CN106997149A - Colored curable resin composition, colour filter and the display device comprising the colour filter - Google Patents

Abstract

A kind of colored curable resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization initiator (D), comprising the dyestuff with xanthene skeleton as above-mentioned colouring agent (A), above-mentioned polymerizable compound (C) is used as more than 100mgKOH/g polymerizable compound comprising hydroxyl value.

Description

Colored curable resin composition, colour filter and the display device comprising the colour filter

Technical field

The colour filter formed the present invention relates to colored curable resin composition and by the colored curable resin composition Device and display device.

Background technology

In recent years, the exploitation comprising dyestuff as the colored curable resin composition of colouring agent is being actively pushed forward.So And, the heat resistance of dyestuff itself can not be said fully, it is necessary to be supplemented using the transparent compositions beyond colouring agent heat resistance.

A kind of color cured composition for color filter is disclosed in Japanese Unexamined Patent Publication 2009-237151 publications, it contains (A) colouring agent, (B) resin glue, (C) have the photopolymerizable compound of ethylenic unsaturated bond, (D) Photoepolymerizationinitiater initiater and (E) solvent, the photopolymerizable compound that (C) has ethylenic unsaturated bond has hydroxyl, and the hydroxyl value of the photopolymerizable compound is 90mgKOH/g~140mgKOH/g.The number range of the hydroxyl value is considered as in view of the development of cured composition for color is removed Property.

The content of the invention

The present invention provides colored curable resin composition, colour filter and display device as shown below.

[1] a kind of colored curable resin composition, which contain toner (A), resin (B), polymerizable compound (C) and Polymerization initiator (D), wherein,

Comprising the dyestuff with xanthene skeleton as the colouring agent (A),

Comprising hydroxyl value the polymerizable compound (C) is used as more than 100mgKOH/g polymerizable compound.

[2] colored curable resin composition as described in [1], wherein, hydroxyl value is more than 100mgKOH/g polymerism Compound is pentaerythritol triacrylate.

[3] colored curable resin composition as any one of [1]~[3], wherein,

The content of polymerizable compound (C) is relative to the ratio between content of resin (B) (content/tree of polymerizable compound (C) The content of fat (B)) it is 0.6~5 by quality ratio.

[4] colored curable resin composition as any one of [1]~[3], wherein,

The content of polymerizable compound (C) is relative to the ratio between content of resin (B) (content/tree of polymerizable compound (C) The content of fat (B)) it is 0.75~5 by quality ratio.

[5] colored curable resin composition as any one of [1]~[4], wherein,

Colouring agent (A) also includes C.I. pigment blue 15s：6.

[6] colored curable resin composition as any one of [1]~[5], wherein,

The content of dyestuff with xanthene skeleton is 1~50 mass % in the mass % of colouring agent (A) 100.

[7] as any one of [1]~[6] colored curable resin composition is comprising oxime compound is made For polymerization initiator (D).

[8] a kind of colour filter, it is as the colored curable resin composition shape any one of above-mentioned [1]~[7] Into.

[9] a kind of display device, it includes the colour filter described in above-mentioned [8].

Embodiment

＜ colored curable resin compositions ＞

The colored curable resin composition of the present invention is comprising colouring agent (A), resin (B), polymerizable compound (C) and gathers Initiator (D) is closed, colouring agent (A) includes the dyestuff with xanthene skeleton and is used as above-mentioned colouring agent (A).In addition, in the present invention, Comprising hydroxyl value polymerizable compound (C) is used as more than 100mgKOH/g polymerizable compound.

According to the colored curable resin composition, it can be formed and show good brightness (lightness) even and if comprising dye Material, heat resistance also excellent colour filter.

It should be noted that the compound illustrated in this manual as each composition as long as no special declaration with regard to energy Enough it is used singly or in combination two or more.

[1] colouring agent (A)

Colouring agent (A) includes dyestuff.

The colored curable resin composition of the present invention includes the dyestuff with xanthene skeleton and (dyestuff is referred to as into Xanthones below Ton dyestuff) it is used as the dyestuff.The colored curable resin composition of the present invention is due to containing polymerizable compound described later and Xanthones Ton dyestuff, thus good brightness can be obtained.Xanthene dye can enumerate C.I. CI 45430s, 52,87,92,289,388, C.I. acid violet 9,30, C.I. alkalescence red 8, C.I. medium reds 27, rose red b, Sulforhodamine G, rhodamine 6G, Japanese Unexamined Patent Publication Xanthene dye, xanthene dye of No. 4492760 records of Japanese Patent No. that 2010-32999 publications are recorded etc..Colouring agent (A) One kind or two or more xanthene dye can be included.

Wherein, the compound (below also referred to as " compound (1) ") that xanthene dye is preferably comprised shown in formula (1) is used as main Composition.

In formula (1), R¹~R⁴Hydrogen atom ,-R are represented independently of one another⁸Or the monovalence aromatic hydrocarbyl of carbon number 6~10, or Person R¹And R²And R³And R⁴The ring for including nitrogen-atoms is each formed together.The hydrogen atom included in the aromatic hydrocarbyl can be through Halogen atom ,-R⁸,-OH ,-OR⁸,-SO₃ ^-,-SO₃H ,-SO₃ ^-M⁺,-CO₂H ,-CO₂R⁸,-SO₃R⁸Or-SO₂NR⁹R¹⁰ Substitution.Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.

R⁵Expression-OH ,-SO₃ ^-,-SO₃H ,-SO₃ ^-M⁺,-CO₂H ,-CO₂ ^-M⁺,-CO₂R⁸,-SO₃R⁸Or- SO₂NR⁹R¹⁰。

M represents 0~5 integer.In the case of integers of the m for more than 2, multiple R⁵Can with it is identical can also mutually not Together.

R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of one another.

M⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺.X represents halogen atom.Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms, Iodine atom.A represents 0 or 1.

R⁸Represent that the hydrogen atom included in the univalent saturated hydrocarbon radical of carbon number 1~20, the saturated hydrocarbyl can be through carbon number 6~10 Aromatic hydrocarbyl or halogen atom substitution ,-the CH included in the saturated hydrocarbyl₂- can be by-S- ,-O- ,-CO- Or-NR¹¹- displacement.R¹¹Represent the aralkyl of hydrogen atom, the univalent saturated hydrocarbon radical of carbon number 1~20 or carbon number 7~10.Exist Multiple R¹¹In the case of, they all or part of can be with identical.

R⁹And R¹⁰Represent to include in the univalent saturated hydrocarbon radical of hydrogen atom or carbon number 1~20, the saturated hydrocarbyl independently of one another Hydrogen atom can replace through-OH or halogen atom ,-the CH included in the saturated aliphatic hydrocarbons₂- can by-S- ,- O- ,-CO- ,-NH- or-NR⁸- displacement, R⁹And R¹⁰It can be mutually bonded and form 3~10 yuan of rings comprising nitrogen-atoms Heterocycle.Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.

R¹~R⁴In the monovalence aromatic hydrocarbyl of carbon number 6~10 can enumerate phenyl, tolyl, xylyl, equal front three Phenyl, propyl group phenyl and butyl phenyl etc..

R¹~R⁴In carbon number 6~10 monovalence aromatic hydrocarbyl preferably have be selected from by-SO₃ ^-,-SO₃H ,-SO₃ ^-M⁺ With-SO₂NR⁹R¹⁰It is at least one kind of as substituent in the group of composition, more preferably with selected from by-SO₃ ^-M⁺With-SO₂NR⁹R¹⁰ At least one kind of in the group of composition is used as substituent.- SO now₃ ^-M⁺Preferably-[SO₃ ^-][⁺N(R¹¹)₄].If R¹~R⁴For These groups, then it is favourable in terms of the colour filter of excellent heat resistance is formed.

R¹And R²The ring and R formed together³And R⁴The ring formed together can for example enumerate following ring.

R⁸~R¹¹In carbon number 1~20 univalent saturated hydrocarbon radical can enumerate methyl, ethyl, propyl group, isopropyl, butyl, Isobutyl group, amyl group, isopentyl, neopentyl, hexyl, heptyl, octyl group, 2- ethylhexyls, nonyl, decyl, dodecyl, 16 The alkyl of the carbon numbers such as alkyl, eicosyl 1~20；Cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl etc. The cycloalkyl of carbon number 3~20.

On R⁸, the aromatic series for the carbon number 6~10 that the hydrogen atom in the univalent saturated hydrocarbon radical of carbon number 1~20 can be substituted Alkyl can enumerate phenyl, tolyl, xylyl, mesitylene base, propyl group phenyl and butyl phenyl etc..In addition, R⁸In - CH₂- by-S- ,-O- ,-CO- or-NR¹¹The group of-displacement can for example enumerate following group.

R⁶And R⁷In the alkyl of carbon number 1~6 can enumerate the alkyl of carbon number 1~6 among the alkyl enumerated above.

- SO₂NR⁹R¹⁰Shown group can enumerate the group shown in following formula.

In above-mentioned formula, X¹Represent halogen atom.X¹In halogen atom can enumerate fluorine atom, chlorine atom and bromine atoms.

R in formula (1)¹¹In the aralkyl of carbon number 7~10 can enumerate benzyl, phenylethyl, phenyl butyl etc..

M⁺For⁺N(R¹¹)₄、Na⁺Or K⁺, it is preferably⁺N(R¹¹)₄。⁺N(R¹¹)₄In, preferably 4 R¹¹Among at least two be carbon number 5 ~20 univalent saturated hydrocarbon radical.In addition, 4 R¹¹Total carbon number be preferably 20~80, more preferably 20~60.

Xanthene dye is more preferably used as main component comprising the compound shown in formula (2).

In formula (2), R²¹~R²⁴Hydrogen atom ,-R are represented independently of one another²⁶Or the monovalence aromatic hydrocarbyl of carbon number 6~10, The hydrogen atom included in the aromatic hydrocarbyl can be through-SO₃- ,-SO₃ ^-M^a+,-SO₃H ,-SO₃R²⁶Or-SO₂NHR²⁶Take Generation.X represents halogen atom.Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.A1 represents 0 or 1.M1 represents 0~ 5 integer.In the case of integers of the m1 for more than 2, multiple R²⁵Can with it is identical can also be mutually different.M^a+Represent⁺N(R²⁷)₄、 Na⁺Or K⁺。

R²⁵Expression-SO₃ ^-,-SO₃ ^-M^a+,-SO₃H or SO₂NHR²⁶。

R²⁶Represent the univalent saturated hydrocarbon radical of carbon number 1~20.4 R²⁷The monovalence saturation of carbon number 1~20 is represented independently of one another Alkyl or benzyl.

R in formula (2)²¹~R²⁴In carbon number 6~10 monovalence aromatic hydrocarbyl can enumerate with as R¹~R⁴In The same group of group that aromatic hydrocarbyl is enumerated.Wherein, preferably：R²¹And R²³For hydrogen atom and R²²And R²⁴For carbon number 6~10 Monovalence aromatic hydrocarbyl, in the case that the hydrogen atom included in the aromatic hydrocarbyl is substituted, the group replaced is- SO₃ ^-,-SO₃ ^-M⁺,-SO₃H ,-SO₃R²⁶Or-SO₂NHR²⁶.In addition, more preferably：R²¹And R²³For hydrogen atom and R²²And R²⁴ For the monovalence aromatic hydrocarbyl of carbon number 6~10, the hydrogen atom included in the aromatic hydrocarbyl can be through-SO₃ ^-M⁺Or- SO₂NHR²⁶Substituted group.If R²¹~R²⁴It is for these groups, then favourable in terms of the colour filter of excellent heat resistance is formed.

R²⁶And R²⁷In carbon number 1~20 univalent saturated hydrocarbon radical can enumerate with as R⁸~R¹¹In saturated hydrocarbyl and The same group of the group enumerated.R²¹~R²⁴In-R²⁶It is preferably hydrogen atom, methyl or ethyl independently of one another.

- SO₃R²⁶With-SO₂NHR²⁶In R²⁶The preferably branched-chain alkyl of carbon number 3~20, more preferably carbon number 6~12 Branched-chain alkyl, more preferably 2- ethylhexyls.

M^a+For⁺N(R²⁷)₄、Na⁺Or K⁺, it is preferably⁺N(R²⁷)₄。⁺N(R²⁷)₄In preferably 4 R²⁷Among at least two be carbon number 5 ~20 univalent saturated hydrocarbon radical.In addition, 4 R²⁷Total carbon number be preferably 20~80, more preferably 20~60.

Xanthene dye preferably comprise one or more of compound shown in formula (1-1)~formula (1-16) as it is main into Point.It should be noted that in formula, Ra represents 2- ethylhexyls.

