CN107526249A - Black pigment compositions and the black coating film formation composition containing it - Google Patents

Abstract

The present invention provide it is a kind of without using carbon black, the light of visible region can be absorbed and the good black pigment compositions of the absorption of infrared ray and ultraviolet, solvent resistance can be suppressed and form composition containing its black coating film.Containing at least one kind of black organic pigment in following formula (1) and (2), at least two kinds of coloured organic pigments beyond the black organic pigment, dispersant and solvent black pigment compositions and contain the black pigment compositions and the black coating film of film forming component and form composition.

Description

Black pigment compositions and the black coating film formation composition containing it

Technical field

Composition is formed the present invention relates to a kind of black pigment compositions and containing its black coating film, it is more particularly to a kind of Such as be arranged at liquid crystal display device flat board black intercolumniation every used black pigment compositions and the black containing it Film forms composition.

Background technology

Liquid crystal display device has is filled with liquid crystal material between 2 glass substrates for being provided with opposed transparency electrode Liquid crystal cell structure.Moreover, in order to equably keep gap between the substrate between 2 glass substrates and provide good figure Picture, inserted with intercolumniation every.At present, as this intercolumniation every the pearl interval such as pearl glass can be used.But between using pearl Every mode in, it is indicated that exist：Because only make pearl be irregularly scattered in gap, sometimes produce light leak the problem of, sometimes gap away from From deviation become big, the problems such as the control difficulty of the mechanical characteristic such as elasticity.In addition, to liquid crystal display device requirement in recent years Set out in the market of higher image quality, it is desirable to more accurate gap control.

As the improvement alternative, it is proposed that using black-colored photosensitive resin composition replace pearl interval black intercolumniation every (referring for example to patent document 1,2.).According to black intercolumniation every, it is believed that can be in desired position with the deviation of clearance distance The mode to diminish formed intercolumniation every, the control characteristic such as optical polymerism composition is to be relatively easy to, therefore, the situation phase with pearl interval Than accurate gap can be controlled.Moreover, by intercolumniation in the colouring agent containing black, blocking visible ray (wavelength is set to 380nm~750nm.), the raising of contrast and color developing effect can be expected.As the colouring agent of this black, patent document 1, There is black illustration in 2.In addition, as black one, Patent Document 3 discloses the pigment of specific structure.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2015-191234 publications

Patent document 2：Japanese Unexamined Patent Publication 2007-71994 publications

Patent document 3：No. 4980727 publication of patent

The content of the invention

Invent problem to be solved

But because intercolumniation contacts every with liquid crystal material, therefore it is required that having for solvent contained in liquid crystal material resistance to Property is solvent resistance.In addition, it is also desirable to the characteristic not had an impact to the characteristic of liquid crystal cells.For example, black intercolumniation every it is exhausted When edge is low, the driving to liquid crystal has an impact, and therefore, there is the possibility being had an impact to the characteristic of liquid crystal cells.

And then formed intercolumniation every manufacturing process in, mostly using solidifying the composition of optical polymerism and form high score The method of sub- compound.In this case, generally, due to irradiating ultraviolet makes its solidification, therefore, black photosensitive composition Need to be formed in a manner of absorbing visible ray and pass through ultraviolet.In addition, used mostly using the identification of the infrared rays such as near infrared ray Alignment keys on the display panel substrate of accurate location for judging exposure.At this time, it may be necessary to formed in a manner of also passing through infrared ray.

In patent document 1,2, as black pigment, exemplified with nigrosine, black, titanium is black, phthalocyanine is black, lignin is black, interior Acid amides system Organic Black, the black, carbon blacks of RGB etc..But, it is allowed to using carbon black, in terms of insulating properties, worry to produce shadow to liquid crystal cells Ring.Further, since carbon black also absorbs ultraviolet, the infrared ray beyond visible ray, therefore, it is possible to UV-induced photopolymerization Property composition polymerisation become insufficient, or using infrared ray exposure when positioning become difficult, worry to manufacturing process Have an impact.

In view of the aspect of the above, it is an object of the present invention to provide one kind without using carbon black, visible region can be absorbed Light and can suppress the good black pigment compositions of the absorption of infrared ray and ultraviolet, solvent resistance and containing its Black coating film forms composition.

For solving the method for problem

In patent document 1,2, as black pigment, exemplified with black, but do not recorded on black specific example. Therefore, the present inventor is furtherd investigate, and as a result obtains the difference according to black species, the degree of solvent resistance is not Together, the different opinion of the absorption spectrum of wavelength in addition.Also, it was found that by by the black of specific structure and its beyond coloured face Material can solve above-mentioned problem using at least two kinds of, until completing the present invention.The main points of the present invention are as described below.

The first aspect of the present invention is related to a kind of black pigment compositions, and it contains in following formula (1) and (2) extremely At least two kinds of coloured organic pigment, dispersant and solvents beyond few a kind of black organic pigment, the black organic pigment.

In the preferred embodiment of the present invention, the coloured organic pigment beyond above-mentioned black organic pigment is selected from red Organic pigment, blue organic pigment and purple organic pigment.In addition, in preferred embodiment, the above-mentioned organic face of red Expect to be at least one kind of in following (a) group, above-mentioned blue organic pigment is above-mentioned to be at least one kind of in following (b) group Purple organic pigment is at least one kind of in following (c) group.

(a) group：

C.I. pigment red 149,179,254,255,

(b) group：

C.I. pigment blue 15,15：1、15：2、15：3、15：4、15：5、15：6th, 16,60,

(c) group：

C.I. pigment Violet 23,29.

The second aspect of the present invention is related to a kind of black coating film and forms composition, its contain above-mentioned black pigment compositions and Film forming component.

Invention effect

In accordance with the invention it is possible to provide it is a kind of without using carbon black, the light of visible region can be absorbed and can be suppressed The good black pigment compositions of the absorption of infrared ray and ultraviolet, solvent resistance and the black coating film formation combination containing it Thing.

Embodiment

＜ black pigment compositions ＞

The black pigment compositions of the present invention contain at least one kind of black organic pigment in following formula (1) and (2), At least two kinds of coloured organic pigments beyond the black organic pigment are (below, sometimes referred to simply as " coloured organic pigment ".), it is scattered Agent and solvent.

The black organic pigment of specific structure shown in formula (1), (2) has：In wavelength 380nm~750nm region Effectively absorb visible ray and make transmitance step-down, compared with visible region, (wavelength is less than 380nm area for ultraviolet range Domain) and infrared spectral range (wavelength be more than 750nm region) the absorption characteristic that is suppressed, diminishes.In this visible region The absorption characteristic of light can be confirmed according to the optical concentration (OD values) when being measured with method described later.It is in addition, logical Cross and combined with least two kinds of coloured organic pigments beyond the black organic pigment, visible region can be interdicted without using carbon black The light in domain, compared with visible region, it can effectively suppress the absorption of ultraviolet and infrared ray.Thus, for example using Optical polymerism composition formed as film forming component intercolumniation every when, can utilize ultraviolet make optical polymerism composition fully Positioning when carrying out polymerisation, and can carry out the exposure using infrared ray.In addition, solvent resistance is good.It can also keep away Exempt from the influence of the characteristic to liquid crystal cells due to carbon black.

This black organic pigment can for example use the Lumogen Black FK4280 of BASF AG.

In embodiments of the present invention, from the absorption of the light in visible region with the region of ultraviolet and infrared ray Absorption suppression balance from the viewpoint of, the content of the black organic pigment in black pigment compositions is preferably 1~12 Weight %, more preferably 1~7 weight %.

