 moles of % additions, more preferably make 30～80 moles of % additions.

Time within the above range, residual film ratio and dissolubility during development are abundant, therefore preferably.

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

Additionally, in order to make light sensitivity improve, it is also possible to after the above-mentioned multi-anhydride of addition, make of carboxyl of generation Point with (methyl) glycidyl acrylate or the glycidyl etherified compound addition with polymerism unsaturated group.Relevant This resinoid structure, is documented in such as Japanese Unexamined Patent Publication 8-297366 publication, Japanese Unexamined Patent Publication 2001-89533 publication.

Utilize the weight being converted into polystyrene of the above-mentioned adhesive resin (C-1) that GPC (gel permeation chromatography) measures Average molecular weight (Mw) is preferably 3000～100000, particularly preferably 5000～50000.If in above-mentioned scope, the most heat-resisting Property, film-strength and the favorable solubility in developer solution, from this point on from the point of view of be preferred.

It addition, as the substantially 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 usually 10～200mg-KOH/g, be preferably 15～ 150mg-KOH/g, more preferably 25～100mg-KOH/g.If acid number is too low, then may cause in developer solution is molten Solution reduces.On the contrary, if acid number is too high, then it some times happens that film ftractures.

For (C) adhesive resin content in colored resin composition, in total solid composition, usually 0.1～80 weight %, preferably 1～60 weight %.

It is if in above-mentioned scope, then good to the adaptation of substrate, it addition, the impregnability of exposure portion is closed by developer solution Suitable, the surface smoothness of pixel and sensitivity are good, in terms of these from the point of view of be preferred.

[(D) polymerizable monomer]

The colored resin composition of the present invention preferably comprises (D) polymerizable monomer.

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

Olefinic compounds is when the colored resin composition of the present invention is irradiated by active ray, can gather at aftermentioned light The compound with olefinic double bond closing generation addition polymerization under the effect of initiation composition and solidify.It should be noted that this (D) polymerizable monomer in bright is the concept relative with so-called polymer substance, in addition to the monomer of narrow sense, also comprises two Aggressiveness, trimer, oligomer.

As the olefinic compounds in (D) polymerizable monomer, can enumerate such as: the unsaturated carboxylic acids such as (methyl) acrylic acid； The ester that monohydroxy compound is formed with unsaturated carboxylic acid；The ester that aliphatic polyhydroxy compound is formed with unsaturated carboxylic acid；Fragrance The ester that race's polyol is formed with unsaturated carboxylic acid；Unsaturated carboxylic acid and polybasic carboxylic acid and above-mentioned aliphatic polyhydroxylated The ester that the multi-hydroxy compound such as compound, aromatic polyhydroxy compounds is obtained by esterification；It is esterified by polyisocyanic acid Compound reacts, with the hydroxy compounds containing (methyl) acryloyl group, the olefinic compounds with carbamate skeleton obtained； Etc..

The ester formed with unsaturated carboxylic acid as aliphatic polyhydroxy compound, can enumerate: ethylene glycol bisthioglycolate (methyl) propylene Acid esters, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (first Base) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (first Base) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol (methyl) acrylate such as six (methyl) acrylate, glycerol (methyl) acrylate.It addition, by these (methyl) acrylic acid (methyl) acrylate moiety of ester replaces with the itaconate of itaconic acid moieties, by (the first of these (methyl) acrylate Base) acrylate moiety replaces with the crotonates of .beta.-methylacrylic acid part or by (methyl) of these (methyl) acrylate Acrylate moiety replaces with the maleate etc. of maleic acid moieties.

The ester formed with unsaturated carboxylic acid as aromatic polyhydroxy compounds, can enumerate: hydroquinone two (methyl) third Olefin(e) acid ester, resorcinol two (methyl) acrylate, 1,2,3,-thrihydroxy-benzene three (methyl) acrylate etc..

The ester obtained by esterification with polybasic carboxylic acid and multi-hydroxy compound as unsaturated carboxylic acid, Ke Yiwei Single thing, it is also possible to for mixture.As representative examples, can enumerate: (methyl) acrylic acid, phthalic acid and the condensation of ethylene glycol Thing；(methyl) acrylic acid, maleic acid and the condensation substance of diethylene glycol；(methyl) acrylic acid, p-phthalic acid and tetramethylolmethane Condensation substance；(methyl) acrylic acid, adipic acid, butanediol and the condensation substance etc. of glycerol.

As having of being obtained by polyisocyanate compound and reacting containing the hydroxy compounds of (methyl) acryloyl group The olefinic compounds of carbamate skeleton, can enumerate: hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate Deng aliphatic diisocyanate；The alicyclic diisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate；Toluene The aromatic diisocyanate such as diisocyanate, methyl diphenylene diisocyanate and (methyl) acrylic acid 2-hydroxy methacrylate, 3- The reaction of the hydroxy compounds containing (methyl) acryloyl group such as hydroxyl [1,1,1-tri-(methyl) acryloyloxymethyl] propane Product.

Additionally, as the example of the olefinic compounds used in the present invention, can enumerate: ethylenebis (methyl) acrylamide Deng (methyl) acrylic amide；The pi-allyl esters such as diallyl phthalate；Phthalic acid divinyl ester etc. contains The compound etc. of vinyl.

In above-mentioned, the ester that preferred aliphat polyol is formed with unsaturated carboxylic acid, more preferably tetramethylolmethane or two (methyl) acrylate of tetramethylolmethane, particularly preferred dipentaerythritol six (methyl) acrylate.

It addition, olefinic compounds can also is that the monomer with acid number.As having the monomer of acid number, for example, aliphatic The ester that polyol is formed with unsaturated carboxylic acid, preferably makes the unreacted hydroxyl of aliphatic polyhydroxy compound with non-aromatic The polyfunctional monomer with acidic group that fragrant race carboxylic acid anhydrides reacts and obtains, the particularly preferably aliphatic polyhydroxylated conjunction in this ester Thing is at least one in tetramethylolmethane and dipentaerythritol.

Above-mentioned monomer can be used alone a kind, but owing to being difficult to obtain single compound for manufacture view, the most also Mixture of more than two kinds can be used.

Further, it is also possible to will not there is the polyfunctional monomer of acidic group and there is the polyfunctional monomer group of acidic group as desired Close and use, be used as (D) polymerizable monomer.

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

If in above-mentioned scope, then development dissolution characteristics is difficult to reduce, and manufactures and processing ease.Additionally, light gathers The curable such as conjunction performance is difficult to decline, the surface smoothness of pixel are good, the most preferably.

In the present invention, preferred there is acidic group polyfunctional monomer be such as with dipentaerythritol acrylate, Dipentaerythritol Pentaacrylate, the mixture that succinate is main constituent of Dipentaerythritol Pentaacrylate.Can also be by This polyfunctional monomer is applied in combination with other polyfunctional monomer.

In the colored resin composition of the present invention, the content of above-mentioned (D) polymerizable monomer is as follows: in total solid composition Usually more than 1 weight %, it is preferably more than more than 5 weight %, more preferably 10 weight %, and usually 80 weight % Below, below below below 70 weight %, more preferably 50 weight %, particularly preferably 40 weight % it are preferably.

It addition, for (D) polymerizable monomer for the ratio of above-mentioned (A) dyestuff, with mass ratio range, usually 1 More than weight %, it is preferably more than more than more than 5 weight %, more preferably 10 weight %, particularly preferably 20 weight %, and Usually below 200 weight %, it is preferably below below 100 weight %, more preferably 80 weight %.

Time within the above range, photocuring appropriateness, be difficult to development time cause closely sealed bad, and, the cross section after development It is difficult to become inverted conical shape, and the peeling being not susceptible to be caused by decreased solubility, molding are bad etc., therefore preferably.

[(E) photopolymerization causes composition, thermal polymerization to cause composition]

In order to reach to make the purpose of curing of coating, the colored resin composition of the present invention preferably comprises (E) photopolymerization to be caused Composition and thermal polymerization cause at least one in composition.Wherein, the method for solidification can also be not use the side of these initiators Method.