Among these compounds, the more preferably quaternary ammonium of the sulfonamide compound of C.I. acid reds 289 or C.I. acid reds 289 Salt.Such compound can for example be enumerated shown in formula (1-1)~formula (1-8), formula (1-11) and formula (1-12) respectively Compound.

Alternatively, it is also possible to manufacture by the following method：Make the upper right column by Japanese Unexamined Patent Publication 3-78702 publications page 3 The pigment of method manufacture described in the column of~lower-left carries out after chlorination being reacted with amine as described above.

Other preferred xanthene dyes include one or more of compound shown in formula (1-17)~formula (1-31) It is used as main component.

Compound shown in formula (1-17)~formula (1-31) can be according to Japanese Unexamined Patent Publication 3-78702 publications page 3 Upper right column~lower-left column described in method manufactured.Methods described can for example be enumerated：Make the chemical combination shown in formula (1a) The method that thing is reacted with the compound shown in, formula (1b) and the compound shown in formula (1c).In formula (1b) and formula (1c), R¹ ~R⁴Implication same as above is represented respectively.

Colouring agent (A) can also include pigment beyond the dyestuffs such as xanthene dye.

Pigment can enumerate organic pigment, such as C.I. pigment blue 15s, 15：3、15：4、15：6th, the blue pigment such as 60； C.I. the violet pigment such as pigment violet 1,19,23,29,32,36,38.Wherein, from the viewpoint of good brightness is obtained, pigment Preferably comprise selected from C.I. pigment purples 23, C.I. pigment blue 15s：3、15：At least one kind of pigment in 6, further preferably C.I. Pigment blue 15: 6.Colouring agent (A) can include one kind or two or more pigment.

Pigment can implement rosin processing, be derived using the pigment for being imported with acidic-group or basic group as needed The surface treatment of thing etc., using high-molecular compound etc. to the grafting of surface of pigments processing, utilize the micro- of sulfuric acid particles method etc. Granulated processed utilizes carrying out washing treatment, the utilization ion of ionic impurity for being used for removing the progress such as organic solvent, water of impurity Removing processing of exchange process etc. etc..

Pigment preferable particle size is uniform.By carrying out decentralized processing containing pigment dispersing agent, it is hereby achieved that pigment is molten The dispersible pigment dispersion of dispersed state in liquid.

Pigment dispersing agent can enumerate cation system, anion system, nonionic system, both sexes, Polyester, polynary amine system, third Surfactants such as olefin(e) acid system etc..These pigment dispersing agents can only be used alone a kind, and two or more can also be applied in combination.

Using in the case of pigment dispersing agent, its usage amount be preferably every 100 mass parts of pigment for 100 mass parts with Under, more preferably 5~50 mass parts.If the usage amount of pigment dispersing agent is the scope, has and obtain uniform dispersity The trend of dispersible pigment dispersion.

The content of colouring agent (A) is usually 1~70 in the mass % of solid constituent 100 of colored curable resin composition Quality %, preferably 5~60 mass %, more preferably 8~50 mass %.If the content of colouring agent (A) is in above range, Sufficient colour saturation and mechanical strength are readily obtained when as colour filter." solid constituent of colored curable resin composition " Refer to the total amount of the composition in colored curable resin composition in addition to solvent (E).

The content of xanthene dye in colouring agent (A) etc. is usually more than 1 mass % in the mass % of colouring agent (A) 100, Preferably more than 3 mass %, preferably more than 5 mass %, more preferably more than 10 mass %.The content of above-mentioned dyestuff is in coloring Can be 100 mass % in the mass % of agent (A) 100.

Colouring agent (A) can include pigment, but in this case, the content of dyestuff is in the mass % of colouring agent (A) 100 It can be below 90 mass %, or below 80 mass %, can also be below 70 mass %, or 50 mass % Below.

In the case where colouring agent (A) includes pigment, (dyestuff contains for the mass ratio of the content of dyestuff and the content of pigment The content of amount/pigment) it is usually 1/99~99/1, preferably 3/97~99/1, more preferably 3/97~70/30, it is further excellent Elect 3/97~50/50 as.

Including the C.I. pigment blue 15s as preferred pigments：In the case of 6, content and the C.I. pigment blue 15s of dyestuff：6 Content the mass ratio (content of dyestuff/C.I. pigment blue 15s：6 content) it is preferably 3/97~70/30, more preferably 3/97 ~50/50.It is favourable in terms of high brightness, high-contrast is obtained if mass ratio is the scope.

Colouring agent (A) can contain pigment, as described above, pigment is preferably comprised selected from C.I. pigment Violet 23s, C.I. pigment Indigo plant 15：3、15：At least one kind of pigment in 6, further preferably C.I. pigment blue 15s：6.Go out from the viewpoint for obtaining good brightness C.I. pigment blue 15s in hair, pigment：6 content is preferably more than 50 mass %, more preferably 80 in the mass % of pigment 100 More than quality %, more preferably more than 90 mass %, are still more preferably more than 95 mass %, most preferably 100 matter Measure %.

[2] resin (B)

The colored curable resin composition of the present invention contains one kind or two or more resin (B).Resin (B) is preferably alkali Soluble resin.Alkali-soluble refers to, is dissolved in the property in the developer solution as the aqueous solution of alkali cpd.Such alkali is solvable Property resin can enumerate following resin [K1]~[K6] etc..

Resin [K1]：At least one kind of (a) in the group being made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides [has below When be referred to as " (a) "] with carbon number 2~4 ring-type ether structure and ethylenic unsaturated bond monomer (b) [hereinafter sometimes referred to as " (b) "] copolymer.

Resin [K2]：(a) and (b) and can be from (a) copolymerization monomer (c) (it should be noted that different with (a) and (b)) [hereinafter sometimes referred to as " (c) ") copolymer.

Resin [K3]：(a) with the copolymer of (c).

Resin [K4]：Make (b) and (a) and (c) copolymer reacted obtained from resin.

Resin [K5]：Make (a) and (b) and (c) copolymer reacted obtained from resin.

Resin [K6]：The copolymer of (a) and (b) and (c) is set to be reacted, further be reacted carboxylic acid anhydrides and be obtained Resin.

(a) it can specifically enumerate：

(methyl) acrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to vinyl benzoic acid etc. no Saturation monocarboxylic acid；

The adjacent benzene of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl Dioctyl phthalate, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1st, the unsaturated dicarboxylic such as 4- cyclohexene dioctyl phthalate；

Bicyclic [2.2.1] hept-2-ene" of methyl -5- ENBs -2,3- dicarboxylic acids, 5- carboxyls, 5,6- dicarboxyls Bicyclic [2.2.1] hept-2-ene" of base, 5- carboxyl -5- methyl bicycles [2.2.1] hept-2-ene", 5- carboxyl -5- ethyls Bicyclic [2.2.1] hept-2-ene", 5- carboxyl -6- methyl bicycles [2.2.1] hept-2-ene", 5- carboxyl -6- ethyls are double The bicyclic unsaturated compounds containing carboxyl such as ring [2.2.1] hept-2-ene"；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids Acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic acid The unsaturated dicarboxylic acid anhydrides such as the acid anhydrides (carbic anhydride) of bicyclic [2.2.1] hept-2-ene" of acid anhydride, 5,6- dicarboxyls；

Mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) acryloxy Ethyl] more than the binary such as ester polybasic carboxylic acid single [(methyl) acryloxyalkyl] ester of unsaturation；

Unsaturation (methyl) third of α-(methylol) (methyl) acrylic acid etc containing hydroxyl and carboxyl in identical molecule Olefin(e) acid etc..

Wherein, from copolyreaction from the viewpoint of viewpoint, the dissolubility in alkaline aqueous solution, (a) is preferably (first Base) acrylic acid, maleic anhydride etc..

It should be noted that in this manual, " (methyl) acrylic acid " represents to be selected from by acrylic acid and methacrylic acid It is at least one kind of in the group of composition.It is also same for the statement such as " (methyl) acryloyl group " and " (methyl) acrylate ".

(b) refer to that the ring-type ether structure with carbon number 2~4 (is selected from by oxirane ring, oxetanes ring and four Hydrogen furan nucleus (tetrahydrofuran ring) composition group in it is at least one kind of) and ethylenic unsaturated bond polymerizable compound.(b) it is excellent Elect the monomer of ring-type ether structure and (methyl) acryloxy with carbon number 2~4 as.

(b) can enumerate the monomer (b1) [hereinafter sometimes referred to as " (b1) "] with epoxy ethyl and ethylenic unsaturated bond, Monomer (b2) [hereinafter sometimes referred to as " (b2) "] with oxetanylmethoxy and ethylenic unsaturated bond, with tetrahydrofuran base and alkene Belong to monomer (b3) [hereinafter sometimes referred to as " (b3) "] of unsaturated bond etc..

(b1) can enumerate has the monomer (b1-1) for making the structure after unsaturated fatty hydrocarbons epoxidation [below sometimes Referred to as " (b1-1) "], with the monomer (b1-2) for making the structure after the oxidation of unsaturated lipid ring type hydrocarbon ring [hereinafter sometimes referred to as " (b1-2) "].

(b1-1) (methyl) Glycidyl Acrylate, (methyl) acrylic acid Beta-methyl polyglycidyl, (first can be enumerated Base) propenoic acid beta-ethyl polyglycidyl, glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl Glycidyl ethers, vinyl benzyl vinyl benzyl glycidyl ether, the adjacent vinyl benzyl glycidyl ether of Alpha-Methyl, Alpha-Methyl Glycidyl ethers, Alpha-Methyl are to vinyl benzyl glycidyl ether, 2,3- double (glycidyl oxy methyl) styrene, 2,4- Double (glycidyl oxy methyl) styrene of double (glycidyl oxy methyl) styrene, 2,5-, 2,6- are double, and (shrink is sweet Oil base epoxide methyl) styrene, 2,3,4- tri- (glycidyl oxy methyl) styrene, 2,3,5- tri- (glycidyls Epoxide methyl) styrene, 2,3,6- tri- (glycidyl oxy methyl) styrene, 3,4,5- tri- (glycidyl epoxides Methyl) styrene, 2,4,6- tri- (glycidyl oxy methyl) styrene etc..

(b1-2) it can enumerate：One vinylcyclohexene oxide, 1,2- epoxy -4- vinyl cyclohexanes are (for example CELLOXIDE 2000；Daicel chemical industry Co. Ltd. system), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example CYCLOMERA400；Daicel chemical industry Co. Ltd. system), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example CYCLOMER M100；Daicel chemical industry Co. Ltd. system), the compound shown in formula (I), the compound shown in formula (II) Deng.

In formula (I) and formula (II), R^aAnd R^bRepresent to wrap in the alkyl of hydrogen atom or carbon number 1~4, the alkyl independently of each other The hydrogen atom contained can replace through hydroxyl.X¹And X²Singly-bound, *-R are represented independently of each other^c-, *-R^c- O-, *-R^c- S- or *-R^c- NH-.R^cRepresent the alkane diyl of carbon number 1~6.* the connection position with O is represented.

The alkyl of carbon number 1~4 can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl group etc..

The alkyl that hydrogen atom replaces through hydroxyl can enumerate methylol, 1- hydroxyethyls, 2- hydroxyethyls, 1- hydroxyls Propyl group, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxyls Base butyl, 2- hydroxybutyls, 3- hydroxybutyls, 4- hydroxybutyls etc..

R^aAnd R^bPreferably hydrogen atom, methyl, methylol, 1- hydroxyethyls, 2- hydroxyethyls, more preferably hydrogen atom, Methyl.

Constitute R^cAlkane diyl can enumerate methylene, ethylidene, propane -1,2- diyl, propane -1,3- bis- Base, butane-Isosorbide-5-Nitrae-diyl, pentane -1,5- diyl, hexane -1,6- diyl etc..

X¹And X²Preferably singly-bound, methylene, ethylidene, *-CH₂- O- (* represents the connection position with O) base, *- CH₂CH₂- O- bases, more preferably singly-bound, *-CH₂CH₂- O- bases.

The concrete example of compound shown in formula (I) can enumerate the compound shown in formula (I-1)~formula (I-15).It is preferred that For formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)~formula (I-15), it is more preferably Formula (I-1), formula (I-7), formula (I-9), formula (I-15).

The concrete example of compound shown in formula (II) can enumerate the compound shown in formula (II-1)~formula (II-15). Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)~formula (II- 15), more preferably formula (II-1), formula (II-7), formula (II-9), formula (II-15).

The compound shown in compound and formula (II) shown in formula (I) each can be used alone.They can also with appoint Ratio of anticipating mixing.In the case of being mixed, the blending ratio is with formula (I)：Formula (II) [mol ratio] meter is preferably 5：95~95： 5, more preferably 10：90~90：10, more preferably 20：80~80：20.