As the coloured organic pigment that can be used in the present invention, organic red pigment, the organic face of blueness can be enumerated Material, green organic pigment, purple organic pigment, yellow organic pigment, orange organic pigment, brown organic pigment etc..Use dyestuff When indexing (Colour Index) No. expressions, such as following materials can be illustrated.

Organic red pigment：Paratonere 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,21,22, 23、31、32、38、41、48、48：1、48：2、48：3、48：4、48：5、49、52、52：1、52：2、53：1、54、57：1、58、 60：1、63、64：1、68、81：1、83、88、89、95、112、114、119、122、123、129、136、144、146、147、149、 150、164、166、168、169、170、171、172、175、176、177、178、179、181、183、184、185、187、188、 190、193、194、200、202、206、207、208、209、210、211、213、214、216、220、221、224、226、237、 238、239、242、245、247、248、251、253、254、255、256、257、258、260、262、263、264、266、268、 269、270、271、272、279.Wherein, from above-mentioned black organic pigment and other coloured organic pigments, particularly blueness The raising effect of OD values caused by the combination of organic pigment and the viewpoint of the inhibition of purplish red outside line and the absorption of infrared ray Set out, preferred pigments red 149,179,254,255.

Blue organic pigment：Pigment blue 1,15,15：1、15：2、15：3、15：4、15：5、15：6、16、17：1、24、24： 1st, 25,26,56,60,61,62,63,75,79,80 etc..Wherein, from above-mentioned black organic pigment and other coloured organic face It is excellent from the viewpoint of the raising effect of OD values caused by the combination of material and the inhibition of the absorption of ultraviolet and infrared ray Select pigment blue 15,15：1、15：2、15：3、15：4、15：5、15：6th, 16,60, more preferably pigment blue 15：6、16、60.

Green organic pigment：Naphthol green 1,4,7,8,10,36 etc..

Purple organic pigment：Pigment violet 1,2,3,3：1、3：3、5：1、13、17、19、23、25、27、29、31、32、36、 37th, 38,42,50 etc..Wherein, from OD values caused by the combination with above-mentioned black organic pigment and other coloured organic pigments From the viewpoint of the inhibition for improving the absorption of effect and ultraviolet and infrared ray, preferred pigments purple 23,29, more preferably Pigment violet 29.

Yellow organic pigment：Pigment yellow 1,2,3,4,5,6,7,9,10,12,13,14,15,16,17,24,49,55,60, 61、61：1、62、63、65、73、74、75、77、81、83、87、93、94、95、97、98、99、100、101、104、105、106、 108、109、110、111、113、114、116、117、120、123、124、126、127、128、129、130、133、138、139、 150、151、152、153、154、155、165、167、168、169、170、172、173、174、175、176、179、180、181、 182、183、185、191、191-1、193、194、199、205、206、209、209：1st, 212,213,214,215,219 etc..

Orange organic pigment：Pigment orange 1,2,3,4,5,13,15,16,17,19,24,31,34,36,38,40,43,46, 48th, 49,51,60,61,62,64,65,66,67,68,69,71,72,73,74,81 etc..

Brown organic pigment：Pigment brown 5,23,25,32,41,42 etc..

In the present invention, at least two kinds of coloured organic pigments as described above are preferably comprised.Thus, it is possible to above-mentioned black Organic pigment is combined, and effectively absorbs the light of visible region.Coloured organic pigment can contain more than 3 kinds.This be because For the species of colored pigment is more, it is seen that the assimilation effect of light is bigger.But its species it is more when, sometimes colored pigment point Unfavorable condition is produced in terms of dissipating property.Therefore, the present inventor is furtherd investigate, and is as a result found：By black as defined in above-mentioned Combination is at least two kinds of in organic red pigment, blue organic pigment and purple organic pigment in color organic pigment, can press down The use of color organic pigment is formed with, while the absorption characteristic of defined black organic pigment can be kept, can be effectively absorbed Wavelength 380nm~750nm region-wide visible ray, can suppress the absorption of ultraviolet region and region of ultra-red.In addition, this effect Fruit is at least one kind of in the C.I. pigment red 149s organized as (a), 179,254,255 in organic red pigment, and blueness has Machine pigment is selected from the C.I. pigment blue 15s organized as (b), 15：1、15：2、15：3、15：4、15：5、15：6th, in 16,60 extremely Few a kind, and at least one kind of in the C.I. pigment Violet 23s organized as (c), 29 in the case of, exist and more effectively play Tendency.And then exist further preferred organic red pigment and blue organic pigment be respectively be selected from (a) group in a kind and 1 kind of situation and blue organic pigment and purple organic pigment in (b) group be respectively be selected from (b) group a kind and The tendency of a kind of the situation in (c) group.

In embodiments of the present invention, from region-wide in 380~750nm in effectively absorb visible ray and effectively From the viewpoint of the absorption for suppressing ultraviolet and infrared ray, the content of coloured organic pigment is relative to the weight of black organic pigment 100 It is preferably 50~1000 parts by weight to measure part, more preferably 100~700 parts by weight.In addition, the situation using pigment derivative described later Under, the content of the coloured organic pigment means to include the total amount of pigment derivative.

As the dispersant that can be used in the present invention, can enumerate for example：Resin type dispersant, surfactant type point Powder etc..In addition, there is amine value and be more than 0 for 0 and acid number in resin type dispersant according to the acid number of resin and the difference of amine value The dispersant of the amine value type of the dispersant of acid number type, acid number 0 and amine value more than 0, acid number and amine value are more than 0 dispersant.

As resin type dispersant, can enumerate for example：Polyurethane；Polyester；Unsaturated polyamide；Phosphate；Polycarboxylic acids And its amine salt, ammonium salt, alkylamine salt；Polycarboxylate；Hydroxyl polycarboxylate；Polysiloxanes；Modified polyacrylate；Alginic acid Class, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methylcellulose, polyvinylpyrrolidone The water-soluble high-molecular compounds such as ketone, Arabic gum；Styrene-acrylic resins, styrene-t resin, benzene second Alkene-acrylic acid-acrylic ester resin, styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methyl Acrylate, acrylic acid-acrylic ester resin, isobutylene maleic resin, vinyl -ester resin, Abietyl modified Malaysia The resin containing olefinic double bond such as acid resin；Amine system resin such as PAH, polyvinylamine, polyethylene imine etc..

Resin type dispersant can use commercially available material.The concrete example of commercially available product is as described below, but is not limited to this A bit.

Japanese Lubrizol Co. Ltd. systems：Solsperse 3000、9000、13240、17000、20000、24000、 26000、27000、28000、32000、32500、36000、38500、39000、55000、41000、

BYK-Chemie Japan KK systems：Disperbyk 108、110、112、140、142、145、161、162、163、 164、166、167、171、174、182、190、2000、2001、2015、2050、2070、2150、LPN6919、LPN22101、 LPN21116、

BASF AG's system：EFKA 4401、4403、4406、4330、4340、4010、4015、4046、4047、4050、 4055、4060、4080、5064、5207、5244、PX4701、

Ajinomoto Fine-Techno Co., Inc. systems：AJISPER-PB821(F)、PB822、PB880、

Kawaken Fine Chemical Co., Ltd. systems：HINOACT T-8000、

Nanmu this chemical conversion Co. Ltd. system：DISPARLON PW-36、DISPARLON DA-325、375、7301、

Otsuka Chemical Co., Ltd's system：TERPLUS D2015, MD1000 etc..

In addition, various resins as described above conventionally can be synthesized and used by resin type dispersant.As above Described various resins such as under nitrogen atmosphere in a solvent by more than a kind of monomer, polymerization initiator etc. mixed, Polymerisation is carried out under rated condition, it is hereby achieved that homopolymer, random copolymer, block copolymer, graft copolymer etc..