Particularly, for the colored resin composition of the present invention comprises the tree with olefinic double bond as (C) composition The situation of fat, comprise the situation of olefinic compounds as (D) composition for, preferably comprise that have can directly absorbing light or generation Photosensitization and cause decomposition reaction or dehydrogenation reaction thus produce the function of polymerization activity free radical photopolymerization cause composition and The thermal polymerization producing polymerization activity free radical under heat effect causes at least one in composition.It should be noted that at this In bright, (E) composition of composition is caused to refer to as photopolymerization: group in Photoepolymerizationinitiater initiater (following the most referred to as (E1) composition) It is additional that conjunction employs polymerization accelerator (following the most referred to as (E2) composition), enhanced sensitivity pigment (being the most arbitrarily referred to as (E3) composition) etc. The mixture of agent.

[(E) photopolymerization causes composition]

(E) photopolymerization in the present invention causes composition generally with (E1) Photoepolymerizationinitiater initiater and be added as needed on (E2) mixture of the additives such as polymerization accelerator and (E3) enhanced sensitivity pigment form use, have can directly absorbing light or Third contact of a total solar or lunar eclipse sensitization and cause decomposition reaction or dehydrogenation reaction thus produce the composition of the function of polymerization activity free radical.

Cause (E1) Photoepolymerizationinitiater initiater of composition as composition photopolymerization, can enumerate such as: Japanese Laid-Open Patent Publication 59- Titanocenes derivatives class described in No. 152396 publications, Japanese Laid-Open Patent Publication 61-151197 publications etc.；Japanese Unexamined Patent Publication 10- Six virtues described in No. 300922 publications, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 2000-56118 publications etc. Base diimidazole derivatives class；Halomethylation described in Japanese Unexamined Patent Publication 10-39503 publication etc.Oxadiazole derivative class, halogen N-aryl-alpha-amido the acids such as methyl Striazine derivative class, N-phenylglycine, N-aryl-a-amino acid salt, N-virtue Free radical activity agent, the alpha-aminoalkyl benzophenone derivatives classes such as base-a-amino acid esters；Japanese Unexamined Patent Publication 2000-80068 publication Oxime ester system derivatives class described in Deng etc..

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

In these Photoepolymerizationinitiater initiaters, more preferably alpha-aminoalkyl benzophenone derivatives class, oxime ester system derivatives class, di- Imidazole derivatives species, acetophenone derivs class and thioxanthone species.

It addition, as oxime ester system derivatives class, can enumerate: 1-[4-(thiophenyl) phenyl]-1,2-octanedione 2-(O-benzene Carbamoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ketenes-1-(O-acetyl group oxime) and The compound etc. that following formula (XI) represents.

[chemical formula 13]

(in formula (XI), R¹⁰¹Represent that hydrogen atom, the alkyl of carbon number 1～20, the thiazolinyl of carbon number 2～25, carbon are former The heteroaryl of subnumber 3～20 or the heteroaryl alkyl of carbon number 4～25, these groups the most optionally have substituent group.Or, R¹⁰¹Can also be bonded with X or Z and form ring.

R¹⁰²Represent the alkanoyl of carbon number 2～20, the enoyl-of carbon number 3～25, the cycloalkanes of carbon number 4～8 Acyl group, the aroyl of carbon number 7～20, the alkoxy carbonyl group of carbon number 2～10, the aryloxy carbonyl of carbon number 7～20, carbon The heteroaryl of atomic number 2～20, the 4-hetaroylpyrazol of carbon number 3～20 or the alkyl amino-carbonyl of carbon number 2～20, these Group the most optionally has substituent group.

X represents that the divalent aromatic cyclic hydrocarbon group by the cyclic condensation of more than 2 optionally with substituent group is rolled into a ball and aromatic series At least one in heterocyclic group.

Z represents the aromatic ring group optionally with substituent group.)

It should be noted that in the compound that represents of above-mentioned formula (XI), preferably X is the carbazole ring optionally with substituent group Compound, specifically can enumerate the compound etc. that following formula (XII) represents, wherein, the change that particularly preferred following formula (XIII) represents Compound.

[chemical formula 14]

(in formula, R¹⁰¹、R¹⁰²And the definition synonym in Z and above-mentioned formula (XI).R¹⁰³～R¹⁰⁹Represent hydrogen atom independently of one another Or arbitrary substituent group.)

[chemical formula 15]

(in formula, R^101aThe group that the alkyl of expression carbon number 1～3 or following formula (XIIIa) represent.

[chemical formula 16]

(in formula, R¹⁰³And R¹⁰⁴Represent hydrogen atom, phenyl or N-acetyl group-N-acetoxyl group amino independently of one another.

* bonding position is represented.)

R^102aRepresent the alkanoyl of carbon number 2～4, X^aRepresent the 3,6-click that nitrogen-atoms is optionally replaced by the alkyl of 1～4 Oxazolyl.Z^aRepresent the phenyl optionally replaced by alkyl or the naphthyl optionally replaced by morpholinyl.)

As oximes initiator, it is possible to use commercially available product.As the example of commercially available product, OXE-01, OXE-02 can be enumerated (BASF AG's manufacture), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305 (Changzhou strength electricity Sub-new material company limited (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) manufactures).

As Photoepolymerizationinitiater initiater, additionally can enumerate: benzoin alkyl ethers, anthraquinone-derivative species；2-methyl-(4 '- Methyl mercapto phenyl) thiophenes such as acetophenone derivs class, 2-ethyl thiaxanthone, 2,4-diethyl thioxanthone such as-2-morpholinyl-1-acetone Ton ketone derivatives class, benzoate derivatives class, acridine derivatives class, phenazene derivative class, anthracyclinone derivatives class etc..These draw Send out agent and can also use 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 to manufacture) etc..

In above-mentioned Photoepolymerizationinitiater initiater, more preferably alpha-aminoalkyl benzophenone derivatives class, thioxanthone species, oxime ester system Derivatives class.Particularly preferably oxime ester system derivatives class.

As (E2) polymerization accelerator used as desired, can enumerate such as: N, N-dimethylaminobenzoic acid second The N such as ester, N-dialkyl amido benzoic acid alkyl esters；2-mercaptobenzothiazole, 2-sulfydryl benzoAzoles, 2-mercaptobenzimidazole Etc. the sulfhydryl compound with heterocycle；The sulfhydryl compound classes etc. such as the multifunctional sulfhydryl compound of aliphatic.

Above-mentioned (E1) Photoepolymerizationinitiater initiater and (E2) polymerization accelerator can individually use a kind, it is also possible to by two or more It is applied in combination.

Additionally, in order to improve induction sensitivity, (E3) enhanced sensitivity pigment can be used as desired.As enhanced sensitivity pigment, can Wavelength according to image exposure light source and use suitable enhanced sensitivity pigment, can enumerate such as: Japanese Unexamined Patent Publication 4-221958 public affairs Ton class pigment described in report, Japanese Unexamined Patent Publication 4-219756 publication etc.；Japanese Unexamined Patent Publication 3-239703 publication, Japan The Coumarins pigment with heterocycle described in Unexamined Patent 5-289335 publication etc.；Japanese Unexamined Patent Publication 3-239703 public affairs 3-ketocoumarin pigment described in report, Japanese Unexamined Patent Publication 5-289335 publication etc.；Japanese Unexamined Patent Publication 6-19240 public affairs Methylene pyrrole class pigment described in report etc.；Japanese Laid-Open Patent Publication 47-2528 publication, Japanese Laid-Open Patent Publication 54-155292 public affairs Report, Japanese Patent Publication 45-37377 publication, Japanese Laid-Open Patent Publication 48-84183 publication, Japanese Laid-Open Patent Publication 52-112681 public affairs Report, Japanese Laid-Open Patent Publication 58-15503 publication, Japanese Laid-Open Patent Publication 60-88005 publication, Japanese Laid-Open Patent Publication 59-56403 public affairs Report, Japanese Unexamined Patent Publication 2-69 publication, Japanese Laid-Open Patent Publication 57-168088 publication, Japanese Unexamined Patent Publication 5-107761 publication, day Described in this Unexamined Patent 5-210240 publication, Japanese Unexamined Patent Publication 4-288818 publication etc., there is dialkyl amido benzene skeleton Pigment etc..