Monomer (b2) with oxetanylmethoxy and ethylenic unsaturated bond is preferably to have oxetanylmethoxy and (methyl) third The monomer of alkene acyloxy.(b2) preference can enumerate 3- methyl -3- (methyl) acryloyloxymethyls oxetanes, 3- ethyls -3- (methyl) acryloyloxymethyls oxetanes, 3- methyl -3- (methyl) acrylyl oxy-ethyl oxa- ring Butane, 3- ethyls -3- (methyl) acrylyl oxy-ethyl oxetanes.

Monomer (b3) with tetrahydrofuran base and ethylenic unsaturated bond is preferably to have tetrahydrofuran base and (methyl) third The monomer of alkene acyloxy.

(b3) preference can enumerate tetrahydrofurfuryl acrylate (such as VISCOAT V#150, Osaka Organic Chemical Industry Co. Ltd. system), tetrahydrofurfuryl methacrylate etc..

(c) concrete example can be enumerated：

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding Ester, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) dodecylacrylate, (methyl) Lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) Acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decane -8- base esters [in the technical field, " (methyl) acrylic acid bicyclopentyl ester " is referred to as trivial name.In addition, being sometimes referred to as " the ring last of the ten Heavenly stems of (methyl) acrylic acid three Ester "], the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decene -8- base esters [in the technical field, are referred to as trivial name " (methyl) acrylic acid dicyclopentenyl base ester "], (methyl) acrylic acid bicyclopentyl epoxide ethyl ester, (methyl) isobomyl acrylate Ester, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) acrylic acid (methyl) acrylate such as phenyl ester, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；

(methyl) acrylic acid of the hydroxyls such as (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters Ester；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate；

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycles [2.2.1] hept-2-ene", 5- ethyls are bicyclic [2.2.1] Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5- hydroxyls, bicyclic [2.2.1] hept-2-ene" of 5- methylols, 5- (2 '- Hydroxyethyl) bicyclic [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- methoxyl groups, 5- ethyoxyls be bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5,6- dihydroxy, 5,6- bis- (methylol) bicyclic [2.2.1] Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5,6- bis- (2 '-hydroxyethyl), 5,6- dimethoxys are bicyclic [2.2.1] Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5,6- diethoxies, bicyclic [2.2.1] hept- of 5- hydroxy-5-methyl bases Bicyclic [2.2.1] hept-2-ene" of 2- alkene, 5- hydroxyl -5- ethyls, 5- methylol -5- methyl bicycles [2.2.1] hept- Bicyclic [2.2.1] hept-2-ene" of 2- alkene, 5- tert-butoxycarbonyls, bicyclic [2.2.1] hept-2-ene" of 5- hexamethylene oxygen carbonyls, Bicyclic [2.2.1] hept-2-ene" of 5- carbobenzoxies, 5,6- double (tertbutyloxycarbonyl) bicyclic [2.2.1] hept-2-ene", 5,6- The bicyclic unsaturated compounds such as double (hexamethylene oxygen carbonyls) bicyclic [2.2.1] hept-2-ene"；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimides Base -3- maleimidobenzoyls ester, N- succinimido -4- malimidobutanoates, N- succinimides Base -6- maleimidohexanoic acids ester, N- succinimido -3- maleimidopropionic acids ester, N- (9- acridinyls) horse Carry out the dicarbonyl imides derivative such as acid imide；

Styrene, α-methylstyrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene Ethene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3- dimethyl -1,3-butadiene etc..

Wherein, from the viewpoint of copolyreaction and heat resistance, (c) is preferably (methyl) benzyl acrylate, (methyl) Acrylic acid tricyclodecyl, styrene, N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides Amine, bicyclic [2.2.1] hept-2-ene" etc..In addition, developability when being formed for pattern is excellent, (c) is more preferably (methyl) third Olefin(e) acid benzyl ester, (methyl) acrylic acid tricyclodecyl.

In resin [K1], the ratio from respective construction unit is preferably in the entire infrastructure unit for constituting resin [K1] In following scope.

Construction unit from (a)：2~50 moles of % (more preferably 10~45 moles of %),

Construction unit from (b), the construction unit for being especially derived from (b1)：50~98 moles of % (more preferably 55~90 Mole %).

If the ratio of the construction unit of resin [K1] is in above range, there are storage stability, developability, gained pattern Excellent solvent resistance trend.

Resin [K1] may be referred to document " experimental method of Polymer Synthesizing " (big Jin Longhangzhu sale rooms Co., Ltd. chemistry With the printing of people the 1st edition the 1st time distribution on March 1st, 1972) described in method and the citation recorded in the publication enter Row manufacture.

Specifically, following method can be enumerated：By (a) and (b) (especially (b1)) ormal weight, polymerization initiator and molten In the input reaction vessel such as agent, it is stirred, heats, is incubated under deoxidizing atmosphere.It should be noted that polymerization used herein Initiator and solvent etc. are not particularly limited, and in the field, usually used polymerization initiator and solvent etc. can be used.It is poly- Azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo pair (2,4- methyl pentane nitrile) can be enumerated by closing initiator Deng), organic peroxide (benzoyl peroxide etc.).As long as solvent dissolves each monomer, colored curable resin group is used as The solvent of compound can use solvent (E) for being described below etc..

Resulting copolymer can directly use reacted solution, can also use the solution after concentration or dilution, The solid (powder) taken out using methods such as reprecipitations can also be used.Particularly, in the polymerization, by using described later molten Agent (E) can directly use reacted solution, can simplify manufacturing process as solvent.

In resin [K2], the ratio from respective construction unit is preferred in the entire infrastructure unit for constituting resin [K2] In following scope.

Construction unit from (a)：4~45 moles of % (more preferably 10~30 moles of %),

Construction unit from (b), the construction unit for being especially derived from (b1)：2~95 moles of % (more preferably 5~80 rub You are %),

Construction unit from (c)：1~65 mole of % (more preferably 5~60 moles of %).

If the ratio of the construction unit of resin [K2] is in above range, there are storage stability, developability, gained pattern Solvent resistance, the trend of heat resistance and mechanical strength.

Resin [K2] can be manufactured in the same manner as the method that the manufacture method as resin [K1] is recorded.It is specific next Say, following method can be enumerated：(a), (b) (especially (b1)) and (c) ormal weight, polymerization initiator and solvent are put into and reacted In container, it is stirred, heats, is incubated under deoxidizing atmosphere.Resulting copolymer can directly use reacted solution, The solution after concentration or dilution can also be used, the solid (powder) taken out using methods such as reprecipitations can also be used.

In resin [K3], the ratio from respective construction unit is preferred in the entire infrastructure unit for constituting resin [K3] In following scope.

Construction unit from (a)：2~55 moles of % (more preferably 10~50 moles of %),

Construction unit from (c)：45~98 moles of % (more preferably 50~90 moles of %).

Resin [K3] can be manufactured in the same manner as the method that the manufacture method as resin [K1] is recorded.

Resin [K4] can be manufactured as follows：(a) and (c) copolymer are obtained, makes the cyclic ether for the carbon number 2~4 that (b) have Thus the oxirane cycloaddition that structure, especially (b1) have manufactures in (a) carboxylic acid having and/or carboxylic acid anhydrides.It is specific next Say, first, (a) and (c) copolymer are manufactured in the same manner as the method that the manufacture method as resin [K1] is recorded.The situation Under, the ratio from respective construction unit is preferably in following in the entire infrastructure unit of (a) with the copolymer of (c) is constituted Scope.

Construction unit from (a)：5~50 moles of % (more preferably 10~45 moles of %),

Construction unit from (c)：50~95 moles of % (more preferably 55~90 moles of %).

Then, make the ring-type ether structure for the carbon number 2~4 that (b) have, oxirane ring that especially (b1) has with it is above-mentioned common A part for carboxylic acid from (a) and/or carboxylic acid anhydrides in polymers is reacted.Specifically, and then (a) and (c) are total to The manufacture of polymers, air is replaced as by atmosphere in flask by nitrogen, by (b) (especially (b1)), carboxylic acid or carboxylic acid anhydrides and cyclic ether knot Catalysts (three (dimethylamino methyl) phenol etc.) and polymerization inhibitor (hydroquinones etc.) of structure etc. add flask in, by The reaction of 60~130 DEG C of progress 1~10 hour, it is hereby achieved that resin [K4].

(b) usage amount, especially (b1) usage amount are preferably 5~80 moles relative to 100 moles of (a), more preferably 10~75 moles.By setting the scope, then there are storage stability, developability, solvent resistance, heat resistance, mechanical strength and spirit The good trend of balance of sensitivity.Reactive high, unreacted (b) for ring-type ether structure is difficult residual, preferably (b1) work For (b) used in resin [K4], more preferably (b1-1).

The usage amount of above-mentioned catalysts is preferably 0.001 relative to (a), (b) (especially (b1)) and the total amount of (c) ~5 mass %.The usage amount of above-mentioned polymerization inhibitor is preferably 0.001~5 mass % relative to the total amount of (a), (b) and (c).

The reaction conditions such as feeding method, reaction temperature and time can contemplate manufacturing equipment, the caloric value obtained by polymerization Deng appropriate adjustment.It should be noted that manufacturing equipment, the caloric value obtained by polymerization etc. can be considered in the same manner as polymerizing condition Suitably adjust feeding method, reaction temperature.

For resin [K5], as the first stage, carry out, obtain in the same manner as the manufacture method of above-mentioned resin [K1] To the copolymer of (b) (especially (b1)) and (c).Same as above, resulting copolymer can be directly using reacted molten Liquid, can also use the solution after concentration or dilution, can also use the solid (powder) taken out using methods such as reprecipitations.

The ratio of construction unit from (b) (especially (b1)) and (c) is relative to the entire infrastructure for constituting above-mentioned copolymer Total mole of unit is preferably in following scope.

Construction unit from (b), the construction unit for being especially derived from (b1)：5~95 moles of % (more preferably 10~90 rub You are %),

Construction unit from (c)：5~95 moles of % (more preferably 10~90 moles of %).

In addition, under conditions of same with the manufacture method of resin [K4], making carboxylic acid or carboxylic acid anhydrides and (b) that (a) has The ring-type ether structure from (b) that the copolymer of (especially (b1)) and (c) has is reacted, it is hereby achieved that resin [K5].Above-mentioned (a) that makes to be reacted with copolymer usage amount is preferably 5 relative to 100 moles of (b) (especially (b1))~ 80 moles.For ring-type ether structure reactive high, unreacted (b) be difficult residual, preferably (b1) as resin [K5] system Middle (b) used is made, more preferably (b1-1).

Resin [K6] is carboxylic acid anhydrides is carried out reacted resin with resin [K5].

Reacted carboxylic acid anhydrides and the hydroxyl produced by the reaction of ring-type ether structure and carboxylic acid or carboxylic acid anhydrides.

Carboxylic acid anhydrides can enumerate maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- second Alkenyl phthalic anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl four Acid anhydrides (carbic anhydride) of bicyclic [2.2.1] hept-2-ene" of hydrogen phthalic anhydride, 5,6- dicarboxyls etc..

Among resin [K1]~[K6], as resin (B) it is preferred that resin be [K1] or [K2].Resin (B) can be by 1 Plant resin to constitute, resin of more than two kinds can also be included.

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000~100,000, more preferably 5,000~ 50,000, more preferably 5,000~30,000.If molecular weight is in above range, there is unexposed portion in developer solution Dissolubility height, the residual film ratio of gained pattern, hardness also high trend.Molecular weight distribution [the weight average molecular weight of resin (B) (Mw)/number-average molecular weight (Mn)] it is preferably 1.1~6, more preferably 1.2~4.

The solution acid number of resin (B) is preferably 5~180mg-KOH/g, and more preferably 10~100mg-KOH/g enters one Step is preferably 12~50mg-KOH/g.Acid number is the value determined as the amount (mg) of the potassium hydroxide needed for neutralization resin 1g, It can for example use potassium hydroxide aqueous solution to be titrated thus to obtain.

The content of resin (B) is preferably 5~50 matter in the mass % of solid constituent 100 of colored curable resin composition Measure %, more preferably more preferably 10~40 mass %, 15~30 mass %.If the content of resin (B) is in above-mentioned model Enclose, then have the high trend of dissolubility of the unexposed portion in developer solution.

[3] polymerizable compound (C)

Polymerizable compound (C) is can be by the living radical produced using light irradiation etc. by polymerization initiator (D) Deng the compound being polymerize.The colored curable resin composition of the present invention includes the polymerization that hydroxyl value is more than 100mgKOH/g Property compound is used as polymerizable compound (C).Utilize the colored curable tree of the invention containing the polymerizable compound (C) Oil/fat composition, even if can also form the colour filter of excellent heat resistance as colouring agent (A) comprising dyestuff.

