CN109283790A

CN109283790A - Cyan colored curable resin composition, colour filter and display device

Info

Publication number: CN109283790A
Application number: CN201810803342.5A
Authority: CN
Inventors: 大家健郎; 大家健一郎; 冈本信之; 朴昭妍
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2017-07-20
Filing date: 2018-07-20
Publication date: 2019-01-29
Anticipated expiration: 2038-07-20
Also published as: CN109283790B; KR102385559B1; KR20190010440A

Abstract

Problem of the present invention is that the colour filter formed by cyan colored curable resin composition and display device is made to meet high brightness in high chroma region.Cyan colored curable resin composition, it is characterized by: including colorant, resin, polymerizable compound and polymerization initiator, colorant is the colorant comprising compound Y and cyan colorant, when the compound Y measures the spectrophotometric spectra of the cyclohexanone solution of the compound Y containing 0.001 mass % under the optical path length of 1.0cm, meet condition 1 below)~3): condition 1) a length of 380nm or more of maximum absorption wave and 450nm or less, condition 2) maximum absorption wave strong point absorbance be 3 or more, condition 3) absorbance at 460nm is 0.2 or less.

Description

Cyan colored curable resin composition, colour filter and display device

Technical area

The present invention relates to colored curable resin compositions.More particularly to cyan colored curable resin composition.

Background technique

The display devices such as liquid crystal display device, el display device and plasma display, CCD, CMOS sensing Colour filter used in the solid-state imagers such as device is manufactured by colored curable resin composition.As formation cyan colour filter The cyan colored curable resin composition of device contains the C.I. pigment blue 15 for being used as colorant: the group of 6 and C.I pigment yellow 150 Closing object is known (patent document 1).

Patent document 1 discloses using yellow uitramarine the brightness for reducing cyan filter, to reach adjustment white balance Purpose especially adjusts the purpose of tri- colour balance of RGB.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2004-279617 bulletin

Summary of the invention

Problems to be solved by the invention

However, research has been carried out in recent years to extend the colour gamut of display device etc., therefore, for filtering used in it Color device is also required to further improve chroma.The present invention is by the colour filter formed by cyan colored curable resin composition high color Degree meets high brightness as project in region.

The means used to solve the problem

To solve the above problems, inventor's discovery contains compound Y and blueness by cyan colored curable resin composition Chromatic colorant agent is as colorant, so as to be formed in the colour filter in high chroma region with excellent brightness, so as to complete this Invention.

That is, main points of the invention are as follows:

(1) a kind of cyan colored curable resin composition, which is characterized in that include colorant, resin, polymerism chemical combination Object and polymerization initiator, colorant is the colorant comprising compound Y and cyan colorant, when under the optical path length of 1.0cm When the spectrophotometric spectra of the cyclohexanone solution of the compound Y of the measurement containing 0.001 mass %, the compound Y meets below Condition 1)~3):

Condition 1) a length of 380nm or more of maximum absorption wave and 450nm or less

Condition 2) maximum absorption wave strong point absorbance be 3 or more

Condition 3) absorbance at 460nm is 0.2 or less.

(2) the cyan colored curable resin composition according to (1), wherein the content of the cyan colorant exists It is 80 mass of mass %~99.99 % in 100 mass % of colorant.

(3) the cyan colored curable resin composition according to (1) or (2), wherein the compound Y's always contains Amount is 0.01 mass of mass %~20 % in 100 mass % of colorant.

(4) a kind of colour filter, the cyan colored curable resin composition as described in (1) or (2) are formed.

(5) colour filter according to (4), wherein the CIE1931 colour system measured using the characteristic function of illuminant-C In xy chromatic diagram in coordinate (x, y) meet x²+y²≤ 0.035 relationship.

(6) a kind of display device, it includes the colour filters described in (5).

The effect of invention

In accordance with the invention it is possible to provide a kind of cyan colored curable resin composition, it can be used to form high chroma Colour filter of high brightness in region.

Specific embodiment

Cyan colored curable resin composition of the invention contains colorant (hereinafter sometimes referred to colorant (A1)), tree Rouge (hereinafter sometimes referred to resin (B)), polymerizable compound (hereinafter sometimes referred to polymerizable compound (C)) and polymerization initiator (hereinafter sometimes referred to polymerization initiator (D)), colorant (A1) contain compound Y and cyan colorant.

Cyan colorant is preferably dispersed in solvent.

Colorant (A1) contains colorant (the hereinafter sometimes referred to colorant other than compound Y and cyan colorant (A2))。

Cyan colored curable resin composition of the invention can contain solvent (E).

Cyan colored curable resin composition of the invention can contain polymerization trigger auxiliary agent (D1).

Cyan colored curable resin composition of the invention can further contain levelling agent.

Cyan colorant is preferably the compound (hereinafter sometimes referred to compound (A-I)) indicated by formula (A-I).Compound It (A-I) further include its tautomer in.

[in formula (A-I),

R^1A~R^8AEach independently represent-SO₃ ^-, saturated hydrocarbyl that hydrogen atom or carbon atom number are 1~10.

R^9AAnd R^10AIt each independently represents hydrogen atom, the saturated hydrocarbyl that carbon atom number is 1~10, can have substituent group The aryl or can have the aralkyl that the carbon atom number of substituent group is 7~30 that carbon atom number is 6~20, the aryl and should The substituent group that aralkyl can have can be-SO₃ ^-。

R^11A~R^20AEach independently represent-SO₃ ^-, hydrogen atom, the saturated hydrocarbyl that carbon atom number is 1~10 or halogen it is former Son.

In above-mentioned R^1A~R^20AIn, methylene contained in the saturated hydrocarbyl can be substituted by oxygen atom or-CO-.

R⁴⁵And R⁴⁶Each independently represent hydrogen atom, carbon atom number be 1~10 saturated hydrocarbyl or can have substituent group The aryl that carbon atom number is 6~20, the substituent group which can have can be-SO₃ ^-。

R⁵⁵It indicates saturated hydrocarbyl that hydrogen atom, carbon atom number are 1~10 or can have the carbon atom number of substituent group to be 6~20 Aryl, the substituent group which can have can be-SO₃ ^-。

In the R⁴⁵、R⁴⁶And R⁵⁵In, methylene contained in the saturated hydrocarbyl can be substituted by oxygen atom or-CO-.

M^r+Indicate the metal ion of r valence.

K indicates SO possessed by the compound indicated as formula (A-I)₃ ^-The number of base.

But, there are at least two SO by the compound that formula (A-I) is indicated₃ ^-Base.

R indicates 2 or more integer.]

By R^1A~R^20A、R⁴⁵、R⁴⁶And R⁵⁵The saturated hydrocarbyl of expression can be any one in straight chain, branch and ring-type. As linear chain or branched chain saturated hydrocarbyl, can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, The straight-chain alkyls such as n-nonyl, positive decyl；Isopropyl, sec-butyl, tert-butyl, isopentyl, 1- methyl amyl, 2- ethyl-butyl, Branched-chain alkyls such as 1- butyl, 2- ethylhexyl etc..The carbon atom number of the saturated hydrocarbyl is 1~10, preferably 1~8, more Preferably 1~6.