(E3) enhanced sensitivity pigment can also be used alone a kind, it is also possible to two or more is applied in combination.

In the colored resin composition of the present invention, for the content that above-mentioned (E) photopolymerization causes composition, total solid Body composition is usually more than 0.1 weight %, is preferably more than more than 0.2 weight %, more preferably 0.5 weight %, and lead to It is often below 40 weight %, is preferably below 30 weight %, is more preferably the scope of below 20 weight %.

Time within the above range, the sensitivity to exposure light is good, and the dissolving that unexposed portion is in developer solution Property good, be not susceptible to poor visualization etc., therefore preferably.

[(E) thermal polymerization causes composition]

Cause the concrete example of composition as (E) thermal polymerization contained by the colored resin composition of the present invention, can enumerate Azo compound, organic peroxide and hydrogen peroxide etc..In the middle of these, azo compound is preferably used.More specifically and Speech, it is possible to use the such as International Publication the 2009/107734th thermal polymerization described in grade causes composition.

Above-mentioned thermal polymerization causes composition to can be used alone a kind, it is also possible to two or more be applied in combination.

[other any composition]

In addition to above-mentioned each composition, the colored resin composition of the present invention can also contain: surfactant, organic In carboxylic acid and organic carboxyl acid acid anhydride at least one, heat-curable compounds, plasticizer, thermal polymerization preventing agent, preserving stabilizer, surface Protective agent, closely sealed raising agent, development modifying agent etc..As above-mentioned any composition, it is possible to use such as Japanese Unexamined Patent Publication 2007- The various compounds that No. 113000 publications are recorded.It addition, in the case of containing (F) described later pigment, it is also possible to containing dispersion Agent, dispersing aid.

[(F) pigment]

In order to improve the thermostability etc. of obtained light filter, the colored resin composition of the present invention can also not damage Containing (F) pigment in the range of effect of the present invention.

As (F) pigment, such as in the case of forming the pixel etc. of light filter, it is possible to use blueness, purple etc. are various The pigment of color.It addition, as its chemical constitution, can enumerate such as phthalocyanines, quinacridine ketone, benzimidazole ketone, twoThe organic pigments such as piperazine class, indanthrone kinds, perylene kinds.Further, it is also possible to use various inorganic pigments etc..Hereinafter, use Pigment call number illustrates the ability to the concrete example of the pigment used.

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

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 case of the colored resin composition of the present invention contains blue pigment, preferably with respect to blue pigment Total content, C.I. pigment blue 15: 6 be more than more than 80 weight %, particularly preferably 90 weight %, especially preferably 95～100 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, preferably the two of purplePiperazine pigment, as this twoPiperazine pigment, preferably enumerates C.I. pigment violet 19,23 etc., more preferably C.I. pigment Violet 23.

Therefore, in the case of the colored resin composition of the present invention contains violet pigment, always containing relative to violet pigment Amount, preferably C.I. pigment Violet 23 is more than more than 80 weight %, particularly preferably 90 weight %, especially preferably 95～100 weights Amount %.

They can be used alone a kind, it is also possible in any combination and ratio mix two or more use.

From the standpoint of the pixel that can form high-contrast, (F) face used in the colored resin composition of the present invention Expecting the little person of preferred average primary particle diameter, specifically, preferably average primary particle diameter is below 40nm, more preferably below 35nm.

Particularly, for blue copper phthalocyanine, also, it is preferred that average primary particle diameter is below 40nm, more preferably For below 35nm, more preferably 20～30nm.

It addition, for twoFor piperazine pigment, average primary particle diameter is preferably below 40nm, more preferably 25～35nm. Being difficult to colored resin composition from the standpoint of cohesion from pigment, preferably average primary particle diameter is not wanted the least.

It should be noted that here, the average primary particle diameter of (F) pigment is the value measuring as follows, calculating.

First, (F) pigment is carried out ultrasound wave dispersion in chloroform, be added drop-wise to be fitted with on the screen cloth of collodion membrane, make It is dried, and is observed the primary particle image obtaining pigment by transmission electron microscope (TEM).By this image by each The particle diameter of pigment particles is converted into equal area diameter of a circle, as area equivalent circular diameter, and to multiple (usually 200～ About 300) pigment particles obtain particle diameter respectively.

The value using obtained primary particle diameter calculates number meansigma methods according to following calculating formula, obtains average particle Footpath.

The particle diameter of each pigment particles: X₁、X₂、X₃、X₄、····、X_i、······X_m(m is the individual of particle Number)

[mathematical expression 1]

{ use level }

In the present invention, containing in the case of (F) pigment, for the pigment in colored resin composition content and Speech, is usually below 80 weight %, below preferably 50 weight % in total solid composition.

It addition, be usually below 2000 weight portions relative to the content of above-mentioned (A) dyestuff 100 weight portion, preferably 1000 Below weight portion.

By being in above-mentioned scope, due to dyestuff (I), absorbance will not be brought big impact, the pixel obtained Thermostability easily become better, be preferred from this point of view.

[dispersant]

In the case of the colored resin composition of the present invention comprises (F) pigment, preferably further contain dispersant.

As long as the dispersant of the present invention can make pigment disperse and keep stable, to its kind indefinite.

The dispersant of such as cationic, anionic property, nonionic or both sexes etc. can be used, but preferred polymers is divided Powder.Specifically can enumerate: block copolymer, polyurethane, polyester, the alkylammonium salt of high-molecular copolymer or phosphate ester salt, sun from Sub-sex comb shape graft polymers etc..In these dispersants, the grafting of preferred block copolymer, polyurethane, cationic comb shape is poly- Compound.Particularly preferably block copolymer, wherein, preferably by having the A block of said solvophilic and having the sense comprising nitrogen-atoms The block copolymer that the B block of group is formed.

Specifically, as the B block of the functional group with nitrogen atom, side chain can be enumerated there is quaternary ammonium salt base and amino In the cellular construction of at least one group；On the other hand, as the A block of said solvophilic, can enumerate and not there is quaternary ammonium salt base And the cellular construction of amino.

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

It addition, as described B block, in the case of having quaternary ammonium salt base, this quaternary ammonium salt base can led with Direct Bonding On chain, it is also possible to link group by divalent and be bonded on main chain.

As such block copolymer, the copolymerization such as described in Japanese Unexamined Patent Publication 2009-025813 publication can be enumerated Thing.

It addition, the colored resin composition of the present invention can also comprise dispersant other than the above.Disperse as other Agent, can enumerate the dispersant such as described in Japanese Unexamined Patent Publication 2006-343648 publication.

In the case of the colored resin composition of the present invention contains (F) pigment, preferably make used dispersant total solid Content in body composition is 2～1000 weight % of (F) pigment total content, particularly preferably 5～500 weight %, particularly preferably In the range of 10～250 weight %.

Time within the above range, the thermostability of dyestuff (I) will not be impacted, it can be ensured that good pigment dispersion Property, and it is obtained in that better pigment dispersion stability, therefore preferably.

[dispersing aid]

The colored resin composition of the present invention can also contain dispersing aid.Here described dispersing aid can be face Material derivant, as pigment derivative, can use such as Japanese Unexamined Patent Publication 2001-220520 publication, Japanese Unexamined Patent Publication 2001- No. 271004 publications, Japanese Unexamined Patent Publication 2002-179976 publication, Japanese Unexamined Patent Publication 2007-113000 publication and Japanese Unexamined Patent Publication Various compounds etc. described in 2007-186681 publication etc..