Polymerizable compound (C) can be made up of hydroxyl value for more than 100mgKOH/g a kind of polymerizable compound, can be wrapped Containing the polymerizable compound that hydroxyl value of more than two kinds is more than 100mgKOH/g.In addition, polymerizable compound (C) can be hydroxyl value For more than 100mgKOH/g one kind or two or more polymerizable compound and hydroxyl value be less than a kind or 2 kinds of 100mgKOH/g with On polymerizable compound mixture.In the case of for the mixture, from the viewpoint of heat resistance, polymerizable compound (C) it is more than 100mgKOH/g as the preferred hydroxyl value of the mixture.From the viewpoint of heat resistance, polymerizable compound (C) Hydroxyl value is preferably more than 110mgKOH/g.The hydroxyl value of polymerizable compound (C) is usually below 170mgKOH/g.Hydroxyl value is according to after The record for the embodiment stated is measured.

Polymerizable compound (C) can enumerate the compound of ethylenic unsaturated bond and hydroxyl with polymerism.Polymerism Compound (C) preferably has the ethylenic unsaturated bond of more than 2 in intramolecular, more preferably with more than 3.Hydroxyl value is The concrete example of more than 100mgKOH/g polymerizable compound can be enumerated：The pentaerythritol triacrylate, (first of pentaerythrite two Base) acrylate, ethoxylation pentaerythrite three (methyl) acrylate, pentaerythritol propoxylate triacrylate, three hydroxyls Methylpropane two (methyl) acrylate, ethoxylated trimethylolpropane two (methyl) acrylate, ethoxylated glycerol two (methyl) acrylate, propoxylated glycerol two (methyl) acrylate, two-trimethylolpropane tris (methyl) acrylate, Two-trimethylolpropane tris of ethoxylation (methyl) acrylate, two-trimethylolpropane trimethacrylate of propoxylation etc..

The content of polymerizable compound (C) is with the content relative to the resin (B) in colored curable resin composition Mass ratio (content of content/resin (B) of polymerizable compound (C)) meter is usually 0.2~10, preferably 0.6~8, more excellent Elect 0.6~5, more preferably 0.75~5 as.If above-mentioned mass ratio is within the above range, heat resistance can be obtained More preferably colour film.

[4] polymerization initiator (D)

Polymerization initiator (D) as long as can be produced by the effect of light, heat living radical, acid etc. and trigger polymerization Compound is just not particularly limited, and can use known polymerization initiator.

Polymerization initiator (D) can enumerate the oxime compounds such as O- acyl group oxime compounds, alkyl phenyl assimilation compound, connection Imidazolium compounds, triaizine compounds, acylphosphine oxide compound etc..

Polymerization initiator (D) it is considered that sensitivity, accurate formative of pattern form etc. and and use two or more. For sensitivity and it is accurate make the pattern form with desired line width in terms of it is favourable, polymerization initiator (D) is preferred to be wrapped The oxime compounds such as the oxime compound of acyl group containing O-.

O- acyl groups oxime compound is the compound with the structure shown in formula (d).Hereinafter, * represents connection position.

O- acyl group oxime compounds are preferably selected from as the compound (hereinafter sometimes referred to as " compound shown in formula (d1) (d1) compound shown in compound (hereinafter sometimes referred to as " compound (d2) ") and formula (d3) "), shown in formula (d2) is (following It is sometimes referred to as " compound (d3) ") at least one kind of in the group of composition.

In formula (d1)~(d3),

R^d1Represent can have substituent carbon number 6~18 aromatic hydrocarbyl, can have substituent carbon number 3~36 it is miscellaneous Ring group, can have substituent carbon number 1~15 alkyl or by aromatic hydrocarbyl and by the alkane diyl of the alkyl derivative The methylene (- CH included in the group with substituent of combination, abovementioned alkyl₂-) can be replaced as-O- ,- CO- ,-S- ,-SO₂- or-NR^d5-,

R^d2The alkyl of the aromatic hydrocarbyl, the heterocyclic radical of carbon number 3~36 or carbon number 1~10 of carbon number 6~18 is represented,

R^d3Expression can have the aromatic hydrocarbyl of the carbon number 6~18 of substituent or can have the carbon number 3~36 of substituent Heterocyclic radical,

R^d4Expression can have the aromatic hydrocarbyl of the carbon number 6~18 of substituent or can have the carbon number 1~15 of substituent The methylene (- CH included in aliphatic alkyl, above-mentioned aliphatic alkyl₂-) can be replaced as-O- ,-CO- or- The methine (- CH ＜) included in S-, above-mentioned aliphatic alkyl can be replaced as-PO₃Wrapped in ＜, above-mentioned aliphatic alkyl The hydrogen atom contained can replace through OH bases,

R^d5Represent the methylene (- CH included in the alkyl of carbon number 1~10, the alkyl₂-)-O- can be replaced as Or-CO-.

R^d1The carbon number of shown aromatic hydrocarbyl is preferably 6~15, more preferably 6~12, more preferably 6~10. The aromatic hydrocarbyl can enumerate phenyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl etc., preferably phenyl, naphthyl, more excellent Select phenyl.

R^d1Shown aromatic hydrocarbyl can have the substituent of 1 or more than 2.

Substituent is preferably in the α positions of aromatic hydrocarbyl, γ substitutions, more preferably in γ substitutions.

The substituent can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, ten The alkyl of the carbon numbers such as one alkyl, dodecyl, tridecyl, myristyl, pentadecyl 1~15；Fluorine atom, chlorine atom, iodine The halogen atoms such as atom, bromine atoms；Etc..

It is preferably 1~10 as the carbon number of the alkyl of above-mentioned substituent, more preferably 1~7.It is used as the alkyl of the substituent Can be any of straight-chain, branched and ring-type or by the group of chain and the base of the moiety combinations of ring-type Group.It is used as the methylene (- CH included in the alkyl of the substituent₂-)-O- or-S- can be replaced as.In addition, the alkane The hydrogen atom included in base can replace through halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atoms, preferably be taken through fluorine atom Generation.

In R^d1In shown aromatic hydrocarbyl, group shown in following formula etc. can be enumerated as the alkyl of substituent.Formula In, * represents connection position.

R^d1The shown aromatic hydrocarbyl with substituent can enumerate group shown in following formula etc..In formula, * tables Show connection position.

R^d1The shown aromatic hydrocarbyl with substituent is preferably the group shown in following formula.

(in formula, R^d6Represent the alkyl of carbon number 1~10 that can replace through halogen atom, R^d6In the hydrogen atom that includes can be through halogen Atom replaces.M2 represents 1~5 integer.)

R^d6Shown alkyl can be enumerated and as R^d1The substituent of shown aromatic hydrocarbyl and the alkyl that illustrates is same Group.R^d6Carbon number be preferably 2~7, more preferably 2~5.In addition, R^d6Shown alkyl can be straight-chain, branched Any of with ring-type, preferably chain.

R^d6In halogen atom can enumerate fluorine atom, chlorine atom, iodine atom, bromine atoms, particularly preferred fluorine.It is preferred that R^d6In Comprising more than 2, less than 10 of hydrogen atom replace through halogen atom, more preferably more than 3, less than 6 replace through halogen atom. R^d6The preferred ortho position of the position of substitution of O- bases, contraposition, particularly preferably contraposition.M2 is preferably 1~2, and particularly preferably 1.

R^d1The carbon number of shown heterocyclic radical is preferably 3~20, more preferably 3~10, more preferably 3~5.The heterocycle Base can enumerate pyrrole radicals, furyl, thienyl, indyl, benzofuranyl and carbazyl etc..

R^d1Shown heterocyclic radical can have the substituent of 1 or more than 2.The substituent can be enumerated and as R^d1 Substituent that shown aromatic hydrocarbyl can have and the same group of the group that illustrates.

R^d1The carbon number of shown alkyl is preferably 1~12.R^d1Shown alkyl can enumerate methyl, ethyl, propyl group, fourth Base, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl and pentadecane Base etc..These alkyl can be any of for straight-chain, branched and ring-type, or by the group of chain and ring-type The group of moiety combinations.In addition, R^d1In shown alkyl, methylene (- CH₂-) can be replaced as-O- ,-CO- ,- S- ,-SO₂- or-NR^d5-, hydrogen atom can replace through OH bases or SH bases.

R^d5Represent the alkyl of the alkyl, more preferably carbon number 1~3 of the alkyl, preferably carbon number 1~5 of carbon number 1~10.Should Alkyl can be chain (straight-chain or branched), or ring-type, or appointing in straight-chain, branched and ring-type It is a kind of, or by the group of chain and the group of the moiety combinations of ring-type.R^d5Alkyl in, methylene (- CH₂-) can To be replaced as-O- or-CO-.

R^d1The shown alkyl with substituent can specifically enumerate group shown in following formula etc..* expression connects Connect position.

In addition, R^d1The carbon number of the shown group for combining aromatic hydrocarbyl with alkane diyl is preferably 7~33, more excellent Elect 7~18, more preferably 7~12 as.The group of the combination can have the substituent of 1 or more than 2, the substituent The group same with the group illustrated as the substituent that aromatic hydrocarbyl, alkyl can have can be enumerated.The R^d1Shown The group that aromatic hydrocarbyl is combined with alkane diyl can enumerate aralkyl, can specifically enumerate shown in following formula Group.In formula, * represents connection position.

Wherein, R^d1Can preferably have the aromatic hydrocarbyl of substituent or there can be the alkyl of substituent, more preferably can Aromatic hydrocarbyl with substituent.

R^d2The carbon number of shown aromatic hydrocarbyl is preferably 6~15, more preferably 6~12, more preferably 6~10. The aromatic hydrocarbyl can enumerate phenyl, naphthyl, anthryl, phenanthryl, xenyl and terphenyl etc..

R^d2The carbon number of shown heterocyclic radical is preferably 3~20, more preferably 3~10, more preferably 3~5.The heterocycle Base can enumerate pyrrole radicals, furyl, thienyl, indyl, benzofuranyl and carbazyl etc..

R^d2The carbon number of shown alkyl is preferably 1~7, more preferably 1~5, more preferably 1~3.The alkyl can be with Enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl etc..The alkyl can for straight-chain, Any of branched and ring-type, can be by the group of the group of chain and the moiety combinations of ring-type.

R^d2The preferably chain of the chain-like alkyl of chain-like alkyl, more preferably carbon number 1~5, more preferably carbon number 1~3 Shape alkyl, particularly preferably methyl.

R^d3The carbon number of shown aromatic hydrocarbyl is preferably 6~15, more preferably 6~12, more preferably 6~10. The aromatic hydrocarbyl can enumerate phenyl, naphthyl, anthryl, phenanthryl, xenyl and terphenyl etc., more preferably phenyl, naphthyl.

R^d3Shown aromatic hydrocarbyl can have the substituent of 1 or more than 2.Substituent is preferably in aromatic hydrocarbyl α positions, γ substitution.The substituent is preferably the aliphatic alkyl of carbon number 1~15, specifically, can enumerate methyl, second The alkyl of the carbon numbers such as base, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl 1~15；Vinyl, acrylic, fourth The alkenyl of the carbon numbers 1~15 such as alkenyl, pentenyl, hexenyl, heptenyl, nonenyl and decene base；Etc..

R^d3Shown aromatic hydrocarbyl can have aliphatic alkyl.The carbon number of the aliphatic alkyl is more preferably 1~7, The aliphatic alkyl can be any of straight-chain, branched and ring-type, can be by the base of the group of chain and ring-type The group of group's combination.In addition, the methylene (- CH included in the aliphatic alkyl₂-)-O- ,-CO- can be replaced as Or-S-, methine (- CH ＜) can be replaced as-N ＜.

The aliphatic alkyl can enumerate group shown in following formula etc..In formula, * represents connection position.

R^d3The shown aromatic hydrocarbyl with substituent can enumerate group shown in following formula etc..In formula, * tables Show connection position.

R^d3The carbon number of shown heterocyclic radical is preferably 3~20, more preferably 3~10, more preferably 3~5.The heterocycle Base can enumerate pyrrole radicals, furyl, thienyl, indyl, benzofuranyl and carbazyl etc..In addition, R^d3Shown heterocycle Base can have the substituent of 1 or more than 2, and the substituent can be enumerated and as R^d1Shown aromatic hydrocarbyl can have Substituent and the same group of the group that illustrates.

Wherein, R^d3Preferably there is the aromatic hydrocarbyl of substituent, the substituent is preferably that carbon number 1~7 (is more preferably carbon The chain-like alkyl of number 1~3), the number of substituent is preferably more than 2, less than 5.