In addition, in embodiments of the present invention, can use comprising containing the construction unit from cyclic amine compound Polymer blocks (A) and containing the construction unit from nonionic water soluble compound and from anionic property water solubility chemical combination The construction unit of thing and the block copolymer for being free of the polymer blocks (B) of the construction unit from above-mentioned cyclic amine compound (I) the resin type dispersant as active ingredient., can be with by using the resin type dispersant for including the block copolymer (I) Reduce other dispersants, the usage amount of pigment derivative described later.Because pigment derivative is imported with functional group in pigment, because This, has an impact sometimes according to the characteristic of pigment and functional group to the characteristic of liquid crystal cells.But by using embedding comprising this The resin type dispersant of section copolymer (I), can reduce other dispersants, the usage amount of pigment derivative, therefore, can reduce Influence to the characteristic of liquid crystal cells.

When block copolymer (I) is described in detail, as described below.

Block copolymer (I) can be the triblock copolymer of the diblock copolymer of A-B types, A-B-A types or B-A-B types Thing, the Tetrablock copolymer of A-B-A-B types, A-B-A-B-A types or five block copolymers of B-A-B-A-B types so its more than Segmented copolymer etc. it is any number of, but from pigment, the particularly viewpoint such as dispersiveness of miniaturization pigment, preferably at one End configures polymer blocks (A), polymer blocks (B) block copolymer (I) is configured with another end.

Polymer blocks (A) is by the homopolymers or cyclic amine compound of cyclic amine compound and the change that can be copolymerized with it The block that the copolymer of compound is formed.The copolymer can be random copolymer, or block copolymer.Above-mentioned homopolymer It can be carried out as needed with ring-type amine unit contained in copolymer quaternary ammoniated., can be without spy as cyclic amine compound Not Xian Zhi ground using with the group (hereinafter sometimes referred to " polymerizable group ") containing polymerism double bond nitrogen heterocyclic, Wherein, 5 yuan more preferably with polymerizable group or 6 yuan of nitrogen-containing heterocycle compound.Polymerizable group is preferably alkenyl, more excellent Elect vinyl as.

As 5 yuan or the concrete example of 6 yuan of nitrogen-containing heterocycle compound with polymerizable group, can enumerate for example：2- Vinylpyridine, 4-vinylpridine, 1- vinyl imidazoles, 1- vinyl -1H- pyrazoles, 1- vinyl -2- imidazolines, 2- second Alkenyl -2- imidazolines, 2- vinylpyrazines, 2- vinyl -4,6- diaminostilbenes, 3,5- triazines etc..Wherein, seen from dispersiveness etc. Point sets out, preferably 2- vinylpyridines, 4-vinylpridine etc..Cyclic amine compound can be used alone, or combination makes Use two or more.

The content of ring-type amine unit in block copolymer (I) is not particularly limited, from viewpoints such as dispersivenesses, relatively In block copolymer (I) total amount, preferably 5~30 weight %, more preferably 5~25 weight %, more preferably 7~20 Weight %.

Furthermore it is possible to allow in the range of effect caused by block copolymer (I) is not damaged and cyclic amine compound The compound of copolymerization is copolymerized with cyclic amine compound.As the compound that can be copolymerized, nonionic for example described later can be enumerated Property non-water soluble compounds, wherein, preferably butyl acrylate, methyl methacrylate, styrene etc..These changes that can be copolymerized Compound can be used alone, or two or more is applied in combination.

On the other hand, polymer blocks (B) be by containing nonionic water solubility unit and anionic property water solubility unit, Preferably comprise nonionic water solubility unit, anionic property water solubility unit and the knot from nonionic non-water soluble compounds Structure unit (hereinafter sometimes referred to " the water-insoluble unit of nonionic ") and without ring-type amine unit copolymer form it is embedding Section.Polymer blocks (B) can be random copolymer, or block copolymer, but from film forming component described later Resin, photopolymer, the viewpoint such as compatibility of dispersion resin etc. set out, preferably random copolymer.

Nonionic water solubility unit is the construction unit of the divalent from nonionic water soluble compound.As it is non-from Sub- property water soluble compound, as long as nonionic and water solubility and being polymerizable organic compound, just do not limit especially It is fixed, but preferably there is at least one kind of hydrophilic radical (hereinafter sometimes referred to simply as " hydrophily base in hydroxyl and amide groups Group ") and polymerizable nonionic water-soluble organic compounds.Nonionic water-soluble organic compounds can have polymerization Property group, polymerizable group is preferably alkenyl, more preferably vinyl.

As with hydrophilic radical and the nonionic water-soluble organic compounds that can polymerize, can enumerate for example： PAG, PAG (methyl) acrylate, (methyl) hydroxyalkyl acrylates, (methyl) acrylamide Compound, NVP, epoxyalkane etc..These materials can be used alone, or be applied in combination 2 kinds with On.

As PAG, can enumerate for example：The alkylidene chains such as polyethylene glycol, polypropylene glycol, polybutene glycol Carbon number be 2~4 PAG.

As PAG (methyl) acrylate, the carbon number that can enumerate such as alkylidene chain is 2~4 The simple function or polyfunctional ester of PAG and acrylic or methacrylic acid, more specifically, can be enumerated：Poly- second Monomethacryiate, methoxy poly (ethylene glycol) monomethacrylates, polyethylene glycol dimethacrylate, phenoxy group Polyethylene glycol acrylate, polypropylene glycol monomethacrylate, polypropyleneglycol diacrylate etc..

As (methyl) hydroxyalkyl acrylates, can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) propylene The moieties such as sour 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls are (methyl) of the chain-like alkyl of carbon number 1~4 Hydroxyalkyl acrylates.

As (methyl) acrylamide compound, can enumerate for example：(methyl) acrylamide, N- methyl (methyl) propylene Acid amides, N- ethyls (methyl) acrylamide, N- propyl group (methyl) acrylamide, N- isopropyls (methyl) acrylamide, the positive fourths of N- Base propylene (methyl) acid amides, the N- tert-butyl groups (methyl) acrylamide, N- cyclohexyl (methyl) acrylamide, N- (2- methoxyl group second Base) (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- phenyl (first Base) acrylamide, N- benzyls (methyl) acrylamide, diacetone acrylamide etc..

As epoxyalkane, can enumerate for example：Oxirane, expoxy propane, epoxy butane etc..

For the content of the nonionic water solubility unit in block copolymer (I), formed from using film described later Composition formed such as intercolumniation every when developability viewpoint set out, relative to block copolymer (I) total amount, preferably 40~ 80 weight %, more preferably 45~75 weight %, more preferably 45~73 weight %.

Anionic property water solubility unit is the construction unit of the divalent from anionic property water soluble compound.As the moon from Sub- property water soluble compound, as long as being anionic property and organic compound water-soluble and with polymerizable group, just without spy Do not limit, there is preferably 1 intramolecular at least one kind of acidic group in carboxylic acid group, sulfonic group and phosphate (to be hereinafter sometimes referred to simply as " acidic group ") and polymerizable group anionic property water solubility organic oxygen compound.It is explained, polymerizable group is preferably Alkenyl, more preferably vinyl.

As the concrete example with acidic group and the anionic property water solubility organic oxygen compound of polymerizable group, can enumerate Such as：Carboxylic acid compound, sulfoacid compound, phosphate cpd etc..These materials can be used alone, or be applied in combination 2 More than kind.

As carboxylic acid compound, can enumerate for example：Acrylic acid, methacrylic acid, butenoic acid, methacrylate, fumaric acid, Maleic acid, cinnamic acid, 2- citraconic acids, itaconic acid, 2- methyl itaconics, sorbic acid, α, Beta-methyl glutaric acid, maleic acid Acid anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride and their salt etc..