By R^1A~R^20A、R⁴⁵、R⁴⁶And R⁵⁵The cricoid saturated hydrocarbyl indicated can be monocycle or polycyclic.It is cricoid as this Alkyl can enumerate the ester ring types saturated hydrocarbyl such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, adamantyl.This is cricoid full Carbon atom number with alkyl is preferably 3~10, and more preferably 6~10.

By R^1A~R^20A、R⁴⁵、R⁴⁶、R⁵⁵In the saturated hydrocarbyl of expression, as methylene quilt contained in the saturated hydrocarbyl The group of oxygen atom or-CO- (preferably oxygen atom) substitution, such as the group being expressed from the next can be enumerated.In following formula, * table Show bonding end.

Methylene contained in the saturated hydrocarbyl is by the carbon atom of oxygen atom or-CO- (preferably oxygen atom) group substituted Number preferably 1~10, more preferably 1~6.The saturated hydrocarbons substituted as methylene by oxygen atom or-CO- (preferably oxygen atom) Base, preferably straight-chain alkyl.When multiple methylene are substituted by oxygen atom, the carbon atom number between oxygen atom is preferably 1~4, More preferably 2~3.

By R^9A~R^10A、R⁴⁵、R⁴⁶、R⁵⁵The carbon atom number with the aryl of substituent group indicated is preferably 6~20, more Preferably 6~15, further preferably 6~12.As aryl, phenyl, tolyl, xylyl, naphthalene, anthracene can be enumerated Base, phenanthryl, xenyl, terphenyl etc., preferably phenyl, naphthalene, tolyl, xylyl, more preferably phenyl, naphthalene, Further preferably phenyl.

As by R^9A~R^10AThe aralkyl of expression can enumerate the group and methylene, Asia illustrated as above-mentioned aryl The carbon atom numbers such as ethyl, propylidene are the group etc. that the alkylidene of 1~10 (preferably carbon atom number is 1~5) is combined into.The virtue The carbon atom number of alkyl is preferably 7~30, and more preferably 7~20, further preferably 7~17.As the aryl, preferably benzene Base, naphthalene etc..

As by R^9ATo R^10ASubstituent group in the aryl and aralkyl of expression can enumerate halogen atom, such as fluorine original Son, chlorine atom and iodine etc.；The alkoxy that carbon atom number is 1~6, such as methoxyl group, ethyoxyl；Hydroxyl；Sulfamoyl；Carbon atom The alkyl sulphonyl that number is 1~6, such as mesyl；The alkoxy carbonyl that carbon atom number is 1~6, such as methoxycarbonyl, second Epoxide carbonyl etc.；-SO₃ ^-Deng preferably-SO₃ ^-.But-SO₃ ^-It is preferred that the aromatic hydrocarbon ring Direct Bonding with aryl, that is, replace with The hydrogen atom of aromatic hydrocarbon ring bonding.

As by R^9A~R^10AThe specific example of the aryl with substituent group indicated, can enumerate and be expressed from the next Group.In following formula, * indicates bonding end.

As the specific example of the aralkyl optionally replaced, methylene can be enumerated and be bonded with the bonding end of following aryl Made of group.

As by R⁴⁵、R⁴⁶、R⁵⁵Substituent group in the aryl of expression can enumerate halogen atom, as fluorine atom, chlorine are former Son, iodine etc.；The alkoxy that carbon atom number is 1~6, such as methoxyl group, ethyoxyl；Hydroxyl；Sulfamoyl；Carbon atom number is 1~6 Alkyl sulphonyl, such as mesyl；The alkoxy carbonyl that carbon atom number is 1~6, such as methoxycarbonyl；-SO₃ ^-Deng excellent Choosing-SO₃ ^-.But-SO₃ ^-It is preferred that the aromatic hydrocarbon ring Direct Bonding with aryl, that is, replace the hydrogen atom being bonded with aromatic hydrocarbon ring.As By R⁵⁵Substituent group in the aryl of expression, preferably halogen atom.R⁵⁵Can preferably have halogen atom and/or carbon atom The phenyl of the halogenated alkyl of number 1~6.

As the specific example for the aryl that there can be substituent group, the group being expressed from the next can be enumerated.In following formula In, * indicates bonding end.

As by R^11A~R^20AThe halogen atom of expression can enumerate fluorine atom, chlorine atom, bromine atom and iodine atom etc., It is preferred that fluorine atom.

R^1A~R^8AIt is each independently preferably-SO₃ ^-, saturated hydrocarbyl that hydrogen atom or carbon atom number are 1~10, more preferably For-SO₃ ^-, hydrogen atom or methyl, further preferably hydrogen atom or methyl.

R^9A~R^10AIt is each independently preferably the saturated hydrocarbyl that carbon atom number is 1~10, the carbon atom that can have substituent group Number for 6~20 aryl or can have the aralkyl that the carbon atom number of substituent group is 7~30, more preferably carbon each independently Saturated hydrocarbyl, phenyl, tolyl, naphthalene, methyl naphthalene of the atomicity for 1~8；Unsubstituted aralkyl；Or it is selected from halogen One or more of atom, methoxyl group, ethyoxyl, sulfamoyl, mesyl, methoxycarbonyl and ethoxy carbonyl, particularly 1 kind substitution aralkyl, each independently further preferably carbon atom number be 1~4 straight-chain alkyl.

From heat resistance and sunproof aspect, R^11A~R^12APreferably at least any one is halogen atom or carbon atom number For 1~10 saturated hydrocarbyl, the saturated hydrocarbyl that more preferably at least any one is halogen atom or carbon atom number is 1~8, further The saturated hydrocarbyl that preferably at least any one is fluorine atom or carbon atom number is 1~4.

From heat resistance and sunproof aspect, R^13A~R^14APreferably at least any one is halogen atom or carbon atom number For 1~10 saturated hydrocarbyl, the saturated hydrocarbyl that more preferably at least any one is halogen atom or carbon atom number is 1~8, further The saturated hydrocarbyl that preferably at least any one is fluorine atom or carbon atom number is 1~4.

From the aspect being readily synthesized, R^15A~R20^APreferably hydrogen atom or carbon atom number are 1~10 each independently Saturated hydrocarbyl, more preferably hydrogen atom or carbon atom number be 1~4 saturated hydrocarbyl, further preferably hydrogen atom or methyl.

R⁴⁵、R⁴⁶、R⁵⁵It is each independently preferably the saturated hydrocarbyl or the carbon that can have substituent group that carbon atom number is 1~10 The aryl that atomicity is 6~20, more preferably can be by halogen atom, alkoxy, hydroxyl or the first that carbon atom number is 1~4 The saturation that the saturated hydrocarbyl that the aryl or carbon atom number that sulfonyl replaces are 1~8, further preferably carbon atom number are 1~8 Alkyl or the aryl being expressed from the next.Particularly, R⁵⁵Preferably there is the aromatic hydrocarbons that the carbon atom number of halogen atom is 6~20 The aryl that base, the more preferably carbon atom number with 2 or more halogen atoms are 6~20.By R⁵⁵The aryl of expression has The number of halogen atom be preferably 1~6, more preferably 1~4, further preferably 2~3.The halogen atom is preferably fluorine original Son.

R⁵⁵Aryl particularly preferably as shown by.In following formula, * indicates bonding end.