R^d4The carbon number of shown aromatic hydrocarbyl is preferably 6~15, more preferably 6~12, more preferably 6~10. The aromatic hydrocarbyl can enumerate phenyl, naphthyl, anthryl, phenanthryl, xenyl and terphenyl etc., more preferably phenyl and naphthyl, Further preferred phenyl.In addition, R^d4Shown aromatic hydrocarbyl can have the substituent of 1 or more than 2.The substituent can To enumerate and R^d1The same group of the substituent that can have of aromatic hydrocarbyl.

R^d4The carbon number of shown aliphatic alkyl is preferably 1~13, more preferably 2~10, more preferably 4~9. R^d4Shown aliphatic alkyl can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, The alkyl such as undecyl, dodecyl, tridecyl, myristyl and pentadecyl；Vinyl, acrylic, cyclobutenyl, amylene Base, hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, dodecenyl succinic, tridecylene base, 14 carbon The alkenyl such as alkenyl and 15 carbene bases；Etc..These aliphatic alkyls can be chain (straight-chain or branched), or Ring-type, or by the group of chain and the group of the moiety combinations of ring-type.R^d4Aliphatic alkyl in, methylene (- CH₂-)-O- ,-CO- or-S- can be replaced as, methine (- CH ＜) can be replaced as-PO₃＜, above-mentioned aliphatic The hydrogen atom included in alkyl can replace through OH bases.

R^d4The shown aliphatic alkyl with substituent can enumerate group shown in following formula etc..In formula, * tables Show connection position.

R^d4Can preferably have the chain fatty race alkyl of substituent, the more preferably chain-like alkyl without substituent, Do not have the branched-chain alkyl of substituent more preferably.

Compound (d1) can enumerate the compound shown in formula (d1), can specifically enumerate with (d1-1) column Compound~formula (d1) institute with each substituent described in (d1-67) column shown in the formula (d1) for each substituent recorded The compound shown.In table 1~7, * represents connection position.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Wherein, it is however preferred to have the compound of the substituent described in (d1-3) column~have described in (d1-6) column The compound of substituent, the compound with the substituent described in (d1-18) column~there is taking described in (d1-52) column Dai Ji compound, the compound with the substituent described in (d1-55) column, with the substitution described in (d1-56) column The compound of base, the compound with the substituent described in (d1-60) column, with the substituent described in (d1-61) column Compound,

More preferably have (d1-3) column described in substituent compound~have (d1-6) column described in taking Dai Ji compound, the compound with the substituent described in (d1-18) column~with the substitution described in (d1-41) column The compound of base,

More preferably have (d1-24) column described in substituent compound, with described in (d1-36) column Substituent compound~have (d1-40) column described in substituent compound,

Particularly preferably there is the compound of the substituent described in (d1-24) column.

Compound (d1) can for example be carried out by the manufacture method described in Japanese Unexamined Patent Application Publication 2014-500852 publications Manufacture.

Compound (d2) is preferably：

R^d1For can have substituent carbon number 1~15 alkyl,

R^d2For the alkyl of carbon number 1~10,

R^d3For can have substituent carbon number 6~18 aromatic hydrocarbyl,

R^d4For that can have the compound of the aliphatic alkyl of the carbon number 1~15 of substituent,

More preferably：

R^d1Expression methyl, ethyl or propyl group,

R^d2Expression methyl, ethyl or propyl group,

R^d3Represent through methyl substituted phenyl,

R^d4For the compound of methyl, ethyl or propyl group,

More preferably：

R^d1And R^d2For methyl, R^d3For o-tolyl and R^d4For the compound of ethyl.

Compound (d3) is preferably：

R^d1For can have substituent carbon number 1~15 alkyl,

R^d2For the compound of the aromatic hydrocarbyl of carbon number 6~18,

More preferably：

R^d1For hexyl and R^d2For the compound of phenyl.

Such O- acyl groups oxime compound can enumerate N- benzoyloxys -1- (4- phenylmercaptos phenyl) fourth Alkane -1- ketone -2- imines, N- benzoyloxys -1- (4- phenylmercaptos phenyl) octane -1- ketone -2- imines, N- benzoyloxys -1- (4- phenylmercaptos phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetyl oxygen Base -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethane -1- imines, N- acetyl Oxy-1-[9- ethyls-6- { 2- methyl-4- (3,3- dimethyl-2,4- dioxolyl methoxyl group) benzene first Acyl group } -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methylbenzenes Formoxyl) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines, N- benzoyloxys -1- [9- second Base -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc.. The cities such as IRGACURE OXE01, OXE02, OXE03 (being above BASF AG's system), N-1919 (ADEKA company systems) can be used Sell product.If these O- acyl group oxime compounds, then have the trend for obtaining the excellent colour filter of lithography performance.

Alkyl phenyl assimilation compound is the compound with the structure shown in the structure shown in formula (d4) or formula (d5).These In structure, phenyl ring can have substituent.

Compound with the structure shown in formula (d4) can enumerate 2- methyl -2- morpholinyls -1- (4- methyl mercaptos Base phenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morpholino phenyls) -2- benzyl butane -1- ketone, 2- (two Methylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone etc..It can make With commercially available products such as IRGACURE369,907,379 (being above BASF AG's system).

Compound with the structure shown in formula (d5) can enumerate 2- hydroxy-2-methyl -1- phenyl-propanes - 1- ketone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxy-cyclohexyls Oligomer, the α of phenyl ketone, 2- hydroxy-2-methyls -1- (4- isopropenyls phenyl) propane -1- ketone, α-diethoxy Benzoylformaldoxime, benzoin dimethylether etc..

From the viewpoint of sensitivity, alkyl phenyl assimilation compound is preferably the chemical combination with the structure shown in formula (d4) Thing.

United imidazole can enumerate 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, see Japanese Unexamined Patent Publication 6-75372 public affairs Report, Japanese Unexamined Patent Publication 6-75373 publications etc.), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4, 4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy benzene Base) bisglyoxaline (for example, see Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc.), 4, 4 ', 5, the imidazolium compounds that the phenyl of 5 '-position replaces through alkoxy carbonyl group is (for example, see Japanese Unexamined Patent Publication 7-10913 publications Deng) etc..Wherein, preferably shown in following formula compound or their mixture.

Triaizine compounds can enumerate double (trichloromethyl) -6- (4- the methoxyphenyls) -1,3,5-triazines of 2,4-, 2,4- double (trichloromethyl) -6- (4- methoxyl groups naphthyl) -1,3,5-triazines, double (the trichloromethyl) -6- peppers of 2,4- Base -1,3,5-triazines, 2,4- double (trichloromethyl) -6- (4- methoxyl-styrenes) -1,3,5-triazines, 2,4- Double (three chloromethanes of double (trichloromethyl) -6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5-triazines, 2,4- Base) -6- [2- (furans -2- bases) vinyl] -1,3,5-triazines, double (trichloromethyl) -6- [2- (4- of 2,4- Lignocaine -2- aminomethyl phenyls) vinyl] -1,3,5-triazines, double (trichloromethyl) -6- [2- (3,4- bis- of 2,4- Methoxyphenyl) vinyl] -1,3,5-triazines etc..

Acylphosphine oxide compound can enumerate TMDPO etc..

In addition, polymerization initiator (D) can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, The benzoin compound such as benzoin isobutyl ether；Benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenones, 4- benzene Formoxyl -4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 2,4,6- front threes The benzophenone cpds such as base benzophenone；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs, camphorquinone；10- butyl- 2- chloro-acridines ketone, benzyl, phenylglyoxalates methyl esters, titanocenes compound etc..They preferably polymerize initiation auxiliary agent with described later (D1) (especially amine) is applied in combination.

The content of polymerization initiator (D) is excellent relative to the mass parts of total amount 100 of resin (B) and polymerizable compound (C) Elect 0.1~30 mass parts, more preferably more preferably 5~25 mass parts, 10~20 mass parts as.If polymerization initiator (D) content is the trend for then having high-sensitivity and shortening the time for exposure in above range, therefore is improved colour filter The trend of productivity ratio.

[5] polymerization triggers auxiliary agent (D1)

Polymerization triggers auxiliary agent (D1) to be for entering to the polymerization for triggering the polymerizable compound of polymerization using polymerization initiator Compound or sensitizer that row promotes.In the case where triggering auxiliary agent (D1) comprising polymerization, it can be combined with polymerization initiator (D) Use.

Polymerization triggers auxiliary agent (D1) to enumerate amines, alkoxy anthracene compound, thioxanthone compounds and Carboxylation Compound etc..Wherein, preferred thioxanthone compounds.The polymerization that two or more kinds may be used triggers auxiliary agent (D1).

Amines can enumerate triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminobenzoic acid first Ester, 4- dimethyl ethyl aminobenzoates, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminoethyls, 4- bis- Methylamino acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) benzophenone (common name rice Family name's ketone), 4,4 '-bis- (lignocaine) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone etc., wherein, preferably 4, 4 '-bis- (lignocaine) benzophenone.The commercially available products such as EAB-F (Baotugu Chemical Industrial Co., Ltd's system) can be used.

Alkoxy anthracene compound can enumerate 9,10- dimethoxys anthracene, EDMO, 9, 10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene, the fourth of 2- ethyls -9,10- bis- Epoxide anthracene etc..

Thioxanthone compounds can enumerate ITX, ITX, 2,4- diethyl thioxanthenes Ketone, the clopenthixal ketones of 2,4- bis-, the chloro- 4- propoxythioxanthones of 1- etc..

Carboxylic acid compound can enumerate phenylmercapto acetic acid, aminomethyl phenyl TGA, ethylphenyl TGA, methyl Ethylphenyl TGA, 3,5-dimethylphenyl TGA, methoxyphenyl TGA, Dimethoxyphenyl TGA, Chlorphenyl TGA, dichlorophenyl TGA, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N- naphthyls Glycine, naphthoxy acetic acid etc..

Polymerization triggers total amount 100 mass parts of the content relative to resin (B) and polymerizable compound (C) of auxiliary agent (D1) Preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If the content of polymerization initiation auxiliary agent (D1) is in above range, The trend of the productivity ratio of colour filter then can be improved further with high sensitivity formation colored pattern.

[6] mercaptan compound (T)

The colored curable resin composition of the present invention can contain mercaptan compound (T), and mercaptan compound (T) can have There is one kind or two or more mercaptan compound.Mercaptan compound (T) is the oximes such as O- acyl group oxime compounds in polymerization initiator (D) Particularly preferably used when based compound and/or united imidazole.Mercaptan compound (T) is to have at least one mercapto in intramolecular The compound of base (- SH).Mercaptan compound (T) is preferably the compound for having 1 sulfydryl in intramolecular.

The compound for having 1 sulfydryl in intramolecular can enumerate 2- Qiu Ji oxazoles, 2- thyroidans, 2- sulfydryl benzene And imidazoles, 2-mercaptobenzothiazole, 2- mercaptobenzoxazoles, 2- mercaptonicotinic acids, 2- mercaptopyridines, 2- mercaptopyridines- 3- alcohol, pyrithione, 4- Amide-6-hydroxy-2s-mercaptopyrimidine, 4- amino -6- hydroxyls - 2- mercaptopyrimidines, 4- amino-2-mercapto phenyl formics pyrimidine, 6- amino -5- nitroso -2- paper substrates, 4,5- diaminos Base -6- hydroxyl -2- mercaptopyrimidines, 4,6- diaminourea -2- mercaptopyrimidines, 2,4- diaminourea -6- mercaptopyrimidines, 4, 6- dihydroxy -2- mercaptopyrimidines, 4,6- dimethyl -2- mercaptopyrimidines, 4- hydroxyl -2- sulfydryl -6- methyl are phonetic Pyridine, 4- hydroxyl -2- sulfydryl -6- propyl group pyrimidine, 2- sulfydryl -4- methylpyrimidines, 2- mercaptopyrimidines, the thio urine of 2- are phonetic Pyridine, 3,4,5,6- tetrahydropyrimidine -2- mercaptan, 4,5- diphenyl-imidazole -2- mercaptan, 2- mercaptoimidazoles, 2- sulfydryls - 1- methylimidazoles, 4- amino -3- diazanyl -5- sulfydryls -1,2,4- triazoles, 3- amino -5- sulfydryls -1,2,4- Triazole, 2- methyl -4H-1,2,4- triazole -3- mercaptan, 4- methyl -4H-1,2,4- triazole -3- mercaptan, 3- Sulfydryl 1H-1,2,4- triazole -3- mercaptan, 2- amino -5- sulfydryls -1,3,4- thiadiazoles, 5- amino -1,3,4- Thiadiazoles -2- mercaptan, 2,5- dimercapto-1,3,4-thiadiazoles, (furans -2- bases) methyl mercaptan, 2- sulfydryls -5- Thiazolidone, 2-mercaptothiazoline, 2- sulfydryls -4 (3H)-quinazolinone, 1- phenyl -1H-TETRAZOLE -5- mercaptan, 2- quinoline thiols, 2- sulfydryl -5- tolimidazoles, 2- sulfydryl -5- nitrobenzimidazoles, 6- amino -2- mercaptos The chloro- 2-mercaptobenzothiazole of base benzothiazole, 5-, 6- ethyoxyls -2-mercaptobenzothiazole, 6- nitro -2- sulfydryls Benzothiazole, 2- sulfydryl naphtho-s imidazoles, 2- mercaptonaphthalenes and oxazole, 3- sulfydryls -1,2,4- triazoles, 4- amino -6- mercaptos Base pyrazolo [2,4-d] pyridine, 2- amino -6- purine mercaptan, Ismipur and 4- sulfydryl -1H- pyrazolos [2, 4-d] pyrimidine etc..