As sulfoacid compound, can enumerate for example：Vinyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2- propylene Acid amides -2- methyl propane sulfonic acids, allyl sulphonic acid, methallylsulfonic acid, allyloxy benzene sulfonic acid, methallyl sulfonic acid, (methyl) allyloxy benzene sulfonic acid, 2- allyloxy -2- hydroxypropanesulfonic acids, 3- allyloxy -2- hydroxyl -1- propane sulfonic acids, 2- methacryloxies ethane sulfonic acid and their salt etc..

As phosphate cpd, can enumerate for example：2- methacryloxyethyls phosphoric acid, 2- methacryloxies Ethylphenyl phosphoric acid, 10- methacryloxy decamethylenes phosphoric acid, 4- vinyl benzyls phosphoric acid, the season penta of five acryloyl group two Tetrol phosphoric acid and their salt, 2- (methyl) acryloyl-oxyethyl phosphate, diethyl (ethenylphenyl) phosphate, 4- Phosphates such as vinyl benzene diethyl phosphonate, diphenyl -2- methacryloxyethyl phosphates etc..

It is explained, phosphate can also turn into polymerizable group [=P (O) (OH)], therefore, phosphoric acid, trimethyl sometimes Phosphate, triethyl phosphate, Tributyl phosphate ester, trioctyl phosphate, three butoxyethyl phosphates, triphenyl phosphoric acid The phosphoric acid esters such as ester, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate can also be used as it is cloudy from Sub- property water solubility organic oxygen compound uses.

For the content of the anionic property water solubility unit in block copolymer (I), from the viewpoints such as dispersiveness, phase For block copolymer (I) total amount, preferably 0.5~20 weight %, more preferably 0.5~15 weight %, further preferably For 1~10 weight %.

The water-insoluble unit of nonionic is the construction unit of the divalent from nonionic non-water soluble compounds.It is non-from The sub- water-insoluble unit of property is used for example in order to adjust the hydrophilic degree of polymer blocks (B).In addition, in nonionic In the case that the hydrophily of the water-insoluble unit of property is higher, the hydrophilic effect of polymer blocks (B) is improved.As it is non-from Sub- property non-water soluble compounds, as long as nonionic and organic compound water-insoluble and with polymerizable group, just do not have It is particularly limited to, there is at least one kind of hydrophobicity base in chain alkyl, cyclic hydrocarbon group, aromatic hydrocarbyl in preferably 1 molecule Group (hereinafter sometimes referred to simply as " hydrophobic group ") and the water-insoluble organic compound of nonionic of polymerizable group.Give With explanation, polymerizable group is preferably alkenyl, more preferably vinyl.

, can as the water-insoluble organic compound of nonionic in 1 molecule with hydrophobic group and polymerizable group To enumerate for example：Chain-like alkyl (methyl) acrylate, cycloalkyl (methyl) acrylate, aryl (methyl) acrylate, benzene Vinyl compound etc..These materials can be used alone, or two or more is applied in combination.

As chain-like alkyl (methyl) acrylate, can enumerate for example：(methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) isopropyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) acrylic acid The carbon number of the moieties such as ethylene oxidic ester is 1~17 alkyl (methyl) acrylate.

As cycloalkyl (methyl) acrylate, can enumerate for example：(methyl) acrylic acid ring propyl ester, (methyl) acrylic acid Ring butyl ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid cycloheptyl ester, (methyl) acrylic acid The carbon number of the cycloalkyl moieties such as ring monooctyl ester, (methyl) acrylic acid ring nonyl ester, (methyl) acrylic acid ring last of the ten Heavenly stems ester is 3~10 ring Alkyl (methyl) acrylate.

As aryl (methyl) acrylate, can enumerate for example：(methyl) benzyl acrylate, (methyl) acrylic acid benzene oxygen Base ethyl ester etc..

As distyryl compound, such as styrene, α-methylstyrene, methyl styrene, 3- methylbenzenes can be enumerated Ethene, 4- methyl styrenes, 3- ethyl styrenes, 4- ethyl styrenes, 4- aminostyryls, 4- dimethylaminostyrenes, Methoxy styrene, 1-chloro-4-methyl-benzene, chlorostyrene, 4- t-butyl styrenes, vinyltoluene, vinyltoluene etc. have At least one in chain-like alkyl selected from carbon number 1~4, the chain alkoxy of carbon number 1~4, halogen atom and amino Distyryl compound as substituent.

For the content of the water-insoluble unit of nonionic in block copolymer (I), from viewpoints such as dispersivenesses, Relative to block copolymer (I) total amount, preferably 10~50 weight %, more preferably 15~45 weight %, further preferably For 20~40 weight %.

As described above, preferable form of the block copolymer (I) as the content of each unit, has following form：Contain The weight % of ring-type amine unit 5~30 (more preferably 5~25 weight %, further preferred 7~20 weight %), nonionic are water-soluble The weight % of unit 40~80 (more preferably 45~75 weight %, further preferred 45~73 weight %) and anionic property are water-soluble The property weight % of unit 0.5~20 (more preferably 0.5~15 weight %, further preferred 1~10 weight %) the 1st form；With with The ratio of 1st homomorphosis contains ring-type amine unit, nonionic water solubility unit and anionic property water solubility unit, enters one Step contains the nonionic water-insoluble weight % of unit 10~50 (more preferably 15~45 weight %, further preferred 20~40 weight Measure %) the 2nd form.

Block copolymer (I) such as can using active (control) radical polymerization known to polymerization synthesize. When substantially being distinguished to living radical polymerization, there are ATRP (ATRP) method, RAFT (reversible additions Breaking type chain transfer polymerization) method, NMP (Nitroxide radical polymerizations：Nitroxide-Mediated Radical Polymerization) method, TERP (organic tellurium regulation and control radical polymerization) method, RTCP (reversible chain tra nsfer catalytic polymerization) method etc., As long as these methods are suitably selected to be synthesized.

Active free radical polymerization for example can -100~250 DEG C, preferably 0~200 DEG C, more preferably room temperature~200 DEG C, enter Implement at a temperature of preferably 50~150 DEG C of one step, in solvent-free in (polymerisation in bulk) or solvent.

As solvent, it is inactive solvent that can use for polymerisation, can be enumerated for example：Benzene, toluene etc. The halogenation such as the ether series solvents such as hydrocarbon system solvent, diethyl ether, tetrahydrofuran, dichloromethane, chloroform hydrocarbon system solvent, acetone, Methylethyl The alcohol series solvents such as the ketone series solvents such as ketone, methyl iso-butyl ketone (MIBK), methanol, ethanol, propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, acetonitrile, The carbonic esters such as the ester series solvents such as the nitrile series solvents such as propionitrile, benzonitrile, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate Acid amides series solvents such as series solvent, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..

In order to using living radical polymerization manufacture block copolymer (I), enumerate：Gradually it is added to each structure The method of the ormal weight of the starting compound of the group of unit；Using a pre-synthesis polymer blocks as high molecular polymerization Initiator, the method for polymerizeing another polymer blocks；Polymer blocks are by reacting into line unit obtained from polymerizeing respectively Method of conjunction etc..In the case of gradually addition using starting compound, the conversion preferably in the starting compound being previously charged into At the time of rate is 80~95%, load follow-up starting compound.Conversion ratio for example by chromatography, nuclear magnetic resonance spectrometry, Gravimetric method etc. is obtained.