As by M^r+The r valence metal ion of expression can enumerate the alkaline earths such as magnesium ion, calcium ion, strontium ion, barium ions gold Belong to ion；The transition metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ions, nickel ion, copper ion； The typical metals ion such as zinc ion, cadmium ion, aluminium ion, indium ion, tin ion, lead ion, bismuth ion, preferably alkaline-earth metal from Son, transition metal ions or typical metal ion, more preferably magnesium ion, strontium ion, barium ions, manganese ion or zinc ion, into One step is preferably barium ions.

R is preferably 2~5, and more preferable 2~4, further preferably 2~3.

In formula (A-I), M^r+Number be the-SO being had by the compound that formula (A-I) is indicated₃ ^-Number (k) subtract 1 again The number ((k-1)/r) obtained divided by r.Therefore, the chemical valence of compound (A-I) is 0, as electroneutral compound.

In formula (A-I) ,-SO₃ ^-Number (k) be 2 or more, preferably 6 hereinafter, more preferably 4 or less.

-SO₃ ^-It is preferred that (a) is used as R^1A~R^8A、R^11A~R^20AAny of and contain, or (b) with by R^9A、R^10AShown in Can have substituent group carbon atom number be 6~20 aryl and by R^9A、R^10AShown in can have the carbon atom number of substituent group It is combined for 7~30 any of aralkyl, or (c) and by R⁴⁵、R⁴⁶、R⁵⁵Shown in can have the carbon atom number of substituent group Combine for 6~20 any of aryl, or exist with the combination of above-mentioned (a)~(c), more preferably with (a), (b) or (a)~(b) combination exists, and further preferably exists with (a).In addition, R^1A~R^8A、R^11A~R^20AIn, particularly preferred R^16AWith R^19A。

In above-mentioned (a)~(c) ,-SO₃ ^-Preferably direct bonding is in the aromatic hydrocarbon ring of aryl or aralkyl.That is,-SO₃ ^-It is preferred that Replace the hydrogen atom being bonded with aromatic hydrocarbon ring.

More than two-SO₃ ^-It can be bonded with same aromatic hydrocarbon ring, but preferably it is bonded with different aromatic hydrocarbon rings.

As compound (A-I), as shown in the following table 1~table 9, the chemical combination indicated by formula (A-I-1) can be enumerated 1~compound of object 514 etc..In formula, * represents bonding end.

Wherein, by formula (A-I-1) indicate compound tool there are two-SO₃ ^-, R^hAnd R^11A~R^14ATwo or more be hydrogen Atom, and any two of them is by-SO₃ ^-Replace, preferably R^hFor hydrogen atom, and any two of them is by-SO₃ ^-Replace, more preferably R^hFor hydrogen atom and in the phenyl ring with nitrogen atom bonding, relative to the bonding position with nitrogen-atoms, positioned at the R of contraposition^hBy- SO₃ ^-Replace.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

For table 1 into table 9, Me indicates that methyl, Et indicate that ethyl, iPr indicate that isopropyl, Bt indicate normal-butyl, Ph1 to Ph10 Respectively indicate the group being expressed from the next.

Wherein, as the compound indicated by formula (A-I),

31~compound of preferred compound 90,121~compound of compound 180,211~compound of compound 334, chemical combination 365~compound of object 424, compound 455~514,

46~compound of more preferable compound 60,61~compound of compound 90,136~compound of compound 150, chemical combination 226~compound of object 240,271~compound of compound 334,380~compound of compound 394, compound 470~484,

Further preferred compound 46~60,61~compound of compound 90,136~compound of compound 150, compound 226~compound 240,271~compound of compound 304,380~compound of compound 394, compound 470~484,

Still more preferably compound 46~60, compound 61~90, compound 136~150, compound 226~240, Compound 271~294, compound 380~394, compound 470 to 484,

Particularly preferably 46~compound of compound 60,61~compound of compound 90,136~compound of compound 150, 226~compound of compound 240,279~compound of compound 294,380~compound of compound 394, compound 470~ 484。

Compound (A-I) for example can obtain the salt indicated by formula (A-x) by the salt sulfonation that will be indicated by formula (A-y), And then make the metal ions M of itself and r valence^r+Acetate, carbonate, phosphate, sulfate, silicate, cyanide or halide (preferably chloride) reacts to manufacture.

[in formula (A-y),

R^1B~R^8BHydrogen atom or carbon atom number are each independently represented as 1~10 saturated hydrocarbyl.

R^9BAnd R^10BIt each independently represents hydrogen atom, the saturated hydrocarbyl that carbon atom number is 1~10, can have substituent group The aryl or can have the aralkyl that the carbon atom number of substituent group is 7~30 that carbon atom number is 6~20, the aryl and should Aralkyl does not have-SO₃ ^-As substituent group.

R^11B~R^20BEach independently represent hydrogen atom, the saturated hydrocarbyl or halogen atom that carbon atom number is 1~10.

In above-mentioned R^1B~R^20BIn, methylene contained in above-mentioned saturated hydrocarbyl can be substituted by oxygen atom or-CO-.

R^45BAnd R^46BEach independently represent hydrogen atom, carbon atom number be 1~10 saturated hydrocarbyl or can have substituent group Carbon atom number be 6~20 aryl, the aryl do not have-SO₃ ^-As substituent group.

R^55BIndicate saturated hydrocarbyl that hydrogen atom, carbon atom number are 1~10 or can have the carbon atom number of substituent group be 6~ 20 aryl, the aryl do not have-SO₃ ^-As substituent group.

In above-mentioned R^45B、R^46BAnd R^55BIn, methylene contained in above-mentioned saturated hydrocarbyl can be replaced by oxygen atom or-CO- Generation.

A_B ^j-Indicate arbitrary j valence anion.

J indicates 1 or more and 5 integers below.]

As A_B ^j-, such as chloride ion, phosphate ion, sulfate ion, benzene sulfonic acid ion, naphthalene sulfonic acids ion, height can be enumerated Chlorate ions, BF₄ ^-、PF₆ ^-Deng.

[in formula (A-x), R^1A~R^20A、R⁴⁵、R⁴⁶、R⁵⁵And k is identical as aforementioned definitions.

A_A ^z+Indicate arbitrary z valence cation.Z indicates 1 or more and 5 integers below.]

A_A ^z+Preferably hydrogen ion (hydrone).

As the method for sulfonation, various well known methods, such as Journal of Organic can be enumerated Chemistry, (1994), the method for volume 59, #11, the 3232-3236 pages record.

Other cyan colorants can be known colorant, is also possible to dyestuff or pigment, can also be face The mixture of material and dyestuff.Wherein, it is preferable to use pigment from the viewpoint of heat resistance, lightness.

As green pigment, color index can be specifically enumerated (by The Society of Dyers and Colourists is published) in be classified as the compound of pigment (Pigment), record in Japanese Unexamined Patent Publication 2017-16100 bulletin Compound.

Specifically, such as the green pigments such as C.I. pigment blue 15,15:3,15:4,15:6,60 can be enumerated etc..Wherein, excellent It selects and contains C.I. pigment blue 15: 6.In addition, as violet pigment, such as C.I. pigment violet 19,23 can be contained.

In addition, can enumerate in color index as dyestuff (by The Society of Dyers and Colourists is published) in be classified as the compound of acid dyes, direct dyes, basic dye, disperse dyes, oil-soluble dyes. For example, can enumerate

Acid alizarine purple N；

C.I. acid black 1,2,24,48；

Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92, 96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、267、 278,280,285,290,296,315,324:1,335,340；

Acid chrome violet K；

Acid fuchsin；

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；

C.I. directly indigo plant 57,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107, 108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、 164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、 210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、 257,259,260,268,274,275,293；Or the derivative of these dyestuffs.