The compound for having more than 2 sulfydryls in intramolecular can enumerate ethanthiol, the mercaptan of the last of the ten Heavenly stems two, Isosorbide-5-Nitrae-bis- (methyl Sulfydryl) benzene, butanediol double (3-thiopropionate), butanediol double (3- mercaptoacetates), double (the 3- TGAs of ethylene glycol Ester), trimethylolpropane tris (3- mercaptoacetates), butanediol double (3-thiopropionate), trimethylolpropane tris (3- Mercaptopropionic acid ester), trimethylolpropane tris (3- mercaptoacetates), pentaerythrite four (3-thiopropionate), pentaerythrite Four (3- mercaptoacetates), trihydroxyethyl three (3-thiopropionate), pentaerythrite four (3- mercaptobutylates) and Isosorbide-5-Nitrae- Double (3- sulfydryls butoxy) butane etc..

The content of mercaptan compound (T) is preferably 0.5~50 mass parts relative to the mass parts of polymerization initiator (D) 100, more Preferably 5~45 mass parts, more preferably 10~40 mass parts.If the content of mercaptan compound (T) is in above range It is interior, then there is sensitivity rise and developability also becomes good trend.

[7] solvent (E)

The colored curable resin composition of the present invention preferably comprises solvent (E), solvent (E) preferably comprise a kind or 2 kinds with On solvent.Solvent (E) can enumerate beyond ester solvent (solvent for including-COO-), ester solvent ether solvents (comprising- O- solvent), ether-ether solvent (solvent comprising-COO- and-O-), the ketone solvent beyond ester solvent is (comprising-CO- Solvent), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide etc..

Ester solvent can enumerate methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, ethyl acetate, N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyric acid fourth Ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and Gamma-butyrolacton etc..

Ether solvents can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, two Glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propane diols list Propyl ether, propylene glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, tetrahydrofuran, tetrahydrochysene pyrrole Mutter, Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol dipropyl ether, Dibutyl ethylene glycol ether, methyl phenyl ethers anisole, phenetole and methylanisole etc..

Ether-ether solvent can enumerate methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethyoxyl second Sour methyl esters, ethoxy ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- second Epoxide methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2- methyl Ethyl propionate, acetic acid 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, propylene glycol methyl ether acetate, the third two Alcohol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, two Ethylene glycol monoethylether acetate, butyl carbitol acetate and dipropylene glycol methyl ether acetic acid esters etc..

Ketone solvent can enumerate 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone and isophorone etc..

Alcoholic solvent can enumerate methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and glycerine etc.. Aromatic hydrocarbon solvents can enumerate benzene,toluene,xylene and trimethylbenzene etc..Amide solvent can enumerate N, N- dimethyl formyls Amine, DMA and 1-METHYLPYRROLIDONE etc..

For coating, the viewpoint of drying property, boiling point when solvent (E) preferably comprises 1atm is more than 120 DEG C and 180 DEG C Following organic solvent.Wherein, solvent (E) is preferably comprised selected from by propylene glycol methyl ether acetate, ethyl lactate, propane diols list Methyl ether, 3- ethoxyl ethyl propionates, glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetic acid 3- methoxies What base butyl ester, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones and DMF were constituted It is at least one kind of in group, more preferably comprising selected from by propylene glycol methyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether What acetic acid esters, ethyl lactate, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol and 3- ethoxyl ethyl propionates were constituted It is at least one kind of in group.

The content of solvent (E) in colored curable resin composition be preferably 70~95 mass %, more preferably 75~ 92 mass %.In other words, the solid constituent of colored curable resin composition is preferably 5~30 mass %, more preferably 8~25 Quality %.If the content of solvent (E) is within the above range, flatness during coating becomes good, and is forming colour filter Colour saturation will not be not enough during device, thus has display characteristic to become good trend.

[8] levelling agent (F)

The colored curable resin composition of the present invention can include one kind or two or more levelling agent (F).Levelling agent (F) Can enumerate (without fluorine atom) silicone based surfactants, fluorine system surfactant and the organosilicon with fluorine atom It is surfactant etc..They can have polymerizable group in side chain.

Silicone-based surfactant can enumerate surfactant for having siloxanes key in intramolecular etc..Specifically, Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA, Toray Silicone SH8400 (trade names：The beautiful DOW CORNING Co. Ltd. system in east), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemial Co., Ltd's system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan company systems) etc..

Fluorine system surfactant can enumerate surfactant for having fluorocarbon chain in intramolecular etc..Specifically, can be with Enumerate FLUORAD (registration mark) FC430, FLUORAD FC431 (Sumitomo 3M Co. Ltd. systems), Megafac (registration mark) F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、 Megafac F554, Megafac R30, Megafac RS-718-K (Dainippon Ink Chemicals's system), F top (registration mark) EF301、F top EF303、F top EF351、F top EF352(Mitsubishi Materials Electronic Chemicals Co. Ltd. systems), Surflon (registration mark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd's system) and E5844 (Daikin Fine Chemical Laboratory Co. Ltd. systems) etc..

Silicone-based surfactant with fluorine atom can enumerate the table for having siloxanes key and fluorocarbon chain in intramolecular Face activating agent etc..Specifically, can enumerate Megafac (registration mark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (Dainippon Ink Chemicals's system) etc..

The content of levelling agent (F) is usually more than 0.001 mass % and 0.2 matter in colored curable resin composition Measure below %, preferably more than 0.002 mass % and below 0.1 mass %, more preferably more than 0.005 mass % and 0.05 matter Measure below %.It should be noted that the content is not included in the content of above-mentioned pigment dispersing agent.

[9] antioxidant (G)

From the viewpoint of the heat resistance and light resistance for improving colouring agent (A), colored curable resin composition preferably contains There is antioxidant.As long as the antioxidant that antioxidant is industrially typically used just is not particularly limited, phenol system can be used Antioxidant, phosphorous antioxidant and sulphur system antioxidant etc..Antioxidant can use two or more.

Phenol antioxidant can enumerate (the Irganox 1010 of イ Le ガ ノ ッ Network ス 1010：Pentaerythrite four [3- (3, 5- di-tert-butyl-hydroxy phenyls) propionic ester], BASF Co. Ltd. systems), (Irganox of イ Le ガ ノ ッ Network ス 1076 1076：3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl, BASF Co. Ltd. systems), イ Le ガ ノ ッ クス1330(Irganox 1330：3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-(trimethylbenzene -2,4,6- tri- Base) three paracresol, BASF Co. Ltd. systems), (Irganox 3114 of イ Le ガ ノ ッ Network ス 3114：1,3,5- tri- (3,5- bis- Tertiary butyl-4-hydroxy benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones, BASF Co. Ltd. systems), イ Le ガノックス3790(Irganox 3790：1,3,5- tri- ((the 4- tert-butyl group -3- hydroxyls -2,6- xylyl) first Base) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones, BASF Co. Ltd. systems), イ Le ガ ノ ッ Network ス 1035 (Irganox 1035：Thiodiethylene double [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], BASF plants of formulas Commercial firm's system), (Irganox 1135 of イ Le ガ ノ ッ Network ス 1135：Phenylpropyl alcohol alkanoic acid 3, double (1,1- the dimethyl ethyl) -4- of 5- Hydroxyl C7-C9 pendant alkyl groups ester, BASF Co. Ltd. systems), イ Le ガ ノ ッ Network ス 1520L (Irganox 1520L：4,6- is double (pungent butylthiomethyl) orthoresol, BASF Co. Ltd. systems), (Irganox 3125, the BASF plants of formula meetings of イ Le ガ ノ ッ Network ス 3125 Society's system), (Irganox 565 of イ Le ガ ノ ッ Network ス 565：2,4- double (just pungent sulfenyl) -6- (4- hydroxyls -3 ', 5 '-two Tertiary-butyl anilino) -1,3,5-triazines, BASF Co. Ltd. systems), ア デ カ ス タ Block AO-80 (ADEKA STABAO- 80：3,9- double (2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono epoxide) -1,1- dimethyl second Base) -2,4,8,10- tetra- oxaspiro (5,5) hendecanes, Asahi Denka Co., Ltd.'s system), ス ミ ラ イ ザ ー BHT (Sumilizer BHT, Sumitomo Chemical Co's system), ス ミ ラ イ ザ ー GA-80 (Sumilizer GA-80, Sumitomo Chemical Co System), ス ミ ラ イ ザ ー GS (Sumilizer GS, Sumitomo Chemical Co's system), (Cyanox of シ ア ノ ッ Network ス 1790 1790th, Co., Ltd. C ytec systems) and vitamin E (Eisai Co. Ltd. systems) etc..

Phosphorous antioxidant can enumerate (the Irgafos 168 of イ Le ガ Off ォ ス 168：Three (2,4- di-tert-butyl-phenyls) Phosphite ester, BASF Co. Ltd. systems), (Irgafos 12 of イ Le ガ Off ォ ス 12：Three [2- [[2,4,8,10- tetra-terts Dibenzo [d, f] [1,3,2] dioxa phosphine -6- bases] epoxide] ethyl] amine, BASF Co. Ltd. systems), イ Le ガ Off ォ ス 38 (Irgafos 38：Double (2,4- double (1,1- dimethyl ethyl) -6- aminomethyl phenyls) ethyl ester phosphorous acid, BASF plants of formula meetings Society's system), ADEKA STAB 329K (Asahi Denka Co., Ltd.'s system), ADEKASTAB PEP36 (Asahi Denka Co., Ltd.'s system), ADEKASTAB PEP-8 (Asahi Denka Co., Ltd.'s system), Sandstab P-EPQ (Clariant company systems), ウ ェ ス ト Application 618 (Weston 618, GE company systems), ウ ェ ス ト Application 619G (Weston 619G, GE societies system), ウ Le ト ラ ノ ッ Network ス 626 (Ultranox 626, GE societies system) and ス ミ ラ イ ザ ー GP (Sumilizer GP：6- [3- (the 3- tert-butyl group -4- hydroxyls Base -5- aminomethyl phenyls) propoxyl group] -2,4,8,10- tetra--tert-butyl group dibenzo [d, f] [1.3.2] dioxaphosphepin cycloheptyls Diene) (Sumitomo Chemical Co's system) etc..

Sulphur system antioxidant can enumerate dilauryl thiodipropionate, the myristin of thio-2 acid two or thio dipropyl The dialkyl thiodipropionate compounds such as sour distearyl ester and four [methylene (3- dodecylthios) propionic ester] methane etc. are more The β of first alcohol-alkylmercaptopropionates compound etc..

[10] other compositions

One kind or two or more filler, tree can be contained in the colored curable resin composition of the present invention as needed High-molecular compound, closely sealed accelerator, ultra-violet absorber, anticoalescent, organic acid, organic amine compound beyond fat (B), The additives such as curing agent.

Filler can enumerate glass, silica, aluminum oxide etc..High-molecular compound beyond resin (B) can be lifted Go out polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether and poly- perfluoroalkyl acrylate Arrcostab etc..

Closely sealed accelerator can enumerate vinyltrimethoxy silane, the VTES, (2- of vinyl three Methoxy ethoxy) silane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino second Base) -3- TSL 8330s, APTES, 3- glycidoxypropyl group trimethoxies Base silane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silicon Alkane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl front threes TMOS and 3-mercaptopropyi trimethoxy silane etc..

Ultra-violet absorber can enumerate 2- (the 2- hydroxyl -3- tert-butyl group -5- aminomethyl phenyls) -5- chlorobenzenes and three The BTA based compound such as azoles；The benzophenone based compounds such as 2- hydroxyl -4- octyloxy benzophenone；2,4- bis- uncles The benzoic ether based compounds such as butyl phenyl -3,5- di-tert-butyl-4-hydroxybenzoic acid ester；2- (4,6- diphenyl- 1,3,5-triazines -2- bases) the triazine based compound such as -5- hexyloxy-phenols；Etc..Anticoalescent can enumerate polypropylene Sour sodium etc..