It should be noted that relative to the total solid component amount of pigment, the dispersion in the colored resin composition of the present invention The content of auxiliary agent is usually more than 0.1 weight %, it addition, usually below 30 weight %, be preferably below 20 weight %, more excellent Elect below below 10 weight %, more preferably 5 weight % as.By addition being controlled in above-mentioned scope, can play Go out the effect as dispersing aid, and be obtained in that the best dispersibility and dispersion stabilization, therefore preferably.

[dispersion resin]

Can be containing selected from above-mentioned (C) adhesive resin or other adhesive resin in the colored resin composition of the present invention In part or all of resin as following dispersion resin.

Specifically, in [preparation method of colored resin composition] described later, by containing above-mentioned dispersant etc. Containing (C) adhesive resin while composition, can be conducive to by being somebody's turn to do the synergy of (C) adhesive resin and dispersant (F) dispersion stabilization of pigment.It is thereby possible to make the addition of dispersant reduce, therefore preferably.It addition, it is aobvious to also act as raising Shadow, improves the adaptation of pixel and substrate without remaining the effect of undissolved thing in the non-pixel portion of substrate, therefore preferably.

So, also (C) adhesive resin being used for disperseing treatment process is referred to as dispersion resin.Relative to pigmentary resin Pigment total amount in compositions, the consumption of dispersion resin is preferably about 0～200 weight %, more preferably in 10～100 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, it is possible to by will comprising Mix together with (A) dyestuff of compound (I) and (C) adhesive resin and (B) solvent and any composition used as required Prepare.

It addition, as the preparation method comprised in the case of (F) pigment, following method can be enumerated: comprising (F) pigment In solvent, in the presence of dispersant and the dispersing aid that adds as desired, in some cases with (C) adhesive resin A part together, uses such as paint shaker, sand mill, ball mill, roller mill, burrstone mill, airflow milling, homogenizer etc. to carry out Carry out while pulverizing mixing, disperseing, thus prepare dispersible pigment dispersion, in this dispersible pigment dispersion, add inclusion compound (I) (A) dyestuff, (C) adhesive resin, (D) polymerizable monomer, (E) Photoepolymerizationinitiater initiater and thermal polymerization as required In at least one etc., and mix, thus prepare colored resin composition.

[application of colored resin composition]

The colored resin composition of the present invention is generally in the state that repertoire is all dissolved or dispersed in solvent. Such colored resin composition is fed on substrate, forms the structures such as light filter, liquid crystal indicator, organic EL display Become parts.

Hereinafter, as the application examples of the colored resin composition of the present invention, for its as the pixel of light filter application, And employ their liquid crystal indicator (panel) and organic EL display illustrates.

＜ light filter ＞

The light filter of the present invention has the pixel formed by the colored resin composition of the present invention.

Method below for the light filter forming the present invention illustrates.

The pixel of light filter may utilize various method and formed.Here, to use the colored resin composition of optical polymerism also Utilize photoetching process to illustrate in case of forming pixel, but manufacture method is not limited to the method.

First, on a surface of a substrate, in the way of marking off the part of pixel to be formed, black square is formed as required Battle array, and it is coated with the colored resin composition of the present invention on the substrate, then, carry out prebake so that solvent evaporates, thus shape Become film.Then, across mask, this film is exposed, then uses alkaline developer to develop, dissolve and remove film Unexposed portion, bakees after then carrying out, and is consequently formed redness, green, blue each pattern of pixels, thus can be made into light filter.

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

As the substrate that uses when forming pixel, as long as transparent and have the substrate of suitable intensity, it is special to there is no Limit, can enumerate such as: polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Fat film-making material, epoxy resin, thermosetting resin, various glass etc..

It addition, for these substrates, it is also possible to implement following suitable pre-treatment as desired: utilize silane coupled The surface process etc. such as thin film formation process that agent, polyurethane based resin etc. are carried out, Corona discharge Treatment, ozone process.

When colored resin composition is coated on substrate, can enumerate spin-coating method, bar (Wire bar) method, flow coat method, Slit spin-coating method (Slit and Spin Coating) method, die coating method, rolling method, spraying process etc..Wherein, preferably slit spin coating Method and die coating method.

The thickness of coated film is usually 0.2～20 μm with dried film thickness gauge, is preferably 0.5～10 μm, particularly preferably It is 0.8～5.0 μm.

Time within the above range, in pattern development and liquid crystal cells chemical industry sequence, easily carry out gap adjustment, and easily Demonstrate desired color, therefore preferably.

The lonizing radiation used during as exposure, can use such as visible ray, ultraviolet, far ultraviolet rays, electron beam, X to penetrate Line etc., optimal wavelength lonizing radiation in the range of 190～450nm.

For can be used for the light source of the lonizing radiation for obtaining wavelength 190～450nm of image exposure, there is no special limit Fixed, can enumerate such as: xenon lamp, Halogen light, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury The lamp source such as lamp, low pressure mercury lamp, carbon arc, fluorescent lamp；Argon laser, YAG laser, excimer laser, N_2 laser, helium cadmium swash The LASER Light Source such as light, semiconductor laser etc..When the light using specific wavelength is irradiated, it is also possible to utilize optical filter.

The light exposure of lonizing radiation is preferably 10～10000J/m²。

It addition, as above-mentioned alkaline developer, the most such as: sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate, carbonic acid Potassium, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, The inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide；Monoethanolamine, diethanolamine, triethanolamine, list Methyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, just Butylamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aziridine, ethylene diimine (ethylene Diimine), the aqueous solution of the organic basic compound etc. such as Tetramethylammonium hydroxide (TMAH), choline.

Appropriate such as isopropanol, benzylalcohol, ethyl cellosolve, the molten fibre of butyl can also be added in above-mentioned alkaline developer Water-miscible organic solvent, the surfactants etc. such as agent, ethylene glycol monophenyl ether, propylene glycol, DAA.It should be noted that alkali shows Movie queen, generally washes.

As development treatment method, immersion development method, spray development method, brushing development method, supersonic wave development method etc. can be used In any means.Development conditions is preferably under room temperature (23 DEG C) 5～300 seconds.

The condition of development treatment there is no particular determination, development temperature be usually more than 10 DEG C, be preferably more than 15 DEG C, more excellent Elect more than 20 DEG C as, and the scope of usually less than 50 DEG C, preferably less than 45 DEG C, more preferably less than 40 DEG C.

It is any that developing method can use in immersion development method, spray development method, brushing development method, supersonic wave development method etc. Method.

When the light filter thus made is used for liquid crystal indicator, can be directly with the shape on image of the state after making The transparency electrodes such as one-tenth ITO, and it is used as a part for the parts such as color display, liquid crystal indicator, but in order to improve table Face flatness and durability, it is also possible to the top coat such as polyamide, polyimides is set as required on image.Additionally, in portion Divide in the purposes such as planar orientation type type of drive (IPS pattern), be the most also formed without transparency electrode.It addition, at vertical orientating type In type of drive (MVA pattern), the most also form rib (rib).Additionally, the most also utilize photoetching process to form rod structure (photosensitive Gap) replace pearl decentralized spacer.

＜ liquid crystal indicator ＞

The liquid crystal indicator of the present invention is the use of the liquid crystal indicator of the light filter of the invention described above.The present invention's Pattern and the structure of liquid crystal indicator there is no particular restriction, and the light filter of the present invention can be used to utilize conventional method to assemble.

Such as, available " liquid crystal apparatus handbook " (daily magazine industry newspaper office (the new society of daily magazine industry), JIUYUE in 1989 29 days Distribution, committee of JSPS the 142nd write) described in method, form the liquid crystal indicator of the present invention.

＜ organic EL display ＞

When making the organic EL display of the light filter comprising the present invention, following method can be used: such as, such as Fig. 1 Shown in, transparent support substrate 10 utilize the colored resin composition of the present invention form pixel 20 and obtain blue color Sheet, and across organic protection layer 30 and inorganic oxide film 40 lamination organic luminorphor 500 on this blue color filter, thus make Make the organic EL element of polychrome.