From the viewpoint of high chroma, in the 100 mass % of solid component of colorant, the content of above-mentioned cyan colorant Preferably 80~99.99 mass %, more preferably 85 mass % or more, further preferably 90 mass % or more.

As needed, rosin processing can be carried out, using introducing acidic-group or basic group to cyan colorant The surface treatment of pigment derivative, the grafting processing that surface of pigments is carried out with high-molecular compound etc., with sulfuric acid atomization etc. The atomization process of progress or the cleaning treatment carried out with organic solvent, water etc. for removing impurity, ionic impurity are adopted With the removing processing etc. of ion-exchange etc..

Blueness is obtained so that cyan colorant is evenly dispersed in solution by carrying out decentralized processing containing dispersing agent Chromatic colorant agent dispersing liquid.

As above-mentioned dispersing agent, surfactant can be enumerated, can be cationic, anionic, it is non-ionic, two Any one surfactant in property type.Specifically, the dispersing agent etc. of Polyester, polyamines system, acrylic acid series etc. can be enumerated. These dispersing agents can be used alone, and can also be used in combination of two or more.It as dispersing agent, is indicated, can be enumerated with trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) production), フローレ Application (common prosperity society chemistry (strain) production), ソ Le スパース (registrar Mark) (ゼネカ (strain) production), EFKA (registered trademark) (BASF AG's production), アジスパー (registered trademark) (Ajinomoto Fine Techno (strain) production), Disperbyk (registered trademark) (production of Bi Ke chemical company) etc..As Following resins (B) also can be used in dispersing agent.

When using a dispersant, be 100 mass parts relative to cyan colorant, usage amount be preferably 100 mass parts with Under, more than more preferably 5 mass parts and 75 below the mass.When the usage amount of dispersing agent is fallen within the above-described range, there is energy Enough obtain the tendency of the dispersion liquid of homogeneously dispersed state.

In 100 mass % of cyan colorant dispersion liquid, the content of cyan colorant is preferably 1~50 mass %, more excellent It is selected as 2~30 mass %, further preferably 3~20 mass %.When using two or more cyan colorants, it can distinguish Dispersion liquid is made, mixes when in use.

In 100 mass % of cyan colored curable resin composition, the content of cyan colorant is preferably 0.1~40 matter Measure %, more preferably 0.5~30 mass %, further preferably 1~20 mass %.

When the spectrophotometric spectra of the cyclohexanone solution of compound Y of the measurement containing 0.001 mass % under the optical path length of 1.0cm When, compound Y is to meet condition 1 below)~3) compound.

Condition 2) maximum absorption wave strong point absorbance be 3 or more

Condition 3) absorbance at 460nm is 0.2 or less

For the maximum absorption wavelength of compound Y and absorbance, the chemical combination of 0.001 mass % can be contained by preparing Then the solution is put into the measurement container (such as cuvette) that such as optical path length is 1.0cm by the cyclohexanone solution of object Y, It is measured using UV, visible light near infrared spectrometer.Absorbance is expressed as using cyclohexanone as blank control relative to it Relative value.

The a length of 380nm or more of the maximum absorption wave of compound Y and 450nm are hereinafter, preferably 385nm or more, more preferably 390nm or more, further preferably 395nm or more, additionally, it is preferred that being 445nm hereinafter, more preferably 440nm or less.Meet phase The compound Y of pass condition can synergistically improve lightness with cyan colorant.

The absorbance of the maximum absorption wave strong point of compound Y is 3 or more, preferably 3.2 or more, more preferably 3.4 or more, Further preferably 3.6 or more, much further preferably from 3.8 or more.

Absorbance at the 460nm of compound Y be 0.2 hereinafter, preferably 0.18 hereinafter, more preferably 0.16 hereinafter, into One step is preferably 0.14 hereinafter, much further preferably from 0.12 or less.

The thermal decomposition temperature of compound Y for example can be 100 DEG C~460 DEG C, or 120 DEG C~440 DEG C, 140 DEG C ~420 DEG C, 160 DEG C~400 DEG C or 180 DEG C~380 DEG C.

Compound Y is preferably porphyrin compound, merocyanine compound or methylidyne compound, more preferably porphyrin Close object.

For porphyrin compound, combination can have the aromatic ring group or heterocyclic group of substituent group on porphin ring Deng.As aromatic ring group, phenyl, naphthalene, tolyl, xylyl, preferably phenyl can be enumerated.It, can as heterocyclic group Enumerate pyridyl group, pyrazinyl, pyrimidine radicals etc..Substituent group can be alkoxy, hydroxyl, the carboxyl etc. that carbon atom number is 1~4.When When being bonded with the aromatic ring group or heterocyclic group that can have substituent group, the number of binding groups preferably 1~8, more preferable 2~4, Further preferred 4.When the bonding such as aromatic ring group or heterocyclic group that can have substituent group is multiple, can it is identical not yet Together, preferably its is identical.

Porphyrin compound can be formed with or without complex compound.When porphyrin compound formed complex compound when, preferably with Cu, Pd, Co, Ni, Fe or Zn are coordinated to form complex compound, more preferably are coordinated to form complex compound with Cu.In addition, porphyrin compound is free of four Aza porphyrin compound.

As porphyrin compound, such as visible light absorbing material (hillside plot chemical industry (strain) FDB-002), 5 can be obtained, 10,15,20- tetraphenyl -21H, 23H- porphines copper (II), tetraphenylporphyrin etc..

Compound Y can contain one kind or two or more.

In 100 mass % of colorant, the total content of compound Y is preferably 0.01~20 mass %, more preferably 15 matter % is measured hereinafter, further preferably 10 mass % or less.

In 100 mass % of cyan colored curable resin composition, the total content of compound Y is preferably 0.001~20 Quality %, more preferably 0.005~15 mass %, further preferably 0.01~10 mass %.

Resin (B) is not particularly limited, preferably alkali soluble resin, more preferably have from selected from unsaturated carboxylic acid with And the resin of the structural unit of at least one of unsaturated carboxylic acid anhydrides (a) (hereinafter sometimes referred to " (a) ").Resin (B) is preferred Also at least one structural unit selected from the following: from the cyclic annular ether structure and olefinic insatiable hunger for being 2~4 with carbon atom number With the structural unit of the monomer (b) (hereinafter sometimes referred to " (b) ") of key, from can be copolymerized with (a) monomer (c) (still, with (a) and (b) is different) structural unit of (hereinafter sometimes referred to " (c) ") and there is the structure list of ethylenic unsaturated bond in side chain Member.

As (a), acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3 specifically can be for example enumerated, 4,5, 6- tetrabydrophthalic anhydride, mono succinate [2- (methyl) acryloyl-oxyethyl] ester etc., preferably acrylic acid, methacrylic acid And maleic anhydride.

(b) the cyclic annular ether structure preferably with carbon atom number 2~4 is (for example, be selected from oxirane ring, oxetanes ring At least one of with tetrahydrofuran ring) and (methyl) acryloxy monomer.