As using a pre-synthesis polymer blocks as polymeric initiator, polymerize another polymer blocks Method, such as following methods can be enumerated：It is the desired moment in the polymerization of polymer blocks, temporary with activated state When reduce and temperature and stop polymerizeing, be evaporated under reduced pressure after the starting compound for removing a polymer blocks, it is poly- to add another The starting compound of compound block.In the case where being polymerize the 3rd later polymer blocks, also enter in the same manner as it Row operation.

The molecular weight of resin type dispersant is not particularly limited, and weight average molecular weight is preferably 1000~100000.Wherein, close In above-mentioned block copolymer (I), from the viewpoint of dispersiveness, not weight average molecular weight but peak top molecular weight is preferred 3000~1,000,000, more preferably 3000~500,000, it is further preferred 4000~100,000, particularly preferred 4000~50,000, most preferably 5000~30,000 scope.The molecular weight of block copolymer (I) can by suitably select each construction unit species and content, Time of the stopping of polymerisation etc. and adjust.

The acid number and amine value of resin type dispersant are according to functional group contained in the resin for forming resin type dispersant and its Content determines.Acid number (acid number when being converted by solid constituent) for example can be by the basis of DIN EN ISO 2114 Method is obtained, and amine value (amine value when being converted by solid constituent) for example can be for example, by the side on the basis of DIN 16945 Method is obtained.The acid number of the dispersant of acid number type is not particularly limited, preferably 20~150mgKOH/g, the dispersant of amine value type Amine value be not particularly limited, preferably 5~30mgKOH/g.In the case of the dispersant of acid number and amine value more than 0, do not have It is particularly limited to, preferred acid number is 5~50mgKOH/g, and preferably amine value is 5~50mgKOH/g.Wherein, it is total on above-mentioned block Polymers (I), from the viewpoint of dispersiveness, preferred acid number is more than 20mgKOH/g, more preferably 20~80mgKOH/g, enters one Step is preferably 25~75mgKOH/g, and amine value is more than 40mgKOH/g, more preferably 40~100mgKOH/g, further preferably For 42~98mgKOH/g.

As surfactant type dispersant, according to ionic, can enumerate：Naphthalenesulfonic acid formalin condensation product salt, virtue Anion active agent (anionic), the polyoxyethylene alkane such as fragrant race's sulfonic acid formaline condensates, polyoxyethylene alkyl phosphate Cationic active agent such as the tweens such as base ether (nonionic), alkylamine salt, quaternary ammonium salt (cationic) etc..Live on surface Formulation dispersant is also commercially available various materials for property, and its concrete example is as described below, but is not limited to these.

Kao Corp's system：DEMOL N、RN、MS、SN-B、EMULGEN 120、430、ACETAMIN 24、86、 QUARTAMIN 24P、

Nikko Chemicals Co., Ltd's system：NIKKOL BPS-20、BPS-30、DHC-30、BPSH-25、

Di-ichi Kogyo Seiyaku Co., Ltd.'s system：PLYSURF AL、A208F、

LION Co. Ltd. systems：ARQUAD C-50, T-28, T-50 etc..

Dispersant as described above both can be a kind, or two or more dispersant combined.In 2 kinds of combination In the case of above, such as in the case of for resin type dispersant, the different material of combination resin can be enumerated each other, combined The material of acid number type and amine value type, in the case of for surfactant type dispersant, it is different combined ionic can be enumerated Material (such as anionic and nonionic etc.) etc., but be not limited to these each other.

For the content (solid constituent or active ingredient) of the dispersant in black pigment compositions, from dispersion stabilization From the viewpoint of, relative to total 100 parts by weight of black organic pigment and coloured organic pigment, preferably 2~20 parts by weight, More preferably 5~10 parts by weight.Wherein, the most suitable addition of dispersant is according to combination of the species of the organic pigment with using etc. Suitably it is adjusted.In addition, in the case of using pigment derivative described later, the content of the coloured organic pigment means to wrap Total amount containing pigment derivative.

In embodiments of the present invention, in addition to above-mentioned dispersant, in order that black organic pigment and coloured organic face Material more stably disperses in black pigment compositions, can use pigment derivative as dispersing aid.Derived using pigment In the case of thing, the pigment derivative for having imported the part for having compatibility with dispersant or polar group is adsorbed in each organic face The surface of material, it can turn into the adsorption site of dispersant.In this case, it can be present in dispersant via pigment derivative Organic pigment surface, therefore, each organic pigment can be more stably scattered in black pigment group in the form of fine particle In compound.In addition, it can also more efficiently prevent from its aggegation again.Wherein, as described above, according to the functional group of pigment and importing Characteristic, there is the possibility being had an impact to the characteristic of liquid crystal cells.Therefore, in the case of using pigment derivative, preferably examine Consider the point and dispersiveness and determine species and usage amount.

Organic pigment has specifically been imported acidic-group, alkali as precursor skeleton, on side chain by pigment derivative The compound of property group, aromatic group as substituent.It can specifically be enumerated as the organic pigment of precursor skeleton：Quinoline Acridone series pigments, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolinone system face Material, quinoline pigments, diketopyrrolo-pyrrole pigment, benzimidazolone pigment, dioxazine series pigments etc..In addition, as parent bone Frame, it is however generally that it is polycyclic also to include the flaxen aromatic series such as the naphthalene system for being not referred to as pigment, anthraquinone system, triazine system, quinoline system Compound.

As pigment derivative, Japanese Unexamined Patent Publication 11-49974 publications, Japanese Unexamined Patent Publication 11-189732 can be used Publication, Japanese Unexamined Patent Publication 10-245501 publications, Japanese Unexamined Patent Publication 2006-265528 publications, Japanese Unexamined Patent Publication 8-295810 Publication, Japanese Unexamined Patent Publication 11-199796 publications, Japanese Unexamined Patent Publication 2005-234478 publications, Japanese Unexamined Patent Publication 2003-240938 Pigment derivative described in number publication, Japanese Unexamined Patent Publication 2001-356210 publications etc..

For the content (solid constituent) of the pigment derivative in black pigment compositions, from the viewpoint of dispersion stabilization Set out, relative to total 100 parts by weight of black organic pigment and coloured organic pigment, preferably 2~15 parts by weight, more preferably For 5~10 parts by weight.Wherein, the most suitable addition of pigment derivative can be according to the organic pigment with using and dispersant The appropriate adjustment such as the combination of species, influence of characteristic to liquid crystal cells.In addition, " black organic pigment and coloured organic pigment Total 100 parts by weight " mean the total amount not comprising pigment derivative.

The particle diameter of black organic pigment and coloured organic pigment can suitably be determined according to purposes etc. it is preferable to use The average grain diameter of general primary particle is the material that average primary particle diameter is 20~200.In addition, for example in intercolumniation every, black matrix Purposes in, when film is formed, from the viewpoint of higher OD values are obtained, more preferably average primary particle diameter be 20~ 80nm.In addition, average primary particle diameter for example can as using through electron microscope (TEM) carry out shooting in it is multiple The arithmetic average of the Breadth Maximum of the primary particle of (such as 50) and calculate.

, can be with from the viewpoint grade that average grain diameter is adjusted according to the species of organic pigment in embodiments of the present invention It is ground processing in advance.Milled processed can conventionally be carried out according to species of organic pigment etc..Ground as this Mill processing, can be enumerated such as solvent salt milling.

In embodiments of the present invention, having in composition is formed from more raising black pigment compositions and black coating film From the viewpoint of machine pigment isodispersity, in addition to above-mentioned dispersant, dispersion resin can also be used as dispersing aid.It is special It is not that the film forming component used in black coating film described later formation composition is polymerizable component, in particular optical polymerism In the case of composition, preferably using this dispersion resin.As the dispersion resin that can be used in the present invention, after can enumerating The alkali soluble resin stated.Dispersion resin both can be of the same race with the alkali soluble resin for black coating film formation composition Resin kind, or not homogenous resins kind.For the content of dispersion resin, relative to black organic pigment and coloured organic Total 100 parts by weight of pigment, preferably 10~50 parts by weight.In addition, in the case of using pigment derivative, black is organic The content of pigment and coloured organic pigment means to include the total amount of pigment derivative.