As the laminating method of organic luminorphor 500, can enumerate: light filter upper surface sequentially form transparent anode 50, Hole injection layer 51, hole transmission layer 52, luminescent layer 53, electron injecting layer 54 and the method for negative electrode 55；Make to be formed at another base Organic luminorphor 500 on plate is fitted in the method etc. on inorganic oxide film 40.The organic EL element 100 thus made is applicable Organic EL display in passive matrix mode, it is possible to be applicable to the organic EL display of active drive mode.

Embodiment

Then, enumerate synthesis example, embodiment and comparative example and further illustrate the present invention, but without departing from main points of the present invention In the range of, the present invention is not limited by following embodiment.

The synthesis ＞ of ＜ dyestuff

(synthesis example 1: the synthesis of dyestuff A)

[chemical formula 17]

(synthesis of compound 2)

1-amino naphthalenes (14.3g) is dissolved in 1-propanol (300ml), adds the first of PS (12.2g) Alcohol (20ml) solution, has been heated to reflux 2 hours.Filter out generated precipitation, clean with 1-propanol, obtained compound 2 (12.3g)。

(synthesis of dyestuff A)

At compound 1 (synthesizing according to the method described in Japanese Unexamined Patent Publication 2011-70171 publication) (8.05g) and 2-third The mixture of alcohol (100ml) adds sodium borohydride (1.0g), has been heated to reflux 18.5 hours.Add sodium borohydride (1.0g), 1.5 hours it are heated to reflux further.Carry out concentrating under reduced pressure, add oxolane (50ml), be heated to reflux 2 hours.Carry out Concentrating under reduced pressure, adds 1N sodium hydrate aqueous solution, extracts with toluene, cleans with saturated aqueous common salt, carries out anhydrous sodium sulfate and be dried, Obtain grease.

In obtained grease (total amount), add compound 2 (3.71g) and 2N hydrochloric acid (40ml), be heated to reflux 2 Hour.After addition sodium hydrate aqueous solution becomes alkalescence, generate tarry insoluble matter.Supernatant is eliminated by decant, Then carry out concentrating under reduced pressure, add water and be stirred, then remove water by decant, obtained solid is dried.

In obtained solid (total amount), add methanol (100ml) and chloranil (3.44g), stir at 50 DEG C 2 hours.Carry out concentrating under reduced pressure, add chloroform and water, isolate chloroform layer, with silica gel chromatography (eluting solvent: chloroform～chlorine Imitative/methanol=10/1) it is purified, obtain dyestuff A (1.30g).

Compound identification methods: mass spectral analysis

Ionization mode: LDI

Posi m/z=586 [M+H]⁺

Neg m/z=585 [M]^-

This compound is at 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=4/6 solution In maximum absorption wavelength (λ max) be 639nm, gram specific absorbance be 125.

(synthesis example 2: the synthesis of dyestuff B)

(synthesis of compound 11)

[chemical formula 18]

By 1,7-Ke Liewei acid (2.23g, Tokyo chemical conversion industry manufacture), 1,1,1-tri-fluoro-4-iodobutane (2.98g, Tokyo Chemical conversion industry manufactures), potassium carbonate (2.76g and Wako Pure Chemical Industries Manufacturing) and N-Methyl pyrrolidone (22mL) mix, at nitrogen 10 hours have been stirred in 80 DEG C under atmosphere.Reactant liquor is cooled to room temperature, then mixes with water (150mL), regulate extremely with concentrated hydrochloric acid PH=5.3, is then extracted by ethyl acetate.Organic layer anhydrous sodium sulfate is dried, is then filtered off desiccant, steam Evaporate and eliminate solvent.With Di Iso Propyl Ether, gained crystal is carried out the cleaning that suspends, separated with solvent by filtration under diminished pressure, and then will Obtained solid under reduced pressure removes residual solvents in 50 DEG C, has 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⁺,C₁₄H₁₅F₃NO₃S)

(synthesis of dyestuff B)

[chemical formula 19]

Compound 1 (8.46g) is dissolved in THF (68mL), adds lithium borohydride (3mol/L, THF solution, 9.2mL), 3 hours have been stirred under nitrogen atmosphere in 50 DEG C.After being cooled to room temperature, add sodium hydrate aqueous solution (1mol/L, 10mL) and go forward side by side Row stirring, then mixes with water (300mL), is extracted by ethyl acetate.Organic layer use water, saturated aqueous common salt are cleaned, It is dried with anhydrous sodium sulfate.Filter out desiccant, solvent is distilled off, resulting in grease (7.96g).

Grease (2.04g) obtained by above-mentioned reaction and compound 11 (2.06g) are dissolved in acetic acid (26mL), 5 hours have been stirred under room temperature.Reactant liquor is mixed with water (150mL), with sodium hydrate aqueous solution (20 weight %) by pH regulator It is 6.5, makes solid separate out.Filter out obtained solid, be under reduced pressure dried in 50 DEG C, obtained light-blue solid (3.16g).2.5g silica gel chromatography therein (eluting solvent: chloroform/methanol=93/7～78/22) is purified, Arrive light-blue solid (1.66g).The result of the LC-MS analysis of this compound is as follows.

LCMS(ESI,posi)m/z 656(M+H⁺,C₃₆H₄₅F₃N₃O₃S)

Light-blue solid (1.64g), chloranil (0.61g) and methanol (33mL) mixing that above-mentioned reaction is obtained, It is stirred at room temperature 4 hours, stirred at 45 DEG C 8 hours.After reactant liquor is cooled to room temperature, solvent is distilled off.Will This crude product purified by silica gel chromatography (eluting solvent: chloroform/methanol=95/5～82/18) is purified, and has obtained navy blue solid The dyestuff B (0.82g) of body.

This compound is molten at 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 Maximum absorption wavelength (λ max) in liquid is 633nm, gram specific absorbance is 126.The LC-MS analysis of this compound Result is as follows.

LCMS(ESI,posi)m/z 654(M+H⁺,C₃₆H₄₃F₃N₃O₃S)

(synthesis example 3: the synthesis of dyestuff C)

(synthesis of compound 12)

[chemical formula 20]

By 1,6-Ke Liewei acid (3.35g, Tokyo chemical conversion industry manufacture), 1,1,1-tri-fluoro-4-iodobutane (3.57g, Tokyo Chemical conversion industry manufactures), potassium carbonate (2.07g and Wako Pure Chemical Industries Manufacturing) and N-Methyl pyrrolidone (27mL) mix, at nitrogen 8 hours have been stirred in 80 DEG C under atmosphere.Then, add 1,1,1-tri-fluoro-4-iodobutane (0.71g), heat at 80 DEG C further 2 hours.

After reactant liquor is cooled to room temperature, mixes with water (150ml), be adjusted to pH=4 with concentrated hydrochloric acid, then use acetic acid second Ester is extracted.The solvent being distilled off in extract layer by rotary evaporator, is carried out the crystal Di Iso Propyl Ether of precipitation Suspend and clean, separated with solvent by filtration under diminished pressure, and then obtained solid is under reduced pressure removed residual solvent in 50 DEG C, Obtain 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⁺, C₁₄H₁₅F₃NO₃S)

(synthesis of dyestuff C)

[chemical formula 21]

Compound 1 (2.71g) is dissolved in THF (22mL), adds lithium borohydride (3mol/L, THF solution, 2.9mL), 2 hours have been stirred under nitrogen atmosphere in 50 DEG C.After being cooled to room temperature, add sodium hydrate aqueous solution (1mol/L, 6mL) and carry out Stirring, then mixes with water (150mL), is extracted by ethyl acetate.Organic layer use water, saturated aqueous common salt are cleaned, uses Anhydrous sodium sulfate is dried.Filter out desiccant, solvent is distilled off, resulting in grease (2.74g).