Organic acid is used for adjustment of developability etc., specifically, can enumerate：

The aliphatic list carboxylic such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, octanoic acid Acid；

Oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, tridecane two Acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl butanedioic acid, cyclohexane cyclohexanedimethanodibasic, clothing The aliphatic dicarboxylic acids such as health acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid；

The aliphatic tricarboxylic acids such as the third three acid, aconitic acid, camphoric acids；

Benzoic acid, methyl benzoic acid, isopropyl acid, 2,3- mesitylenic acids (hemellitic acid), front three The aromatic monocarboxylates such as benzoic acid；

The aromatic dicarboxylic acids such as phthalic acid, M-phthalic acid, terephthalic acid (TPA)；

The aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, inclined benzene tetracarboxylic acid, Pyromellitic Acid；Etc..

Organic amine compound can be enumerated：

It is n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, just pungent The monoalkylamines such as amine, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine；

The monocyclic alkylamines such as cyclohexylamine, 2- methyl cyclohexylamines, 3- methyl cyclohexylamines, 4- methyl cyclohexylamines；

It is methyl ethyl-amine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, two different The dialkylamines such as butylamine, di-sec-butylamine, two tert-butylamines, two n-amylamines, two n-hexylamines；

The monocyclic alkylamine of the monoalkyls such as methyl cyclohexylamine, ethyl cyclohexylamine；

The bicyclic alkyl amine such as dicyclohexyl amine；

Dimethyl amine, methyl-diethyl-amine, triethylamine, dimethyl n propylamine, diethyl n-propylamine, methyl di-n-propylamine, Ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, The trialkylamines such as three n-hexylamines；

The monocyclic alkylamine of the dialkyl group such as dimethyl cyclohexyl amine, diethyl cyclohexylamine；

The monoalkyl bicyclic alkyl amine such as methyldicyclohexylamine, ethyl dicyclohexyl amine, tricyclohexyltin amine；

2- ethylaminoethanols, 3- amino -1- propyl alcohol, 1- amino -2- propyl alcohol, 4- amino-n-butyl alcohol, 5- ammonia The monoalkanolamines such as base -1- amylalcohols, 6- amino -1- hexanols；

The monocyclic alkanolamines such as 4- amino -1- cyclohexanol；

Diethanol amine, two normal propyl alcohol amine, diisopropanolamine (DIPA), two n-butanol amine, two isobutyl hydramine, two n-amyl alcohol amine, two are just The dialkanol amines such as hexanol amine；

The two cycloalkanes hydramine such as two (4- cyclohexanol) amine；

Triethanolamine, three normal propyl alcohol amine, triisopropanolamine, three n-butanol amine, three isobutyl hydramine, three n-amyl alcohol amine, three are just The alkanolamine of hexanol amine etc. three；

The three cycloalkanes hydramine such as three (4- cyclohexanol) amine；

3- amino -1,2-PD, 2- amino-1,3-propanediols, 4- amino -1,2- butanediol, 4- ammonia Base -1,3-BDO, 3- dimethylaminos -1,2-PD, 3- lignocaines -1,2-PD, 2- diformazan ammonia The amino-alkane hydrocarbon glycol such as base -1,3-PD, 2- lignocaines -1,3-PD；

The Aminocycloalkane glycol such as 4- amino -1,2- cyclohexanediol, 4- amino -1,3- cyclohexanediols；

The cyclanone methanol containing amino such as 1- amino cyclopentyl ketone methanol, 4- amino cyclopentyl ketone methanol；

1- aminocyclohexanones methanol, 4- aminocyclohexanones methanol, 4- dimethylaminos cyclopentanemethanol, 4- lignocaines The cycloalkane methanol containing amino such as cyclopentanemethanol, 4- dimethylaminos cyclohexane methanol, 4- lignocaine cyclohexane methanols；

Beta-alanine, 2-amino-butyric acid, 3- aminobutyric acids, 4-Aminobutanoicacid, 2- aminoisobutyric acids, 3- amino are different Butyric acid, 2- aminovaleric acids, 5- aminovaleric acids, 6-aminocaprolc acid, 1- 1-aminocyclopropane-1-carboxylic acids, 1- cyclohexanecarboxylic acids, The amino carboxylic acids such as 4- cyclohexanecarboxylic acids；

Aniline, o-toluidine, m-toluidine, open-chain crown ether, to MEA, to n-propylbenzene amine, to isopropyl Base aniline, to n-butyl aniline, p-tert-butyl-aniline, 1- naphthylamines, 2- naphthylamines, DMA, N, N- bis- MEA, to aromatic amines such as methyl-DMAs；

O-benzyl alcohol, m-aminophenyl methanol, p-aminophenyl methanol, to dimethylamino phenmethylol, to diethylaniline The aminobenzene methanol such as methanol；

O-aminophenol, m-aminophenol, para-aminophenol, to Dimethylaminophenol, to diethylamino phenol etc. Amino-phenol；

Gavaculine, p-aminobenzoic acid, p-(dimethylamino)-benzoic acid, to aminobenzoics such as diethylamino Benzoic Acids Acid；Deng.

Curing agent can be enumerated：It can make to make what resin (B) was crosslinked with the carboxyl progress reaction in resin (B) by heating It compound, can individually carry out polymerizeing compound for solidifying colored pattern etc., epoxide, oxetanes can be enumerated Compound etc..Curing agent can be used only a kind, and can also use two or more.

Epoxide can enumerate bisphenol-A system epoxy resin, hydrogenated bisphenol A system epoxy resin, Bisphenol F system asphalt mixtures modified by epoxy resin Fat, A Hydrogenated Bisphenol A F systems epoxy resin, phenolic resin varnish type epoxy resin, other fragrant family epoxy resin, alicyclic ring family epoxy The epoxy resin such as resin, hetero ring type epoxy resin, ethylene oxidic ester system resin, glycidol amine system resin, epoxidized oil；These Aliphatic, alicyclic or aromatic epoxy beyond bromo derivative, epoxy resin and its bromo derivative of epoxy resin Compound, the epoxides of the (co) polymer of butadiene, the epoxides of the (co) polymer of isoprene, (methyl) propylene (co) polymer, triglycidyl group isocyanuric acid ester of acid glycidyl ester etc..The commercially available product of epoxy resin can enumerate neighbour Cresol novolak type epoxy resin, " SUMI EPOXY (registration mark) ESCN-195XL-80 " (Sumitomo Chemical Co System) etc..

Oxetane compound can enumerate carbonic acid dioxygen azetidine, xylylene dioxygen azetidine, oneself two Sour dioxygen azetidine, terephthalic acid (TPA) dioxygen azetidine, cyclohexane dicarboxylic acid dioxygen azetidine etc..

In the colored curable resin composition of the present invention, make containing epoxide, oxetane compound etc. In the case of for curing agent, can include can make epoxy radicals, the oxa- ring fourth of oxetane compound of epoxide Alkane skeleton carries out the compound of ring-opening polymerisation.The compound can enumerate polybasic carboxylic acid, polybasic acid anhydride, acid agent etc..

Polybasic carboxylic acid can be enumerated：

3,4- dimethyl phthalic acids, Pyromellitic Acid, trimellitic acid, Isosorbide-5-Nitrae, 5,8- naphthalene tetracarboxylic acids, 3,3 ', 4, The aromatic polycarboxylic acids such as 4 '-benzophenone tetrabasic carboxylic acid；

The aliphatic polycarboxylic acids such as 1,2,3,4- ethylene-dimalonic acid；

Hexahydrophthalic acid, 3,4- dimethyl tetrahydros phthalic acid, hexahydro M-phthalic acid, hexahydro terephthaldehyde Acid, 1,2,4- pentamethylene tricarboxylic acids, 1,2,4- hexamethylene tricarboxylic acids, cyclopentane, 1,2,4,5- cyclohexanetetracarboxylic acids Deng ester ring type polybasic carboxylic acid；Deng.

Polybasic acid anhydride can be enumerated：

Phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride Deng aromatic polycarboxylic acid acid anhydride；

Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, the third three acid anhydrides, maleic anhydride, 1,2, Aliphatic polycarboxylic acid's acid anhydrides such as 3,4- ethylene-dimalonic acid dianhydrides；

Hexahydrophthalic anhydride, 3,4- dimethyl tetrahydros phthalic anhydride, 1,2,4- pentamethylene front three acid anhydrides, 1, 2,4- hexamethylene front three acid anhydrides, cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides, 5- double-heptene -2, The ester ring type polybasic acid anhydrides such as 3- dicarboxylic anhydrides (anhydrous Ha イ ミ ッ Network acid), carbic anhydride；

The carboxylic acid anhydrides containing ester group such as the trimellitic acid of ethylene glycol two, the trimellitic anhydride of glycerine three；Deng.

Carboxylic acid anhydrides can use the commercially available product as epoxy curing agent.Epoxy curing agent can enumerate trade name " ADEKA Hardener (registration mark) EH-700 " (Asahi Denka Co., Ltd.'s system), trade name " Rikacid (registration mark) HH " (New Japan Chem Co., Ltd's system), trade name " MH-700 " (New Japan Chem Co., Ltd's system) etc..

Acid agent can enumerate 4- hydroxy phenyl dimethyl sulfoniums tosilate, 4- hydroxy phenyl dimethyl sulfonium hexafluoros Stibate, 4- acetoxyl group phenyl dimethyl sulfoniums tosilate, 4- acetoxyl group phenyl methyl benzyl sulfonium hexafluoro-antimonic acids Salt, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine The salt such as hexafluoro antimonate, nitrobenzyl tosylate, benzoin toluene fulfonate etc..

The manufacture method ＞ of ＜ colored curable resin compositions

The colored curable resin composition of the present invention can be by by colouring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D) and preferable solvent (E) and other compositions as needed are mixed to prepare.

＜ colour filters and its manufacture method, colour filter and display device ＞

The colored curable resin composition of the present invention is useful as the material of colour filter.By the colored curable of the present invention The colour filter of resin combination formation also enters the scope of the present invention.Colour filter could be formed with colored pattern.

Photoetching process, ink-jet can be enumerated by the method for the colored curable resin composition manufacture colored pattern of the present invention Method, print process etc..Wherein, preferred photoetching process.Photoetching process is：Colored curable resin composition is coated on substrate, done Dry formation coloring compositions nitride layer, the method to be developed is exposed to the coloring compositions nitride layer across photomask.Photoetching process In, by the way that in exposure, without using photomask and/or without development, the solidification as above-mentioned coloring compositions nitride layer can be formed The coloring film of thing.Colored pattern, the coloring film formed by the colored curable resin composition of the present invention is of the invention Colour filter.

Substrate can be used quartz glass, borosilicate glass, alumina silicate glass, carry out silica to surface The glass plates such as the soda-lime glass of coating；The resin plates such as makrolon, polymethyl methacrylate, PET； Silicon；The substrate after aluminium, silver, silver/copper/palldium alloy film etc. is formed with aforesaid substrate.It can also be formed on these substrates There are other color-filter layers, resin bed, transistor, circuit etc..

It can be carried out using being formed for photolithographic a variety of colors pixel using known or usual device, condition, for example Making can be carried out as follows.First, colored curable resin composition is coated on substrate, be thermally dried (prebake conditions) And/or be dried under reduced pressure the thus volatile ingredient such as removing solvent and be allowed to drying, obtain smooth coloring compositions nitride layer.Coating method Spin-coating method, slot coated method, slit spin-coating method etc. can be enumerated.

Temperature when being thermally dried is preferably 30~120 DEG C, more preferably 50~110 DEG C.In addition, the heat time is excellent Elect as 10 seconds~5 minutes, more preferably 30 seconds~3 minutes.When being dried under reduced pressure, the pressure preferably in 50~150Pa Under, under 20~25 DEG C of temperature range carry out.The thickness of coloring compositions nitride layer is not particularly limited, can be according to being used as target The thickness of colour filter is suitably selected.

Then, coloring compositions nitride layer is exposed across the photomask for forming target coloration pattern.On the photomask Pattern be not particularly limited, can be used pattern corresponding with the purposes as target.The light source used in exposure is preferably production The light source of the light of raw 250~450nm wavelength.For example, the filter for ending the wave band can be used to the light less than 350nm Ended, the bandpass filter for extracting these wave bands can also be used to the light near 436nm, near 408nm, near 365nm Device carries out the extraction of selectivity.

Specifically, light source can enumerate mercury lamp, light emitting diode, metal halide lamp, halogen lamp etc..