It should be noted that in the present specification, " (methyl) acrylic acid " indicates in acrylic acid and methacrylic acid extremely Few one kind.The records such as " (methyl) acryloyl group " and " (methyl) acrylate " also have the same meaning.

As (b), such as (methyl) glycidyl acrylate, vinylbenzyl glycidyl base ether, (first can be enumerated Base) acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2,6] last of the ten Heavenly stems ester, 3- ethyl -3- (methyl) acryloyloxymethyl oxetanes, (methyl) tetrahydrofurfuryl acrylate etc., preferably (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2,6] last of the ten Heavenly stems ester, 3- ethyl -3- (methyl) acryloyloxymethyl oxetanes.

As (c), such as (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ring can be enumerated Own ester, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, (methyl) third Olefin(e) acid benzyl ester, (methyl) acrylic acid 2- hydroxy methacrylate, N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl horse Come acid imide, styrene, vinyltoluene etc..Preferably styrene, vinyltoluene, N-phenylmaleimide, N- hexamethylene Base maleimide, N- benzyl maleimide etc..

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000~100,000, more preferably 5,000~ 50,000, further preferably 5,000~30,000.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) is preferably 1.1~6, more preferably It is 1.2~4.

The acid value of resin (B) is in terms of solid component conversion, preferably 50~170mg-KOH/g, more preferably 60~ 150mg-KOH/g, further preferably 70~135mg-KOH/g.Acid value herein is with hydrogen-oxygen needed for neutralizing 1g resin (B) Change the value of amount (mg) measurement of potassium, such as can be found out with potassium hydroxide aqueous solution titration.

Relative to the total amount of solid component, the content of resin (B) is preferably 7~65 mass %, more preferably 13~60 matter Measure %, further preferably 17~55 mass %.

Cyan colored curable resin composition of the invention can except colorant (A1) containing dyestuff (A2-1) and Pigment (A2-2) is used as colorant (A2).

Dyestuff (A2-1) is not particularly limited, well known dyestuff can be used, such as solvent dye, acid dye can be enumerated Material, direct dyes, mordant dye etc..As dyestuff, such as can enumerate in color index (TheSociety of Dyers And Colourists publish) in be classified as except pigment the compound with the compound of tone, dyeing notes (color dye Society) in record well known dyestuff.In addition, azo dyes, cyanine dye, triphenyl methane can be enumerated according to chemical structure Dyestuff, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, Squaraine dye, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc..Wherein, preferably organic Solvent-soluble dye.In addition, as dyestuff, it is possible to use Japanese Unexamined Patent Publication 2015-28121 bulletin, Japanese Unexamined Patent Publication 2013- The dyestuff recorded in No. 7032 bulletins, Japanese Unexamined Patent Publication 2013-144724 bulletin, Japanese Unexamined Patent Publication 2013-53292 bulletin etc..

It as pigment (A2-2), is not particularly limited, well known pigment can be used, such as can enumerate in color index The pigment of pigment is classified as in (The Society of Dyers and Colourists publication).

As pigment, for example, can enumerate C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83, 86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214 Equal yellow uitramarines；

C.I. the orange pigments such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215, 216, red pigments such as 224,242,254,255,264,265 etc..

Relative to the total amount of solid component, the content of colorant (A2) is preferably 0.1~60 mass %, and more preferably 0.5 ~55 mass %, further preferably 1~50 mass %.

Here, " total amount of solid component " in this specification refers to the total amount from cyan colored curable resin composition In subtract amount obtained from solvent content.The total amount of solid component and the content of each ingredient relative to the amount can be for example, by Analysis means well known to liquid chromatogram or gas-chromatography etc. measure.

Polymerizable compound (C) is polymerize using living radical and/or the acid generated by polymerization initiator (D) Compound, such as the compound etc. of the ethylenic unsaturated bond with polymerism can be enumerated, preferably (methyl) acroleic acid esterification Close object.

Wherein, polymerizable compound (C) is preferably the polymerizable compound having there are three the above ethylenic unsaturated bond.As This polymerizable compound, such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third can be enumerated Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) Acrylate etc..

The weight average molecular weight of polymerizable compound (C) is preferably 150~2900, and more preferable 250~1,500.

Relative to the total amount of solid component, the content of polymerizable compound (C) is preferably 7~65 mass %, more preferably 13~60 mass %, further preferably 17~55 mass %.

Polymerization initiator (D) can cause polymerization as long as to generate living radical, acid etc. by the effect of light, heat Compound, then there is no particular restriction, and well known polymerization initiator can be used.As generate living radical polymerization initiator, Such as N- benzoyloxy -1- (4- Phenylsulfanyl phenyl) butyl- 1- ketone -2- imines, N- benzoyloxy -1- can be enumerated (4- Phenylsulfanyl phenyl) octyl- 1- ketone -2- imines, N- benzoyloxy -1- (4- Phenylsulfanyl phenyl) -3- cyclopenta Propyl- 1- ketone -2- imines, 2- methyl -2- morpholino -1- (4- methylsulfanyl phenyl) propyl- 1- ketone, 2- dimethylamino -1- (4- Morphlinophenyl) -2- benzyl butyl- 1- ketone, bis- (the trichloromethyl) -6- piperonyls -1,3 of 1- hydroxycyclohexylphenylketone, 2,4-, 5- Triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'- bis- (2- chlorphenyls) -4,4 ', 5,5'- tetraphenyls join miaow Azoles etc..

Relative to 100 mass parts of total amount of resin (B) and polymerizable compound (C), the content of polymerization initiator (D) is preferred For 0.1~30 mass parts, more preferably 1~20 mass parts.When the content of polymerization initiator (D) within the above range when, it is sensitive Degree tends to improve and the time for exposure tends to shorten, therefore the productivity of colour filter improves.

Cyan colored curable resin composition of the invention can contain polymerization trigger auxiliary agent.

Polymerization trigger auxiliary agent (D1) is the change of the polymerization for the polymerizable compound polymerizeing for promoting polymerization initiator to cause Close object or sensitizer.When containing polymerization trigger auxiliary agent (D1), usually it is applied in combination with polymerization initiator (D).

As polymerization trigger auxiliary agent (D1), bis- (dimethylamino) benzophenone (the commonly referred to as rice Chi of 4,4'- can be enumerated Ketone), bis- (diethylamino) benzophenone of 4,4'-, 9,10- dimethoxy anthracene, 2,4- diethyl thioxanthone, N-phenylglycine Deng.

Total amount 100 when using these polymerization trigger auxiliary agent (D1), relative to resin (B) and polymerizable compound (C) Mass parts, content are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.When the amount of polymerization trigger auxiliary agent (D1) exists When within the scope of this, it can tend to improve with more highly sensitive formation colored pattern, the productivity of colour filter.

Cyan colored curable resin composition of the invention preferably comprises solvent.

Solvent (E) is not particularly limited, solvent usually used in the field can be used.Such as ester solvent can be enumerated (containing-COO- and without the solvent of-O- in molecule), ether solvents (containing-O- and without the solvent of-COO- in molecule), ether-ether Solvent (solvent for containing-COO- and-O- in molecule), ketone solvent (containing-CO- and without the solvent of-COO- in molecule), alcohol are molten Agent (containing-OH, the solvent without-O- ,-CO- and-COO- in molecule), aromatic solvent, amide solvent, dimethyl sulfoxide etc..