The grease (2.38g) above-mentioned reaction obtained and compound 12 (2.31g) are dissolved in acetic acid (19mL), in room The lower stirring of temperature 1 hour, then places a night.Second day, reactant liquor is mixed with water (200mL), uses sodium hydrate aqueous solution (20 weight %), by pH regulator to 4.1, makes solid separate out.Filter out obtained solid, be under reduced pressure dried in 50 DEG C, obtain 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⁺,C₃₆H₄₅F₃N₃O₃S)

Light-blue solid (1.44g), chloranil (0.54g) and methanol (29mL) mixing that above-mentioned reaction is obtained, It is stirred at room temperature 4 hours, stirred at 55 DEG C 4.5 hours.Then, add chloranil (0.27g), heat further 10.75 hours.After reactant liquor is cooled to room temperature, filtering reacting liquid, eliminate insoluble matter, solvent is then distilled off.Will This crude product purified by silica gel chromatography (eluting solvent: chloroform/methanol=95/5～85/15) is purified, and has obtained navy blue solid The dyestuff C (0.31g) of body.

This compound is molten at 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 Maximum absorption wavelength (λ max) in liquid is 639nm, gram specific absorbance is 111.The LC-MS analysis of this compound Result is as follows.

LCMS(ESI,posi)m/z 654(M+H⁺,C₃₆H₄₃F₃N₃O₃S)

(synthesis example 4: the synthesis of dyestuff D)

(synthesis of compound 13)

[chemical formula 22]

By 1,8-Ke Liewei acid (3.35g, Tokyo chemical conversion industry manufacture), 1,1,1-tri-fluoro-4-iodobutane (3.57g, Tokyo Chemical conversion industry manufactures), potassium carbonate (2.07g and Wako Pure Chemical Industries Manufacturing) and N-Methyl pyrrolidone (27mL) mix, at nitrogen 7.5 hours have been stirred in 80 DEG C under atmosphere.Then, add 1,1,1-tri-fluoro-4-iodobutane (0.89g), heated 3.75 further Hour.After reactant liquor is cooled to room temperature, mixes with water (150mL), be adjusted to pH=1.3 with concentrated hydrochloric acid, filter out precipitation Solid, is under reduced pressure dried in 50 DEG C, has obtained the compound 13 (4.23g) of white solid.

(synthesis of dyestuff D)

[chemical formula 23]

Compound 1 (1.69g) is dissolved in THF (14mL), adds lithium borohydride (3mol/L, THF solution, 1.8mL), 2 hours are being stirred under nitrogen atmosphere in 50 DEG C.After being cooled to room temperature, add sodium hydrate aqueous solution (1mol/L, 6mL) and go forward side by side Row stirring, then mixes with water (100mL), is extracted by ethyl acetate.Organic layer use water, saturated aqueous common salt are cleaned, It is dried with anhydrous sodium sulfate.Filter out desiccant, solvent is distilled off, resulting in grease (1.76g).

The grease (1.57g) above-mentioned reaction obtained and compound 13 (1.53g) are dissolved in acetic acid (23mL), in room The lower stirring of temperature 1.5 hours, placed a night.Second day, reactant liquor is mixed with water (150mL), with sodium hydrate aqueous solution (20 Weight %) it is 3.83 by pH regulator, make solid separate out.Filter out obtained solid, be under reduced pressure dried in 50 DEG C, obtain Light-blue solid (2.5g).

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

LCMS(ESI,posi)m/z 656(M+H⁺,C₃₆H₄₅F₃N₃O₃S)

Light-blue solid (1.89g), chloranil (0.71g) and methanol (30mL) mixing that above-mentioned reaction is obtained, 4 hours have been stirred at 45 DEG C.After reactant liquor is cooled to room temperature, it is filtered to remove insoluble matter, and solvent has been distilled off.Should Crude product purified by silica gel chromatography (eluting solvent: chloroform/methanol=98/2～92/8) is purified, and has obtained blue solid Dyestuff D (0.75g).

This compound is molten at 10ppm propylene glycol methyl ether acetate (PGMEA)/propylene glycol monomethyl ether (PGME)=35/65 Maximum absorption wavelength (λ max) in liquid is 648nm, gram specific absorbance is 104.The LC-MS analysis of this compound Result is as follows.

LCMS(ESI,posi)m/z 654(M+H⁺,C₃₆H₄₃F₃N₃O₃S)

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

[chemical formula 24]

By compound 21 (6.0g, 25mmol, synthesize according to the method described in International Publication the 2008/003604th), Compound 22 (6.4ml, 50mmol, from Tokyo chemical conversion buy), potassium carbonate (6.9g, 50mmol), METHYLPYRROLIDONE (25ml) mixture is heated and stirred 4 hours at 110～125 DEG C.After being cooled to room temperature, add water, extract with toluene Take, toluene layer dilute hydrochloric acid and saturated aqueous common salt are cleaned, is dried with anhydrous sodium sulfate.Carry out concentrating under reduced pressure, obtain Shallow dark brown oil (9.2g).This shallow dark brown oil is dissolved in ethanol (40ml), adds sodium hydroxide (2g, 52.3mmol) Water (25ml) solution, at 85 DEG C, stirred 1 hour.After natural cooling, extract with toluene, toluene layer is used saturated food Saline cleans, and is dried with anhydrous sodium sulfate.Carry out concentrating under reduced pressure, with silica gel chromatography (hexane/ethyl acetate=3/1) It is purified, has obtained the white powder of compound 23 (5.95g, yield 94%).

[chemical formula 25]

Compound 1 (1.47g, 4.34mmol, is closed according to the method described in International Publication the 2009/107734th Become), after compound 23 (1.1g, 4.34mmol), toluene (30ml), the mixture of phosphoryl chloride phosphorus oxychloride (0.6ml) be heated to reflux 4 hours, It is cooled to room temperature, adds water, extracted with chloroform, by chloroform layer concentrating under reduced pressure, with silica gel chromatography (eluting solvent: chlorine Imitative/methanol=15/1～10/1) it is purified, with hexane, obtained solid is cleaned, obtained compound 25 (1.32g, receipts Rate 50%).

[chemical formula 26]

By compound 25 (8.9g, 14.6mmol), compound 26 (4.2g, 14.6mmol, from Tokyo chemical conversion buy), methanol (50ml) after mixture stirs 1.5 hours at 50 DEG C, concentrating under reduced pressure, solids with methanol/water=1/2 obtained is cleaned, Obtain comparing dyestuff 1 (11.5g, yield 92.3%).

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

[chemical formula 27]

By compound 25 (1.95g), C.I. acid blue 80 (Aldrich manufacture: 1.36g), methanol (25mL) mixed Compound has stirred 30 minutes at 50 DEG C, then carries out concentrating under reduced pressure, by molten for the mixing of solid water/methanol=2/1 obtained Agent is cleaned, and has obtained comparing dyestuff 2 (2.22g).

The synthesis ＞ of ＜ resin

(with reference to synthesis example 3: the synthesis of Resin A)

Replacing while being stirred while propylene glycol methyl ether acetate 145 weight portion to be carried out nitrogen, being warming up to 120 DEG C. Dripped styrene 10 weight portion, glycidyl methacrylate 85.2 weight portion with 3 hours wherein, there is tristane bone Mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s manufacture) 66 weight portions of frame and the double-2-methylbutyronitrile of 2,2 '-azo The mixed liquor of 8.47 weight portions, continues to have stirred 2 hours further at 90 DEG C.Then, put becoming air in reaction vessel Change, acrylic acid 43.2 weight portion puts into three (dimethylaminomethyl) phenol 0.7 weight portion and hydroquinone 0.12 weight portion, Reaction 12 hours is continued at 100 DEG C.Then, tetrabydrophthalic anhydride (THPA) 56.2 weight portion, triethylamine 0.7 weight are added Part, at 100 DEG C, reacted 3.5 hours.Weight average molecular weight Mw of the resin solution obtained above measured by GPC is about 8400, acid number is 80mg-KOH/g.Propylene glycol methyl ether acetate is added so that solid constituent is 44 weights in this resin solution Amount %, uses as Resin A.