As the solvent that can be used in the present invention, can suitably be selected according to species of film forming component described later etc. Select, can enumerate for example：The various organic solvents such as fragrant family, ketone system, ester system, glycol ethers system, alcohol system, fatty family.Wherein, From the viewpoint of film formative, the organic solvent that is preferably selected from fragrant family, ketone system, ester system, glycol ethers system.It is organic molten Agent can be only a kind, or two or more solvent combined.

As the organic solvent of fragrant family, can enumerate for example：Toluene, dimethylbenzene, ethylo benzene etc. are aromatic hydrocarbon.

As the organic solvent of ketone system, can enumerate for example：Methyl ethyl ketone, methylisobutylketone, diisobutyl ketone, acetyl group Acetone, isophorone, acetophenone, cyclohexanone etc..

As the organic solvent of ester system, can enumerate for example：Ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid are different Propyl ester, methyl propionate, acetic acid -3- methoxybutyls, glycol acetic acid esters, propylene glycol methyl ether acetate (PMA), propane diols Monoethyl ether acetate, 3- methyl -3- methoxybutyls acetic acid esters, monochloro acetic acid methyl esters, monochloro acetic acid ethyl ester, monochloro acetic acid fourth Ester, methyl acetoacetate, ethyl acetoacetate, acetate of butyl carbitol, butyl lactate, ethyl -3- ethoxy-cs acid esters, second Glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3 butylene glycol diacetate esters etc..

As the organic solvent of glycol ethers system, can enumerate for example：Ethylene glycol mono-ether, ethylene glycol monoethyl ether, ethylene glycol list Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, ethyleneglycol monopropylether, diethylene glycol list Isopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, the tertiary butyl ether of ethylene glycol list, diethyl two The tertiary butyl ether of alcohol list, 1- methyl isophthalic acids-methoxybutanol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol t-butyl ether, the third two Alcohol list positive propyl ether, monoisopropyl ether, dipropylene glycol monomethyl ether, DPE, DPG list positive propyl ether, dipropyl The water miscible glycol ethers such as glycol mono-iso-propyl ether, propane diols mono-n-butyl ether, DPG mono-n-butyl ether,

Ethylene glycol monohexylether, ethylene glycol -2- ethyls hexyl ether, ethylene glycol phenyl ether, diethylene glycol n-hexyl ether, diethylene glycol -2- Ethyl hexyl ether, propylene glycol monobutyl ether, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol propyl ether, propylene glycol monomethyl ether acetate etc. are water-insoluble Glycol ethers etc..

As the organic solvent of alcohol system, can enumerate for example：The carbon numbers such as ethanol, methanol, butanol, propyl alcohol, isopropanol 1 ~4 alkyl alcohols,

Ethylene glycol, propane diols, diethylene glycol, pentamethylene glycol, trimethylene, 2- butylene-1,4-diols, 2- second Polyethylene glycol below 2000 of base -1,3- hexylene glycols, 2- methyl -2,4-PD, tripropylene glycol, molecular weight, 1,3- propane diols, Isopropanediol, i-butylene glycol, 1,4- butanediols, 1,3 butylene glycol, 1,5- pentanediols, 1,6-HD, glycerine, middle erythrose Alcohol, pentaerythrite etc..

As the organic solvent of fatty family, can enumerate for example：Aliphatic hydrocarbons such as pentane, n-hexane, normal heptane etc..

For the addition of solvent, in the case where forming the preparation of composition for black coating film described later, from behaviour From the viewpoint of the property made, it can add in a manner of the solid component concentration comprising black organic pigment etc. turns into 50~85 weight % Add.

In the embodiment of the black pigment compositions of the present invention, in addition to above-mentioned composition, other add can also be contained Add agent.

Black pigment compositions by above-mentioned each composition such as can be by making an addition to ball mill, sand mill, disperser Known dispersion machine is simultaneously disperseed and obtained.That is, black pigment compositions for black organic pigment in a solvent and coloured have The solid constituents such as machine pigment disperse the dispersion formed in the form of granules.Here, particle mean above-mentioned black organic pigment, The second particle that primary particle of coloured organic pigment etc. carries out aggegation and formed.In addition, the method for the addition of each composition does not have It is particularly limited to, the mixture for being mixed with each composition simultaneously can be subjected to decentralized processing.It is each organic alternatively, it is also possible to be blended with Pigment and solvent and dispersant and/or the mixture of other any conditions are disperseed, and by every kind of pigment, prepare pigment combination Thing, these color compositions are mixed and then secondary disperseed.Can also be other methods.

The average grain diameter for the particle being scattered in the black pigment compositions obtained as described above is (below, sometimes referred to as " scattered average grain diameter ".) it is not particularly limited that it is preferable to use about 30~300nm material.In addition, for example in post Interval, black matrix purposes in, from the viewpoint of the surface smoothness of film, more preferably scattered average grain diameter is 30~ 150nm.In addition, scattered average grain diameter can be for example measured using particle size determination machine.In addition, as particle size determination machine, can To enumerate Otsuka Electronics Co., Ltd.'s system, FPAR-1000 etc..

＜ black coating films form composition ＞

The embodiment that the black coating film of the present invention forms composition includes above-mentioned black pigment compositions and film shape Into composition.So, by the way that comprising black pigment compositions as described above, the above-mentioned organic face of black can be passed through in film The effect of material, visible ray is effectively absorbed in wavelength 380nm~750nm region.Furthermore, it is possible to by ultraviolet range (ripple The long region less than 380nm) and the manufacture that is suppressed to flat board of absorption of infrared spectral range (region of the wavelength more than 750nm) do not have Influential degree.In addition, by being combined with least two kinds of coloured organic pigments beyond the black organic pigment, can apply The light of visible region is interdicted in film without using carbon black, compared with visible region, can effectively suppress ultraviolet and The absorption of infrared ray.And then the solvent resistance of film can also be improved by the effect of above-mentioned black organic pigment.This Outside, the influence of the characteristic to liquid crystal cells due to carbon black can also be avoided.

As workable film forming component in the embodiment of the black coating film formation composition of the present invention, as long as Solvent resistance is good, can suppress influence to the characteristic of liquid crystal cells, can form the composition of film, is just not particularly limited, Both can be the composition of polymerism, or polymer.As the composition of polymerism, from by developing (negative development) and easy Implement from the aspect of patterning, preferably optical polymerism composition.In addition, as polymer, can enumerate for example：Thermoplastic polyurethane It is resin, (methyl) acrylic resin, polyamide series resin, polyimides system resins, styrene maleic acid system resin, poly- Ester system resin, silicone resin, Cardo resins etc..

As workable optical polymerism composition, photopolymerizable compound and Photoepolymerizationinitiater initiater are included.This photopolymerization Property compound and Photoepolymerizationinitiater initiater for example can use Japanese Unexamined Patent Publication 2009-179789 publications described in material.Carry out During detailed description, this photopolymerizable compound is the addition polymerization compound with least one ethylenical unsaturated double bonds, is selected from With at least one, the compound of the terminal ethylenic unsaturated bond of preferably more than 2.This compound group is in the technical field It is it is well known that can be not particularly limited to use these compounds in the present invention.Photopolymerizable compound for example has There are monomer, prepolymer, i.e. dimer, trimer and oligomer or the chemical form such as their mixture and these copolymers.