As solvent, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acid, n-butyl acetate, butyric acid second can be enumerated The ester solutions such as ester, butyl butyrate, ethyl pyruvate, methyl acetoacetate, adnoral acetate and gamma-butyrolacton (contain in molecule There is-COO- and be free of the solvent of-O-)；Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3- methoxyl group -1- fourth The ether solvents such as alcohol, diethylene glycol dimethyl ether, diethylene glycol (DEG) ethyl methyl ether (containing-O- and without the solvent of-COO- in molecule)；

3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, acetic acid 3- methoxybutyl, propylene glycol monomethyl ether acetic acid The ether-ethers solvents such as ester, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid esters (contain the molten of-COO- and-O- in molecule Agent)；

The ketone solvents such as 4- hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2 pentanone, cyclohexanone (contain-CO- in molecule And be free of the solvent of-COO-)；The alcoholic solvents such as butanol, cyclohexanol, propylene glycol (in molecule contain-OH, without-O- ,-CO- and- The solvent of COO-) etc..The acyls such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone can be enumerated Amine solvent.

As solvent, more preferable propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone and 3- second Oxygroup ethyl propionate.

It is molten relative to the total amount of cyan colored curable resin composition of the invention in the case where containing solvent (E) The content of agent (E) is preferably 70~95 mass %, more preferably 75~92 mass %.In other words, cyan colored curable resin The total amount of the solid component of composition is preferably 5~30 mass %, more preferably 8~25 mass %.When the content of solvent (E) exists When in above range, flatness when coating can become well, and when forming colour filter, since colour saturation will not be insufficient, Thus display characteristic tends to be good.

If desired, cyan colored curable resin composition of the invention may include levelling agent, filler, other high scores The additives well known in the art such as sub- compound, closely sealed promotor, antioxidant, light stabilizer, chain-transferring agent.

Cyan colored curable resin composition of the invention can be by by colorant (A1), resin (B), polymerism Object (C), polymerization initiator (D), solvent (E) when necessary and other compositions are closed to mix and prepare.

As the method by cyan colored curable resin composition manufacture colored pattern of the invention, photoetching can be enumerated Method, ink-jet method, print process etc..Wherein, preferred photoetching process.

, it is preferable to use xy in the CIE1931 colour system that the characteristic function of illuminant-C measures in colour filter of the invention Coordinate (x, y) in chromatic diagram meets x²+y²≤ 0.035 relationship, more preferably meets x²+y²≤ 0.030 relationship, further It is preferred that the coordinate (x, y) in xy chromatic diagram in CIE1931 colour system is served as reasons (0.120,0.080), (0.120,0.105), Range encircled by (0.136,0.080) and (0.136,0.105).

Cyan colored curable resin composition can be prepared by containing cyan colorant and compound Y as colorant With the colour filter of especially excellent lightness in high chroma region.The colour filter can be used as display device (such as liquid crystal display dress Set, organic el device, Electronic Paper etc.) and solid-state imager used in colour filter.

[embodiment]

Hereinafter, by enumerating embodiment so that the present invention will be described in more detail, but the present invention is not by following embodiment Limitation, and the present invention can of course be implemented after carrying out modification appropriate in the range of meeting above-mentioned and following objective, And it is all these to be included in technical scope of the invention.

[synthesis example 1]

It reacts and carries out under nitrogen atmosphere below.50 parts of formula (C-I- are put into the flask equipped with condenser and agitating device 2) compound indicated and 188 parts of n,N-Dimethylformamide, are stirred 30 minutes when being cooled with an ice bath.It is thrown into the flask Enter 40 parts of potassium tert-butoxides (Tokyo chemical conversion industry (strain) manufacture), is futher stirred when being cooled with an ice bath 1 hour.Keep ice bath cold But 55.6 parts of iodoethane (Tokyo chemical conversion industry (strain) manufacture) is added dropwise in reaction solution.Reaction solution is warming up to 35 DEG C using oil bath And after stirring 5 hours, it is cooled to room temperature.1000 part of 10% aqueous sodium chloride is added in another flask for having agitating device Liquid instills above-mentioned reaction solution while stirring.After stirring 30 minutes, solid is obtained by filtration.500 parts of ions of obtained solid are handed over It changes water washing three times, and is dried under reduced pressure at 60 DEG C, obtain 53.0 parts of compounds indicated by formula (C-I-3).Yield 93.5%.

Reaction below carries out under nitrogen atmosphere.26.4 parts of sulphur cyanogen are put into the flask equipped with condenser and agitating device Sour potassium and 156 parts of acetonitriles, are then stirred at room temperature 30 minutes.By 40.0 parts of 2,6- difluoro benzoyl chloride (Tokyo chemical conversion industries (strain) manufacture) be added drop-wise in 30 minutes in above-mentioned flask after, 1 hour is stirred at room temperature.By 30.6 parts in 30 minutes N- ethyl-ortho-toluidine (Tokyo chemical conversion industry (strain) manufacture) is added drop-wise in above-mentioned flask, is then stirred at room temperature 1 hour.It will 79.2 parts of chloroacetic acid sodium are dissolved in the aqueous solution prepared in 120 parts of ion exchange waters and are added in above-mentioned flask, are added 60.4 After the sodium hydrate aqueous solution of part 30%, it is stirred at room temperature 18 hours.600 parts of ions are further added into above-mentioned flask to hand over After changing water, stirs 1 hour, the white-yellowish solid of precipitation is collected by filtration.Obtained white-yellowish solid is washed with 120 parts of acetonitriles Afterwards, with 560 parts of ion exchange water washings.By 156 parts of ion exchange waters, 35.0 part of 99% acetic acid (and Wako Pure Chemical Industries (strain) system Make) and 156 parts of toluene be put into the flask equipped with agitating device, be stirred at room temperature 2 hours.It is instilled thereto in 10 minutes Then 80.8 part of 30% sodium hydrate aqueous solution stirs 5 minutes, operated by liquid separation and remove water layer.In resulting organic layer 156 parts of ion exchange waters are added, after liquid separation washing, 156 parts of ion exchange waters is added and 0.1 part of 35% hydrochloric acid carries out liquid separation and washes It washs.It is dried under reduced pressure at 35 DEG C after obtained organic layer is concentrated with evaporator, obtains the compound indicated by formula (B-I-3), For white solid.Yield is 43.4 parts, yield 58.0%.

Reaction below carries out under nitrogen atmosphere.In the flask equipped with condenser and agitating device, be added 13.2 parts by The compound of formula (B-I-3) expression, 19.0 parts of compounds and 38 parts of toluene indicated by formula (C-I-3), are then added 9.2 parts of chlorine Phosphorous oxide stirs 7 hours at 100 DEG C.Then reaction mixture is cooled to room temperature, is then diluted with 29 parts of methyl ethyl ketone.With Afterwards, the mixed solution of 114 parts of ion exchange waters and 10 part of 35% aqueous hydrochloric acid solution is poured into diluted reaction mixture, is passed through Liquid separation operation removes water layer.Obtained organic layer will be dried under reduced pressure at 60 DEG C after dissolving distillation with evaporator, thus The compound indicated by formula (X-II-7) is obtained, for green violet solid.The yield of green violet solid is 39.4 parts.