(with reference to synthesis example 4: the synthesis of resin B)

Replacing while being stirred while propylene glycol methyl ether acetate 145 weight portion to be carried out nitrogen, being warming up to 120 DEG C. Dripped styrene 5.2 weight portion, glycidyl methacrylate 132 weight portion with 3 hours wherein, there is tristane bone Mono acrylic ester FA-513M (Hitachi Chemical Co., Ltd.'s manufacture) 4.4 weight portions of frame and the double-2-methylbutyronitrile of 2,2 '-azo The mixed liquor of 8.47 weight portions, continues stirring 2 hours further at 90 DEG C.Then, air displacement will be become in reaction vessel, Three (dimethylaminomethyl) phenol 1.1 weight portion and hydroquinone 0.19 weight portion is put into, 100 in acrylic acid 67.0 weight portion Continue at DEG C to have reacted 12 hours.Then, tetrabydrophthalic anhydride (THPA) 15.2 weight portion, triethylamine 0.2 weight are added Part, at 100 DEG C, reacted 3.5 hours.The resin solution obtained above measured by GPC is converted into the weight average of polystyrene Molecular weight Mw about 9000, acid number are 25mg-KOH/g.Propylene glycol methyl ether acetate is added in this resin solution so that Gu Body composition is 40 weight %, uses as resin B.

(with reference to synthesis example 5: the synthesis of resin C)

" NC3000H " (Nippon Kayaku K. K's manufacture) (epoxide equivalent 288, softening point 69 is loaded in reaction vessel DEG C) 400 weight portions, acrylic acid 102 weight portion, p methoxy phenol 0.3 weight portion, triphenylphosphine 5 weight portion and propylene glycol list Methyl ether acetate 264 weight portion, stirs, until acid number reaches below 3mg-KOH/g at 95 DEG C.Acid number reaches desired value needs 9 hours (acid number 2.2mg-KOH/g).Then, add tetrabydrophthalic anhydride 151 weight portion further, at 95 DEG C, react 4 Hour, obtained acid number be 102mg-KOH/g, the weight average molecular weight (Mw) being converted into polystyrene that measured by GPC be The resin solution of 3900.In this resin solution, add propylene glycol methyl ether acetate so that solid constituent is 44 weight %, make Use for resin C.

The preparation ＞ of ＜ colored resin composition

By dyestuff A, B, C and D of obtaining in above-mentioned synthesis example 1～4, with reference to the comparison dyestuff 1 obtained in synthesis example 1 and 2 And 2, with reference to the Resin A obtained in synthesis example 3 and the mixing of other composition, making them is the composition described in table 1 below, system For colored resin composition.

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

During mixing, stir more than 1 hour until each composition is sufficiently mixed, finally utilize 5 μm canopy-type filter ( Type Off ィ Le タ) filter, eliminate foreign body.

By dyestuff A, B, C and D of obtaining in above-mentioned synthesis example 1～4, with reference to the comparison dyestuff 1 obtained in synthesis example 1 and 2 And 2, with reference to the resin B obtained in synthesis example 4 and 5 and C and the mixing of other composition, making them is the group described in table 1 below Become, be prepared for colored resin composition.

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

During mixing, stir more than 1 hour until each composition is sufficiently mixed, finally utilize the canopy-type filter of 5 μm to filter, Eliminate foreign body.

Each compound in table 1 is the most as follows.

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

DPHA: dipentaerythritol acrylate

PGMEA: propylene glycol methyl ether acetate

PGME: propylene glycol monomethyl ether

F475 DIC company manufactures: containing the oligomer of perfluoroalkyl

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

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

It should be noted that each compound in table 2 is the most as follows.

DPHA: dipentaerythritol acrylate

PET-P: tetramethylolmethane four (3-thiopropionate)

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

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

Compounds X: 3-(2-Acetyloxyimino-1,5-dioxy-5-methoxypentyl)-9-ethyl-6-(toluoyl Base)-9H-carbazole

F475 DIC company manufactures: containing the oligomer of perfluoroalkyl

JPP-100 Johoku Chemical Co., Ltd. manufactures: tetraphenyl dipropyleneglycol

PGMEA: propylene glycol methyl ether acetate

PGME: propylene glycol monomethyl ether

＜ evaluates ＞

[1] evaluation (embodiment 1～4 and the comparative example of the brightness of the film made by colored resin composition and thermostability 1 and 2)

Spin-coating method is utilized to cut into the pigmentary resin combination of coating such as above-mentioned table 1 preparation on the square glass substrate of 5cm Thing so that dried sy value is 0.120, after drying under reduced pressure, has carried out the prebake (pre-of 3 minutes on hot plate in 80 DEG C bake).Then, with 60mJ/cm²Light exposure whole face is exposed, then, fire 30 with dustless baking oven in 200 DEG C Minute, use spectrophotometer U-3310 (Hitachi's manufacture) to measure spectral transmission, and calculate it at XYZ color specification system Colourity (illuminant-C) in 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	Relatively 1	0.138	0.120	17.0
Comparative example 2	Relatively 2	0.139	0.120	16.4

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

(indium doping stannum oxide closes to use spinner setting speed (300rpm～700rpm) to have ITO at whole evaporation Gold) electrode glass substrate (EHC evaluation glass ITO full version (beta) MN-1392) on be coated with colored resin composition, make The thickness obtaining coated film is 2～3 μm (thickness after heat cure is of about 2 μm), and described colored resin composition comprises embodiment And the dyestuff of comparative example and making with above-mentioned ratio and composition, by the hot plate prebake 3 minutes of 80 DEG C, then in vacuum chamber It is dried 1 minute.

Then, use high-pressure mercury-vapor lamp, photomask is implemented, with 62mJ/cm in the periphery as electrode²Light exposure to painting Film exposure comprises the lonizing radiation 30mW of each wavelength of 303nm, 313nm, 334nm, 365nm, 405nm and 436nm, and then 200 Solidify (hereinafter also referred to as " solidification temperature ") after carrying out at DEG C 60 minutes, make curing of coating, obtained the blue picture of liquid crystal evaluation Element substrate (hereinafter also referred to as " resist film ").

With the warm water of water and 45 DEG C to define blue pixel substrate and only by ITO electrode evaporation for the electricity of shaped After electrode substrate (EHC evaluation glass SZ-B11MIN (B) MN11396) is carried out, it is dried in the baking oven of 105 DEG C, with mixed Close after having the sealant of bead of 5 μm to fit (gap is 5 μm), the baking close annealing 2 hours of 180 DEG C, obtaining Box in inject liquid crystal MLC-7021-000 (manufacture of Merck company), having made electrode area is 1cm²Liquid crystal cell.

Then, utilize liquid crystal evaluation of physical property system 6254 type (TOYO Corporation manufacture), determine at 25 DEG C The voltage retention of liquid crystal cell.Now apply voltage be 5.0V rectangular wave, measure frequency be 60Hz, 2Hz and 0.6Hz.This In described voltage retention is commonly known area ratio and 2 kinds of method for expressing of voltage ratio, have employed area ratio in this application Value (area surrounded to voltage trace and the voltage zero level of 16.7 milliseconds (examples of 60Hz) after 0 millisecond is relative to by 0 The voltage of millisecond keeps observation time 16.7 milliseconds (in the situation that 60Hz measures), observation time (to measure at 2Hz for 0.5 second Situation) or 1.67 seconds (situations of 0.6Hz) and the area ratio that obtains).

Ion concentration uses the device identical with voltage retention to be determined.Apply frequency 0.1Hz, the three of ± 10V Angle ripple, is output calculating the form of waveform of hour change of electric current.In waveform, the direct peak of liquid crystal advances with only The above-mentioned box of liquid crystal measures, and then, is measured the liquid crystal cell of each example.About liquid crystal direct occurred in ion waveform Peak and foreign ion peak and foreign ion density seek method, shown in Figure 2.

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

It addition, the voltage retention of below 2Hz is the characteristic extremely sensitive to ionic impurity.The voltage of this below 2Hz Conservation rate wants intervention of coupled ion etc. and the ion concentration measurement result (direct peak current/foreign ion of ion concentration, liquid crystal Peak current), the behavioral observation of voltage retention under 60Hz and liquid crystal consider its preferred scope.