Due to can be to whole plane of exposure uniform irradiation parallel rays, or carry out photomask and be formed with coloured composition The accurate position alignment of the substrate of layer, therefore exposure preferably uses mask aligner (mask aligner) and stepper (stepper) exposure device such as.

Developed by making the coloring compositions nitride layer after exposure be contacted with developer solution, color-patch map is formed on substrate Case.The unexposed portion of coloring compositions nitride layer is set to be dissolved in developer solution and remove by developing.

Developer solution alkali compounds such as being preferably potassium hydroxide, sodium acid carbonate, sodium carbonate, TMAH The aqueous solution.The concentration of these alkali compounds in aqueous is preferably 0.01~10 mass %, more preferably 0.03~5 matter Measure %.In addition, developer solution can include surfactant.

Developing method can be any of sheathed immersion method, dip coating and spraying process etc..In addition, can be by during development Substrate tilts arbitrary angle.Preferably washed after development.

Furthermore it is preferred that being toasted after being carried out to resulting colored pattern.Baking temperature is preferably 150~250 DEG C afterwards, more excellent Elect 160~235 DEG C as.Post-bake times are preferably 1~120 minute, more preferably 10~60 minutes.

The thickness of resulting colour filter influences due to being produced on adjacent pixel, thus preferably as thin as possible.Especially formed In the case of thick film, when making liquid crystal panel, the light of light source is spilt by pixels more than 2 colors sometimes, is seen from oblique When examining panel, it is possible to lose the vividness of color.Film after toasting afterwards is preferably generally less than 3 μm, more preferably 2.8 μm Below.The lower limit of film is not particularly limited, usually more than 1 μm, can be more than 1.5 μm.

Colour filter of the present invention is as display device (liquid crystal display device, organic el device, Electronic Paper etc.) and admittedly The colour filter used in body photographing element is useful.

Embodiment

Hereinafter, show that embodiment and comparative example carry out more specific description to the present invention, the invention is not restricted to these examples. In example, it is exactly quality criteria as long as no special declaration to represent content or the % of usage amount and part.

＜ synthesis examples 1：The preparation ＞ of xanthene dye

By 40.5 parts of compound shown in above-mentioned formula (1a) and 2,6- dimethylaniline (Tokyo chemical conversion Co. Ltd. system) 60.5 parts mix under dark conditions, are stirred 8 hours in 150 DEG C in 200 parts of N- methylpyridones.By resulting reaction Liquid is cooled to after room temperature, added in 1200 parts of water, the mixed liquor of 75 parts of 35% hydrochloric acid, is stirred at room temperature 1 hour, is as a result crystallized Separate out.The crystallization separated out is obtained as the residue of suction filtration, it is dry in 60 DEG C of decompressions after being washed using 100 parts of methanol At dry 1 night, 49 parts of compound shown in formula (1-2) is obtained.Yield is 85%.

Then, by 28.8 parts of compound shown in formula (1-2), the 24.2 parts of additions of 21.6 parts of 1- N-Propyl Bromides and potassium carbonate In 144 parts of N- methylpyridones, stirred 4 hours at 90 DEG C.Resulting reaction solution is cooled to after room temperature and concentrated, is added Add in 560 parts of water, stirred at 10~15 DEG C 1 hour, as a result crystallization is separated out.The crystallization of generation is taken as the residue of suction filtration After, be dried, after being washed using 1000 parts of ion exchange water, be dried under reduced pressure for 1 night at 60 DEG C, obtained above-mentioned formula 30.0 parts of compound shown in (1-24).Yield is 91%.

[identification of the compound shown in formula (1-24)]

(mass spectral analysis) ionization mode=ESI+：M/z=[M+H]+659.3

Accurate mass (Exact Mass)：658.3

＜ synthesis examples 2：The preparation ＞ of resin (B)

Thus the appropriate nitrogen that circulated into the flask for possessing reflux condenser, dropping funel and mixer be replaced as blanket of nitrogen, 371 parts of propylene glycol methyl ether acetate is added, is stirred while being heated to 85 DEG C.Then, 4 hours used times will make propylene Acid 54 parts, the ring [5.2.1.0 of 3,4- epoxies three^2,6] decane -8- bases acrylate and the ring [5.2.1.0 of 3,4- epoxy three^2,6] The mixture of decane -9- base acrylate (contains than using molar ratio computing as 50：50) 225 parts, vinyltoluene (isomers mix Compound) 81 parts of mixed solutions for being dissolved in 80 parts of propylene glycol methyl ether acetate and preparing are added dropwise in flask.

On the other hand, 5 hours used times, which were added dropwise, makes polymerization initiator 2, and 2- azos double 30 parts of (2,4- methyl pentane nitriles) are molten In 160 parts of solution of propylene glycol methyl ether acetate.After the completion of dropwise addition of the solution, after 85 DEG C are kept for 4 hours, it is cooled to Room temperature, has obtained resin (B) solution.The solid constituent of the solution of resin (B) is 37.5%, is utilized Brookfield viscometer (23 DEG C) The viscosity of measure is 246mPas.The weight average molecular weight of resin (B) is 1.06 × 10⁴, solid constituent conversion acid number be 115mg-KOH/g, molecular weight distribution is 2.01.

The weight average molecular weight (Mw) of resulting resin (B) and the measure of number-average molecular weight (Mn) are using GPC method following Under conditions of carry out.The ratio between weight average molecular weight and number-average molecular weight that the polystyrene obtained under the following conditions is converted (Mw/Mn) as molecular weight distribution.

Device：HLC-8120GPC (TOSOH Co., Ltd's system),

Post：TSK-GELG2000HXL,

Column temperature：40℃、

Solvent：THF、

Flow velocity：1.0mL/min、

It is detected liquid solids content concn：0.001~0.01 mass %,

Injection rate：50μL、

Detector：RI、

Correction standard substance：TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(TOSOH Co., Ltd's system).

The composition used in the present embodiment is as described below, omits represent sometimes below.

Colouring agent (A-1)：The compound (dyestuff) shown in formula (1-24) that is obtained in synthesis example 1,

Colouring agent (A-2)：C.I. pigment blue 15：6 (pigment),

Colouring agent (A-3)：Following shown compounds (thiazole dye),

Colouring agent (A-4)：C.I. solvent blue 45：Savinyl Blue RS (Clariant company systems) (anthraquinone dye)

Resin (B)：The resin (B) that is included in the resin solution obtained in synthesis example 2,

Polymerizable compound (C-1)：Pentaerythritol triacrylate (the commodity of Xin Zhong villages chemical industry Co. Ltd. system Name " A-TMM-3LM-N ", hydroxyl value：110mgKOH/g)、

Polymerizable compound (C-2)：Dipentaerythritol polyacrylate (the business of Xin Zhong villages chemical industry Co. Ltd. system The name of an article " A-9550 ", hydroxyl value：50mgKOH/g)、

Polymerizable compound (C-3)：The mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate (trade name " A-9530 ", the hydroxyl value of Xin Zhong villages chemical industry Co. Ltd. system：40mgKOH/g)、

Polymerization initiator (D)：N- benzoyloxys -1- (4- phenylmercaptos phenyl) octane -1- ketone -2- imines The trade name of (BASF AG " IRGACUREOXE 01 "),

Polymerization triggers auxiliary agent：2, the 4- diethyl thioxanthones (trade name " KAYACURE of Nippon Kayaku K. K DETX-S "),

Solvent (E)：Propylene glycol methyl ether acetate,

Levelling agent (F)：Polyether modified silicon oil (trade name " the Toray Silicone of eastern beautiful DOW CORNING Co. Ltd. system SH8400”)。

(1) preparation of colored curable resin composition

＜ embodiments 1~4 and the ＞ of comparative example 1~4

Each composition described in table 8 is carried out with the match ratio described in table 8 to be obtained by mixing colored curable resin Composition.The unit of the use level of each composition in table 8 is " mass parts ", and use level converts for solid constituent.

The ＞ of ＜ embodiments 5

[preparation of colored curable resin composition]

By the mass parts of colouring agent (A-2) 23.5

The mass parts of acrylic acid series pigment dispersing agent 8.2 and

The mass parts of solvent (E) 194

Mixed, make pigment fully dispersed using ball mill, then,

Progress has been obtained by mixing colored curable resin composition.

The ＞ of ＜ comparative examples 5~6

Except similarly to Example 5 being carried out with addition to being combined into and being changed such as table 8, being prepared for coloring and consolidating The property changed resin combination.

(2) measure of the hydroxyl value of polymerizable compound

Acetylation reagent is added into sample according to JIS K 0070-1992, is heated, is put in glycerol bath Put after cooling, add phenolphthalein solution as indicator, titrated to determine using potassium hydroxide-ethanol solution.Measurement result is such as It is lower described.

(3) making of pattern

On the glass substrate (" EagleXG " of Corning Incorporated) of 2 inch squares staining and curing is coated with using spin-coating method Property resin combination after, the prebake conditions of 3 minutes are carried out at 100 DEG C, coloring compositions nitride layer is formd.After cooling, formation is had The substrate of color composition layer is set to 150 μm with the interval of quartz glass photomask, uses exposure machine (TOPCON Co. Ltd. systems " TME-150RSK ") under air atmosphere with 50mJ/cm²Light exposure (365nm benchmark) carry out light irradiation.Photomask makes With the photomask for being formed with 100 μm of line widths and pitch pattern.Coloring compositions nitride layer after light irradiation is being included into nonionic system table Face activating agent 0.12% in the water system developer solution of potassium hydroxide 0.04% with, in the immersion development of 24 DEG C of progress 60 seconds, washing Afterwards, colored pattern has been obtained in the rear baking of 230 DEG C of progress 20 minutes in an oven.

(4) film thickness measuring

For resulting colored pattern, using film thickness measuring device (ULVAC Corp " DEKTAK3 ") determine thickness.The result of embodiment 1~4 and comparative example 1~4 is shown in table 9, by embodiment 5 and comparative example 5~ 6 result is shown in table 10.

(5) chromaticity evaluation

For resulting colored pattern, surveyed using colour examining machine (" OSP-SP-200 " of Olympus Co., Ltd) Determine spectrum, xy chromaticity coordinates (x, y) and tristimulus values Y in CIE XYZ color specification systems are determined using the characterisitic function of illuminant-C. Y value is bigger to represent that brightness is higher.The result of embodiment 1~4 and comparative example 1~4 is shown in table 9, by embodiment 5 and comparative example 5~6 result is shown in table 10.

(6) Evaluation of Heat Tolerance

By resulting colored pattern in an oven in the heating of 230 DEG C of progress 3 hours.Determine xy colourities afterwards before heating Coordinate (x, y) and Y, according to the measured value by JIS Z 8730：Method described in 2009 (computational methods of 7. aberration) is calculated Aberration Δ Eab*.The result of embodiment 1~4 and comparative example 1~4 is shown in table 9, by embodiment 5 and the result of comparative example 5~6 It is shown in table 10.Δ Eab* is smaller to mean that color change is smaller.In addition, if the heat resistance of coloring film is good, then by identical Colored curable resin composition make colored pattern heat resistance could also say that it is good.

Table 8

Table 9

Table 10

Industrial applicability

Using the colored curable resin composition of the present invention, can provide can show good brightness and heat resistance is excellent Different colour filter and the display device comprising the colour filter.

Claims (9)

1. a kind of colored curable resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization Initiator (D), wherein,

As the colouring agent (A), comprising the dyestuff with xanthene skeleton,

As the polymerizable compound (C), the polymerizable compound that hydroxyl value is more than 100mgKOH/g is included.

2. colored curable resin composition as claimed in claim 1, wherein, hydroxyl value is more than 100mgKOH/g polymerism Compound is pentaerythritol triacrylate.

3. colored curable resin composition as claimed in claim 1 or 2, wherein,

The content of polymerizable compound (C) is relative to content/resin that the ratio between content of resin (B) is polymerizable compound (C) (B) content is 0.6~5 by quality ratio.

4. colored curable resin composition as claimed in claim 1 or 2, wherein,

The content of polymerizable compound (C) is relative to content/resin that the ratio between content of resin (B) is polymerizable compound (C) (B) content is 0.75~5 by quality ratio.

5. colored curable resin composition as claimed in claim 1 or 2, wherein,

Colouring agent (A) also includes C.I. pigment blue 15s：6.

6. colored curable resin composition as claimed in claim 1 or 2, wherein,

The content of dyestuff with xanthene skeleton is 1~50 mass % in the mass % of colouring agent (A) 100.

7. colored curable resin composition as claimed in claim 1 or 2, wherein, as polymerization initiator (D), include oxime Based compound.

8. a kind of colour filter, it is formed as the colored curable resin composition described in claim 1 or 2.

9. a kind of display device, it includes the colour filter described in claim 8.