Reaction below carries out under nitrogen atmosphere.In the flask equipped with condenser and agitating device, be added 38.4 parts by The compound and 112 parts of methylene chloride that formula (X-II-7) indicates stir 30 minutes.Temperature is 10 in ice-cold reaction solution and holding DEG C, after 31.6 parts of chlorosulfonic acids (Tokyo chemical conversion industry (strain) manufacture) is added, reaction solution is warming up to room temperature and is stirred 9 hours. Then reaction solution is ice-cold, 10 DEG C will be kept internal temperature at, with 64 parts of n,N-Dimethylformamide and 4.9 parts of ion exchange waters Mixed solution dilution.Diluted reaction solution is poured into 1120 parts of toluene, after stirring 30 minutes, is settled out viscous solid.It is logical It crosses after discharge oil reservoir is decanted, in the viscous solid that 320 parts of toluene are added to and stirs 30 minutes.Passing through decantation discharge It is solid by the way that cyan is obtained by filtration after 832 part 20% of saline solution is added in the viscous solid obtained after oil reservoir and stirs 1 hour Body.By 576 part of 20% brine It of obtained cyan solid, it is dried under reduced pressure at 35 DEG C.In the burning that agitating device is housed The obtained solid and 128 parts of methanol are put into bottle and are filtered after stirring 30 minutes, and solid and filtrate are separated into.It should Filtrate is known as filtrate A3.The solid of leaching is washed with 128 parts of methanol, is isolated by filtration as solid and filtrate.The filtrate is claimed For liquor B 3.Mixed filtrate A3 and liquor B 3 are dried under reduced pressure at 40 DEG C, obtain by formula (X-I- after removing solvent with evaporator 7) compound as blueness violet solid indicated.The yield of green violet solid is 38.3 parts.

The compound that 28.0 parts are indicated by formula (X-I-7), 43.2 parts of barium chloride dihydrates and 356 parts of ion exchange waters It is added in the flask equipped with condenser and agitating device, after stirring 2 hours at 40 DEG C, filters reaction suspension.By leaching Solid and 350 parts of ion exchange waters are put into the flask equipped with agitating device and after stirring 30 minutes, and suspension is filtered.Will It after 280 parts of ion exchange water washings of the solid arrived, is dried under reduced pressure at 60 DEG C, it is green to obtain the conduct indicated by formula (A-I-7) The compound of violet solid.Yield is 24.5 parts, yield 81.7%.

By the identification of formula (A-I-7) compound indicated

(quality analysis) ionization mode=ESI-:m/z=949.5 [M-Ba+2H]^-

Accurate mass [M-Ba]: 947.28

[synthesis example 2] resin (B-1)

Nitrogen is passed through in right amount in the flask equipped with reflux condenser, dropping funel and blender and is replaced into nitrogen Atmosphere is added 141 parts of ethyl lactates, 178 parts of propylene glycol methyl ether acetates, is heated to 85 DEG C while stirring.Then, small 5 When interior dropwise addition 38 parts of acrylic acid, 25 parts of acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2,6] decyl- 8- base ester and acrylic acid 3,4- epoxy Tricyclic [5.2.1.0^2,6] decyl- 9- base ester mixture (content 1:1), 137 parts of N-cyclohexylmaleimides, 50 parts of methyl-props The mixed solution of olefin(e) acid 2- hydroxy methacrylate, 338 parts of propylene glycol methyl ether acetates.On the other hand, it is added dropwise in 5 hours by 5 parts 2,2- azodiisobutyronitrile is dissolved in mixed solution made of 88 parts of propylene glycol methyl ether acetates.After completion of dropwise addition, identical At a temperature of kept for 4 hours after, be cooled to room temperature, obtain the copolymer of Type B viscosity (23 DEG C) 23mPas, solid component 25.6% (resin (B-1)) solution.The weight average molecular weight Mw of the copolymer of generation is 8000, and solid component acid value is 111mg-KOH/g, point Divergence is 2.1.Resin (B-1) has following structure unit.

[preparation of dispersion liquid 1]

Weigh 8.2 parts of compounds (A-I-7), 6.1 parts of dispersant B YKLPN-6919 (converting by solid component), 2.1 parts of works For resin resin (B-1) (converting by solid component), after 84 parts of propylene glycol methyl ether acetates, 600 parts of 0.4 μm of zirconium oxides are added Pearl is removed by filtration zirconium oxide bead, obtains dispersion liquid 1 after being vibrated 1 hour with coating conditioner (LAU corporation).

[preparation of dispersion liquid 2]

Mix 10 parts of C.I. pigment blue 15s: 6 (pigment), 3.5 parts of acrylic acid series pigment dispersing agents (converting by solid component), 4 parts of resin (B-1) (converting by solid component), 80 parts of propylene glycol methyl ether acetates, 2.6 parts of ethyl lactates as resin make It is with ball mill that pigment is fully dispersed, obtain dispersion liquid 2.

[preparation of dispersion liquid 3]

Mix 13 parts of C.I. pigment yellows 150 (pigment), 3.9 parts of acrylic acid series pigment dispersing agents (converting by solid component), 6.1 parts of resin (B-1) (converting by solid component), 77 parts of propylene glycol methyl ether acetates as resin, will using ball mill Pigment is fully dispersed, obtains dispersion liquid 3.

[embodiment 1]

By mixing following ingredients, cyan colored curable resin composition is obtained.

Cyan colorant: 1 454 parts of dispersion liquid

Cyan colorant: 2 192 parts of dispersion liquid

Compound Y:Y-1: porphyrin compound (FDB-002 (340 DEG C of thermal decomposition temperature)；Hillside plot chemical industry (strain) production)

0.33 part

Resin (B): 33 parts of resin (B-1) (converting by solid portion)

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA；Japanese chemical drug (strain) production) 50 parts

Polymerization initiator (D): N- benzoyloxy -1- (4- Phenylsulfanyl phenyl) octyl- 1- ketone -2- imines (IRGACURE (registered trademark) OXE01；BASF AG's production；O- acyl group oxime compound) 8.0 parts

Solvent (E): 146 parts of cyclohexanone

Solvent (E): 759 parts of propylene glycol methyl ether acetate

Solvent (E): 19 parts of ethyl lactate

Levelling agent (H): polyether modified silicon oil (by solid component conversion) (TORAY SILICONE SH8400；Dong Lidaokang Rather (strain) produces) 0.16 part

[embodiment 2]

In addition to using 0.8 part 5,10,15,20- tetraphenyl -21H, 23H- porphines copper (II) (it is manufactured by Aldrich, Hereinafter referred to as Y-2) it replaces except 0.33 part of Y-1, cyan colored curable resin combination is obtained in the same manner as example 1 Object.

Compound Y, which is dissolved in cyclohexanone, makes its concentration become 0.001 mass %, obtained solution.Use UV, visible light Near infrared spectrometer (V-650；Japan's light splitting (strain) production, uses the quartz cell of 1.0cm square) measure the solution and work For the spectrophotometric spectra of the independent solution of cyclohexanone of blank.The results are shown in Table 10.[table 10]

In the glass substrate (Eagle2000 of 5cm square；Corning Incorporated's production) on, it is solid with spin-coating method coating cyan coloring Change property resin combination after, 100 DEG C prebake 3 minutes, form coloring compositions nitride layer.After letting cool, colour cell will be formd The interval of the substrate and quartz glass photomask that close nitride layer is set as 100 μm, uses exposure machine (TME-150RSK；トプコン (strain) production), under air atmosphere, with 60mJ/cm²Light exposure (on the basis of 365nm) carry out light irradiation.It is covered as light Mould uses the photomask for foring 100 μm of lines and space pattern.Coloring compositions nitride layer after irradiating light at 24 DEG C is containing It impregnates 60 seconds and develops in the aqueous developer solution of 0.12% nonionic surface active agent and 0.04% potassium hydroxide, after washing, In an oven to toast 20 minutes after 230 DEG C, colored pattern is obtained.