Additionally, the voltage retention under 0.6Hz is affected more notable by ionic impurity.This is because, 0.6Hz's In the case of, the movement in liquid crystal of the foreign ion on resist film surface is the most abundant, and the time measuring change in voltage is the longest.

By measuring ion concentration, it is appreciated that the impact of the ionic impurity deriving from resist film.That is, to cation In the case of side and anion side apply voltage, represent in either side it is all that ion concentration is the highest, comprise in liquid crystal Ionic impurity, comprises and hinders factor liquid crystal cell applying voltage and hindering the voltage of liquid crystal cell to keep.That is, ion is close Spending the least, electrical characteristics are the best.It should be noted that only in the case of liquid crystal, ion concentration is 0nC.

Liquid crystal evaluation result is summarized in 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, than liquid crystal for " cannot quantize because of current leakage " Response speed short time, namely apply after voltage in the time of less than 1 millisecond, voltage is decreased below 2V, therefore, liquid The phenomenon that voltage during brilliant box work is not applied on liquid crystal cell, electrical characteristics are significant lower.

It addition, ion concentration refers to for " cannot measure because of current leakage ", it is " because of current leakage in voltage retention Cannot measure " box in, electrical characteristics are significant lower, therefore can not measure ion concentration exactly.

" ion concentration is too high to measure " refers to, owing to there is current leakage, liquid crystal is not responding to, and therefore liquid crystal is straight Connect peak not embody in ion concentration, and, owing to the electric current produced is excessive, quasi-molecular ions is capped and cannot distinguish, beyond The ion concentration determination limit of device, represents that electrical characteristics are low.

As shown in table 3, the brightness using the pixel of the colored resin composition formation of the present invention is high, is good blueness picture Element.It addition, as shown in table 4 and table 5, by the blue pixel substrate (resist film) of the colored resin composition employing the present invention The voltage retention of this liquid crystal cell formed is the highest, and ion concentration is little, has good electrical characteristics.Particularly 200 DEG C such Temperature is slightly lower as the solidification temperature of resin combination, and ionic composition is in liquid crystal or on the boundary of liquid crystal Yu resist film Face dissolution, evaluates characteristic for liquid crystal and there is disadvantageous tendency.Even if using 200 DEG C of such slightly lower solidification temperatures, by having The ion concentration having the liquid crystal cell that the resist film of embodiment compound formed is the lowest, compared with comparative example, exists ionic miscellaneous The repressed tendency of dissolution of matter.Its result, voltage retention is high, is good.Particularly, for comprising the chemical combination of dyestuff B For the colored resin composition (embodiment 6,8,10,14) of thing, its ion concentration is the highest also below 1nC, the electricity under 0.2Hz Pressure conservation rate has exceeded 85%.I.e., it is known that its electrical characteristics are good and voltage retention is the highest.

As previously discussed, there is the light filter of the pixel using the colored resin composition of the present invention to be formed and comprise The liquid crystal indicator of this light filter and organic EL display are high-quality.

With reference to specific embodiment, the present invention is described in detail, but those skilled in the art should understand that It is, in the case of the spirit and scope of the invention, various change or correction can be carried out.The application was based on 2012 Japanese patent application (Patent 2012-077457) that March 29 proposed and complete, its content is as with reference to being introduced in this Shen In please.

Industrial applicibility

According to the present invention it is possible to provide a kind of novel triarylmethane compounds, by this triarylmethane class chemical combination Thing can obtain being simultaneously achieved the pixel of brightness and voltage retention.Additionally, according to the present invention it is possible to provide a kind of novel Chromoresin compositions, be can get, by this colored resin composition, the pixel that brightness is high and voltage retention is the highest.It addition, this Bright can provide light filter and the liquid crystal indicator of high-quality comprising the pixel that brightness is high and voltage retention is the highest And organic EL display.Therefore, the present invention is for light filter and liquid crystal indicator and organic EL display etc. Application aspect is useful.

Claims

The triarylmethane compounds that the most following formula (I) represents,

In above-mentioned formula (I), R¹～R⁶Represent hydrogen atom independently of one another, optionally there is the alkane of the carbon number 1～10 of fluoro substituents Base or the aromatic ring group of carbon number 5～18,

R⁷And R⁸Represent hydrogen atom, halogen atom or the alkyl of carbon number 1～10 independently of one another,

Wherein, R⁷And R⁸In at least one be halogen atom or the alkyl of carbon number 1～10,

M⁺Represent cation,

N represents the integer of 0～4,

[]-SO outward₃ ^-The position of substitution of base is to form the hydrogen atom on the naphthalene nucleus of triarylmethane skeleton or R⁶On substituent group Hydrogen atom.
Triarylmethane compounds the most according to claim 1, wherein, in above-mentioned formula (I), R⁷For hydrogen atom, R⁸For Halogen atom or the alkyl of carbon number 1～10.
Triarylmethane compounds the most according to claim 2, wherein, in above-mentioned formula (I), R⁷For hydrogen atom, R⁸For Halogen atom or the alkyl of carbon number 1～4.
Triarylmethane compounds the most according to claim 2, wherein, in above-mentioned formula (I), R⁷For hydrogen atom, R⁸For Methyl.
Triarylmethane compounds the most according to claim 1 and 2, wherein, in above-mentioned formula (I), R¹～R⁴For optionally There is the alkyl of the carbon number 1～8 of fluoro substituents.
Triarylmethane compounds the most according to claim 1 and 2, wherein, in above-mentioned formula (I), R¹～R⁴For optionally There is the alkyl of the carbon number 1～4 of fluoro substituents.
Triarylmethane compounds the most according to claim 1 and 2, wherein, in above-mentioned formula (I), R¹～R⁴For second Base.
Triarylmethane compounds the most according to claim 1 and 2, wherein, in above-mentioned formula (I), []-SO outward₃ ^- The position of substitution of base is to form the hydrogen atom on the naphthalene nucleus of triarylmethane skeleton.
Triarylmethane compounds the most according to claim 1 and 2, wherein, under the compound that above-mentioned formula (I) represents is State the compound that formula (II) represents,

In above-mentioned formula (II), n, M⁺、R¹～R⁵、R⁷And R⁸With the definition synonym in above-mentioned formula (I),

R¹¹And R¹²Represent hydrogen atom, fluorine atom or the alkyl of carbon number 1～8 independently of one another,

M represents the integer of 1～8.
Triarylmethane compounds the most according to claim 9, wherein, in above-mentioned formula (II), R⁷For hydrogen atom, R⁸ For halogen atom or the alkyl of carbon number 1～4.
11. triarylmethane compounds according to claim 9, wherein, in above-mentioned formula (II), R⁷For hydrogen atom, R⁸ For methyl.
12. triarylmethane compounds according to claim 9, wherein, in above-mentioned formula (II), R¹～R⁴For optionally There is the alkyl of the carbon number 1～8 of fluoro substituents.
13. triarylmethane compounds according to claim 9, wherein, in above-mentioned formula (II), R¹～R⁴For optionally There is the alkyl of the carbon number 1～4 of fluoro substituents.
14. triarylmethane compounds according to claim 9, wherein, in above-mentioned formula (II), R¹～R⁴For ethyl.
15. triarylmethane compounds according to claim 9, wherein, in above-mentioned formula (II), m be 2～5 whole Number.
16. 1 kinds of colored resin compositions, it contains (A) dyestuff, (B) solvent and (C) adhesive resin, wherein,

(A) dyestuff is the triarylmethane compounds according to any one of claim 1～15.
17. colored resin compositions according to claim 16, wherein, possibly together with (D) polymerizable monomer.
18. according to the colored resin composition described in claim 16 or 17, wherein, possibly together with (E) photopolymerization cause composition and Thermal polymerization causes at least one in composition.
19. 1 kinds of light filters, it has what use colored resin composition according to any one of claim 16～18 was formed Pixel.
20. 1 kinds of liquid crystal indicators, it has the light filter described in claim 19.
21. 1 kinds of organic EL displays, it has the light filter described in claim 19.