As monomer and its example of copolymer, unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, clothing can be enumerated Health acid, butenoic acid, methacrylate, maleic acid etc.), its esters, amide-type, preferably using unsaturated carboxylic acid and aliphatic polyol The amide-type of the ester of compound, unsaturated carboxylic acid and aliphatic polybasic amines.In addition, it is also preferred that using with hydroxyl, ammonia The esters of unsaturated carboxylic acids or amide-type and simple function or polyfunctional isocyanate's class or epoxies of the nucleophilic substitution base such as base, sulfydryl Addition reaction and with the dehydration condensation thing of simple function or polyfunctional carboxylic acid etc..In addition, it is also preferred that there is isocyanide The esters of unsaturated carboxylic acids or amide-type and simple function or polyfunctional alcohols, amine of the electrophilicity substituent such as perester radical, epoxy radicals Class, the addition reaction of thio-alcohol so with the esters of unsaturated carboxylic acids of detachment substituent such as halogen, tosyloxy or Amide-type and simple function or polyfunctional alcohols, amine, the substituted reactant of thio-alcohol.In addition, as other examples, also may be used Using above-mentioned unsaturated carboxylic acid is replaced, to be substituted for compound group obtained from unsaturated phosphonic acids, styrene, vinethene etc..

In addition, as described in these specific such as Japanese Unexamined Patent Publication 2009-179789 publications, it is more as aliphatic The concrete example of the monomer of the ester of first alcoholic compound and unsaturated carboxylic acid, as acrylate, has：Glycol diacrylate, three Glycol diacrylate, 1,3 butyleneglycol diacrylate, tetramethylene glycol diacrylate, propane diols diacrylate Ester, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tris (acryloxypropyl) Ether, methylolethane triacrylate, hexanediyl ester, 1,4- cyclohexanediol diacrylates, tetraethylene glycol Diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, two seasons penta 4 Alcohol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, sorb The acrylate of sugar alcohol five, the acrylate of D-sorbite six, three (acryloyl-oxyethyl) isocyanuric acid esters, polyester acrylate are low Polymers, isocyanuric acid EO modified triacrylates etc..

On these addition polymerization compounds, its structure, be used alone or and use or the application method such as addition it is detailed It can carefully be combined with the performance design of final black coating film formation composition and arbitrarily set.

Such as selected from following viewpoint.In terms of sensitivity, the knot more than the unsaturated group mass contg of preferably every 1 molecule Structure, in many cases, preferably more than 2 functions.In addition, in order to improve solidification film strength, materials more than 3 functions, enter And by and with different functional number, different polymerizable groups (such as acrylate, methacrylate, polystyrene Compound, vinethene based compound) material and the method that adjusts both sensitivity and intensity is also effective.

In addition, for other compositions for being formed with black coating film in composition, (such as the adhesive such as alkali soluble resin gathers Compound, Photoepolymerizationinitiater initiater, colouring agent (pigment)) compatibility, dispersiveness, the selection of addition polymerization compound, use method For it is important the reason for, for example, the use of low-purity compound or of more than two kinds and with improving compatibility can be passed through sometimes.

In addition, also sometimes to improve with selecting specific structure for the purpose of the adaptation of base material etc..Photopolymerizable compound The fixedness composition formed relative to film in composition, contains preferably 5~70 weight %, more preferably 10~60 weight %. In addition, these materials can be used alone, and two or more can also be used.In addition, to the size of the inhibition of oxygen, resolution ratio, The viewpoints such as mist, variations in refractive index, surface adhesion are set out, and the use method of photopolymerizable compound can be selected arbitrarily suitably Structure, cooperation, addition.

As above-mentioned Photoepolymerizationinitiater initiater, the material described in Japanese Unexamined Patent Publication 2009-179789 publications can also be used.

That is, as the Photoepolymerizationinitiater initiater that can be adapted to use in the present invention, for example, acetophenone system, ketal system, hexichol first Ketone system, benzoin system, benzoyl system, xanthone system, active halogen compounds (triazine Xi, oxadiazoles system, coumarin series), acridine System, bisglyoxaline system, oxime ester system etc..

Concrete example of these concrete examples as benzophenone series Photoepolymerizationinitiater initiater, can be enumerated for example：Benzophenone, 4, 4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-dichloro benzophenone etc..

The content that black coating film as Photoepolymerizationinitiater initiater is formed in composition, composition is formed relative to black coating film Total solid content, preferably 0.1~10.0 mass %, more preferably 0.5~5.0 mass %.The content of Photoepolymerizationinitiater initiater During in the range of this, polymerisation can be made to carry out well and form the good film of intensity.

The present invention black coating film formed composition embodiment in, containing optical polymerism composition in the case of, except upper Beyond the black pigment compositions and optical polymerism composition stated, alkali soluble resin can also be contained.

When black coating film forms and contains alkali soluble resin in composition, such as in the intercolumniation carried out using photo-mask process Every manufacture in, in the patterning be applicable black coating film formed composition when, can more improve patternability.

As this alkali soluble resin, the alkali described in Japanese Unexamined Patent Publication 2009-179789 publications can be used solvable Property resin.When simply describing, as the alkali soluble resin that can be used for the present invention, such as can be from for the organic high score of wire Sub- polymer and molecule (preferably using acrylic acid series copolymer, styrene based copolymer as main chain molecule) in have at least 1 Suitably selected in the alkali soluble resin of the group (such as carboxyl, phosphate, sulfonic group etc.) of individual promotion alkali-soluble.Wherein, Further preferably dissolve in organic solvent and the alkali soluble resin to be developed using weak base aqueous solution.

As the preferable material of alkali soluble resin, can especially enumerate (methyl) acrylic acid and can be copolymerized with it its The copolymer of its monomer.Here, (methyl) acrylic acid is the general name for being combined acrylic acid and methacrylic acid, it is also same below Sample, (methyl) acrylate is the general name of acrylate and methacrylate.

As alkyl (methyl) acrylate, aryl (first can be enumerated with other monomers of (methyl) acrylic acid copolymer Base) acrylate, vinyl compound etc..Here, the hydrogen atom of alkyl and aryl can be substituted with a substituent.

As abovementioned alkyl (methyl) acrylate and the concrete example of aryl (methyl) acrylate, can enumerate：(first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) toluene toluene, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate etc..

As above-mentioned vinyl compound, can enumerate for example：Styrene, α-methylstyrene, vinyltoluene, methyl Glycidyl acrylate, glycidyl acrylate, acrylonitrile, vinylacetate, NVP, methyl-prop Olefin(e) acid tetrahydro furfuryl ester, Group-capped Polystyrene Macromer, polymethyl methacrylate macromonomer, CH₂=CR⁵R⁶、CH₂=C (R⁵)(COOR⁷) (here, R⁵Represent the alkyl of hydrogen atom or carbon number 1~5, R⁶Represent the aromatic series of carbon number 6~10 Hydrocarbon ring, R⁷Represent the alkyl of carbon number 1~8 or the aralkyl of carbon number 6~12.) etc..

These copolymerizable other monomers can be used singly or in combination of two or more.

From the viewpoint of developability, the weight average molecular weight of alkali soluble resin is preferably 5000~50000.

Alkali soluble resin is commercially available various materials, and its concrete example is as described below, but is not limited to these.

Showa Highpolymer Co., Ltd's system：Ripoxy SPC-2000、

Mitsubishi Rayon Co., Ltd's system：DIANAL NR series,

Diamond hamrock Co.Ltd., system：(the polyurethane acroleic acid oligomer containing COOH of Photomer 6173 (Polyurethane acrylic oligomer))、

Osaka Organic Chemical Industry Co., Ltd.'s system：Viscoat R-264、KS Resist 106、SOP-005、

Daisel chemical industry Co., Ltd's system：CYCLOMER P are serial, PLACCEL CF200 are serial,

Daicel UCB Co. Ltd. systems：Ebecryl 3800、

Nippon Shokubai Co., Ltd：RD-Y-503 etc..