About obtained colored pattern, film thickness measuring apparatus (DEKTAK 3 is used；It is raw by Japanese vacuum technique (strain) Produce) measure film thickness.As a result as shown in table 11.

About obtained colored pattern, colour examining machine (OSP-SP-200 is used；Manufactured by Olympus (strain)) measurement point Light spectrum measures xy chromaticity coordinate (x, y) and values Y in CIE1931 colour system using the characteristic function of illuminant-C.Y's It is higher to be worth bigger expression lightness.As a result as shown in table 11.

[table 11]

[embodiment 3]

Cyan colorant: 1 258 parts of dispersion liquid

Cyan colorant: 2 126 parts of dispersion liquid

Compound Y:Y-1: porphyrin compound (FDB-002；Hillside plot chemical industry (strain) production) 0.24 part

Resin (B): 40 parts of resin (B-1) (converting by solid portion)

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 728 parts of propylene glycol methyl ether acetate

Solvent (E): 23 parts of ethyl lactate

Levelling agent (H): polyether modified silicon oil (by solid component conversion) (TORAY SILICONE SH8400；Dong Lidaokang Rather (strain) produces) 0.13 part

[embodiment 4]

Cyan colorant: 1 241 parts of dispersion liquid

Cyan colorant: 2 140 parts of dispersion liquid

Compound Y:Y-2:5,10,15,20- tetraphenyl -21H, 23H- porphines copper (II) (Aldrich production)

0.76 part

Resin (B): 39 parts of resin (B-1) (converting by solid portion)

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 731 parts of propylene glycol methyl ether acetate

Solvent (E): 23 parts of ethyl lactate

[comparative example 1]

Cyan colorant: 1 175 parts of dispersion liquid

Cyan colorant: 2 379 parts of dispersion liquid

3 11.6 parts of dispersion liquid

Resin (B): 31 parts of resin (B-1) (converting by solid portion)

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 761 parts of propylene glycol methyl ether acetate

Solvent (E): 18 parts of ethyl lactate

Levelling agent (H): polyether modified silicon oil (by solid component conversion) (TORAY SILICONE SH8400；Dong Lidaokang Rather (strain) produces) 0.15 part

In the glass substrate (Eagle2000 of 5cm square；Corning Incorporated's production) on, it is solid with spin-coating method coating cyan coloring Change property resin combination after, 100 DEG C prebake 3 minutes, formed coloring compositions nitride layer.After letting cool, coloring compositions will be formd The substrate of nitride layer and the interval of quartz glass photomask are set as 100 μm, use exposure machine (TME-150RSK；トプコン (strain) production), under air atmosphere, with 60mJ/cm²Light exposure (on the basis of 365nm) carry out light irradiation.It is covered as light Mould uses the photomask for foring 100 μm of lines and space pattern.Coloring compositions nitride layer after irradiating light at 24 DEG C is containing It impregnates 60 seconds and develops in the aqueous developer solution of 0.12% nonionic surface active agent and 0.04% potassium hydroxide, after washing, In an oven to toast 20 minutes after 230 DEG C, colored pattern is obtained.

About obtained colored pattern, film thickness measuring apparatus (DEKTAK 3 is used；It is raw by Japanese vacuum technique (strain) Produce) measure film thickness.As a result as shown in table 12.

About obtained colored pattern, colour examining machine (OSP-SP-200 is used；Manufactured by Olympus (strain)) measurement point Light spectrum measures xy chromaticity coordinate (x, y) and values Y in CIE1931 colour system using the characteristic function of illuminant-C.Y's It is higher to be worth bigger expression lightness.As a result as shown in table 12.

[table 12]

[embodiment 5]

Cyan colorant: 1 285 parts of dispersion liquid

Cyan colorant: 2 190 parts of dispersion liquid

Compound Y:Y-3: tetraphenylporphyrin (Cas No.917-23-7 is produced by Tokyo chemical conversion industry (strain))

0.73 part

Resin (B): 48 parts of resin (B-1) (converting by solid portion)

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA；Japanese chemical drug (strain) production) 61 parts

Polymerization initiator (D): N- benzoyloxy -1- (4- Phenylsulfanyl phenyl) octyl- 1- ketone -2- imines (IRGACURE (registered trademark) OXE01；BASF AG's production；O- acyl group oxime compound) 10 parts

Solvent (E): 146 parts of cyclohexanone

Solvent (E): 876 parts of propylene glycol methyl ether acetate

Solvent (E): 28 parts of ethyl lactate

Compound Y-3 (tetraphenylporphyrin (Cas No.917-23-7 is produced by Tokyo chemical conversion industry (strain))) is dissolved in Make concentration become 0.001 mass % in cyclohexanone, obtains solution.Use UV, visible light near infrared spectrometer (V- 650；By Japan's light splitting (strain) production；The quartz cell of 1.0cm square) measure the solution and cyclohexanone as blank is individually molten The spectrophotometric spectra of liquid.As a result as shown in table 13.

[table 13]

About obtained colored pattern, film thickness measuring apparatus (DEKTAK 3 is used；It is raw by Japanese vacuum technique (strain) Produce) measure film thickness.As a result as shown in table 14.

About obtained colored pattern, colour examining machine (OSP-SP-200 is used；Manufactured by Olympus (strain)) measurement point Light spectrum measures xy chromaticity coordinate (x, y) and values Y in CIE1931 colour system using the characteristic function of illuminant-C.Y's It is higher to be worth bigger expression lightness.As a result as shown in table 14.

[table 14]

Claims

1. a kind of cyan colored curable resin composition, it is characterised in that: comprising colorant, resin, polymerizable compound and Polymerization initiator, colorant are the colorant comprising compound Y and cyan colorant, optical path length of the compound Y in 1.0cm When the spectrophotometric spectra of the cyclohexanone solution of the compound Y of the lower measurement of degree containing 0.001 mass %, meet condition 1 below) ~3):

Condition 1) a length of 380nm or more of maximum absorption wave and 450nm hereinafter,

Condition 2) maximum absorption wave strong point absorbance be 3 or more,

Condition 3) absorbance at 460nm is 0.2 or less.

2. cyan colored curable resin composition according to claim 1, wherein green in 100 mass % of colorant The content of chromatic colorant agent is 80 mass of mass %~99.99 %.

3. cyan colored curable resin composition according to claim 1 or 2, wherein in 100 mass % of colorant In, the total content of compound Y is 0.01 mass of mass %~20 %.

4. a kind of colour filter is formed by cyan colored curable resin composition according to claim 1 or 2.

5. colour filter according to claim 4, wherein the CIE1931 table color measured by using the characteristic function of illuminant-C Coordinate (x, y) in system in xy chromatic diagram meets x²+y²≤ 0.035 relationship.

6. a kind of display device, it includes colour filters according to claim 5.