The content that black coating film as alkali soluble resin is formed in composition, the total of composition is formed in black coating film In solid constituent, preferably 1~20 weight %, more preferably 2~15 weight %, particularly preferably 3~12 weight %.In black Contain sometimes as dispersion resin in color compositions, be total amount.

The present invention black coating film formed composition embodiment in, containing optical polymerism composition in the case of, except upper Beyond the black pigment compositions and optical polymerism composition, alkali soluble resin stated, solvent can also be contained.By using molten Agent, can suitably it prepare.

As this solvent, can enumerate：Esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, formic acid penta Ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl esters, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methoxy menthyl acetate, methoxyl group second Acetoacetic ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate；3- hydroxy methyl propionates, 3- hydracrylic acids The 3- hydroxyalkyl propionate classes such as ethyl ester；3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, 2- methoxypropionic acid first Ester, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- oxygen Base -2 Methylpropionic acid methyl esters, 2- epoxides -2 Methylpropionic acid ethyl ester, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2- first Base ethyl propionate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- oxos Methyl butyrate, 2-Oxobutyric acid ethyl ester etc.；Ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, second two Alcohol list ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetic acid Ester etc.；Ketone, for example, methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone etc.；It is aromatic hydrocarbon, for example, toluene, dimethylbenzene Deng.

Solvent can be used singly or in combination of two or more.

The content that black coating film as solvent is formed in composition, consider the kind of the solvent in black pigment compositions Class, content, total solid content (nonvolatile component) content preferably formed with black coating film in composition turn into 15~50 weights Amount % mode contains.

Situation using polymer as film forming component also with the situation using optical polymerism composition likewise it is possible to Use solvent.As this solvent, the material that can be used in above-mentioned black pigment compositions can be used, can be with light The material that polymerizable component is used together.

In this case, the content that the black coating film as solvent is formed in composition, it is also considered that molten in pigment dispersion Species, the content of agent, preferably with black coating film formed composition in total solid content (nonvolatile component) content turn into 15~ 50 weight % mode contains.

Formed in the black coating film of the present invention in composition, dispersing aid, sensitizer (enhanced sensitivity color can be added as needed on Element), chain-transferring agent, fluorine system organic compound, thermal polymerization, thermal polymerization composition, filler, surfactant, closely sealed rush Enter the various additives such as agent, antioxidant, anti-agglutinant, surface conditioner (levelling agent).It is contained in black pigment compositions In the case of, as long as adjustment addition.

The black coating film of the present invention forms composition by adding film forming component in black pigment compositions, utilizing Disperser etc. is stirred and obtained.

The black coating film of the present invention forms composition as described above, in film, and without using carbon black, it is only visible ray to absorb The light in region, solvent resistance are good.Furthermore it is possible to positioned in manufacturing process using infrared ray.And then use photopolymerization Property composition as film forming component in the case of, using ultraviolet carry out polymerisation it is good, also not to manufacturing process Have an impact.Thus, for example the black intercolumniation as the flat board for liquid crystal display device is every particularly preferred.In addition, as figure As the black matrix of the colored filter of display device also is adapted for.

Embodiment

The manufacture of (Production Example 1) pigment derivative 1

Relative to the parts by weight of chlorosulfonic acid 200, with paratonere 255 (BASF AG's system, product name Irgazin Red L3551HD) turn into 20 parts by weight and thionyl chloride to add as the mode of 10 parts by weight, after being reacted 5 hours with 60 DEG C, be expelled to In 2 liters of frozen water, filtered and washed, obtain the parts by weight of chlorosulfonylation thing 26.9 of paratonere 255.It is set to be scattered in water In 200 parts by weight, the parts by weight of diethyl amino propyl amine 8.3 are added, after being reacted 1 hour with 80 DEG C, is filtered, washed, done Dry and crushing, obtains the pigment derivative 1 shown in the following formula (3) of 31.5 parts by weight.

The manufacture of (Production Example 2) pigment derivative 2

Relative to the parts by weight of chlorosulfonic acid 200, turned into pigment Violet 23 (DIC company systems, the Crude of product name Violet 23) The mode that 20.4 parts by weight and thionyl chloride turn into 20 parts by weight is added, and after being reacted 5 hours with 60 DEG C, is expelled to 2 liters of frozen water In, filtered and washed, obtain the parts by weight of chlorosulfonylation thing 27.2 of pigment Violet 23.It is set to be scattered in the parts by weight of water 200, The parts by weight of diethyl amino propyl amine 15 are added, after being reacted 1 hour with 80 DEG C, is filtered, washed, dried and crushed, obtained Pigment derivative 2 shown in the following formula (4) of 31.9 parts by weight.

The manufacture of (Production Example 3) pigment derivative 3

88% sulfuric acid of 200 parts by weight is loaded after 300ml three-necked flask, paratonere 255 is loaded under water cooling (BASF AG's system, product name Irgazin Red L3551HD) 20 parts by weight, make its reaction 3 hours with 40~45 DEG C and carry out Sulfonation.Then, the synthesis stoste is expelled to after being put into the beaker of 1L water, is filtered, its paste is moved to 2L beakers, water 1.5L is added, after stirring 1 hour and fully disperse with 60~70 DEG C, add cetyl trimethyl chlorination The parts by weight of ammonium 1 and carry out making salt.After stirring 10 minutes or so, filtered and washed, by obtained paste with 100 DEG C of dryings, Obtain the pigment derivative 3 shown in following formula (5).

(DM-3)

The manufacture of (Production Example 4) pigment derivative 4

In the parts by weight of chlorosulfonic acid 200 add raw copper phthalocyanine (Zhuhai Japan company system, product name T-99 Crude Blue, Pigment blue 15：3) 40.2 parts by weight and the parts by weight of thionyl chloride 10, after making its reaction 5 hours with 60 DEG C, it is expelled to 2 liters of frozen water In, filtered and washed, obtain the parts by weight of chlorosulfonylation thing 47 of pigment blue 15.It is scattered in water 200g, add two The parts by weight of dimethylaminopropyl amine 8.3, after making its reaction 1 hour with 80 DEG C, filtered, washed, being dried and being crushed, being obtained Pigment derivative 4 shown in the following formula (6) of 51.5 parts by weight.

The manufacture of (Production Example 5) resin type dispersant 1

By butyl acrylate (the water-insoluble organic compound of nonionic) 192.8 parts by weight, methoxy poly (ethylene glycol) (n ≈ 9) methacrylate (nonionic water-soluble organic compounds) 321.9 parts by weight, (anionic property water solubility has acrylic acid Machine compound) 59.2 parts by weight, N- (2- methyl-propyls)-N- (1- diethyl phosphonyl -2,2- dimethyl propyls)-O- (2- carboxylics Base propyl- 2- yls) hydroxylamine (polymerization regulator) 15.0 parts by weight, the parts by weight of propylene glycol methyl ether acetate (reaction dissolvent) 370 Load the stainless steel detachable flask of 2L volumes, while nitrogen bubbling and stirring are carried out, while system is warming up in oil bath 125 DEG C, after heating terminates, it is set to react 6.5 hours, synthetic polymer B block.It is a small amount of to sample content, carries out GPC measure, As a result peak top molecular weight is 9570, Mw/Mn=1.43.

Then, by the parts by weight of 4-vinylpridine (cyclic amine compound) 56.1, propylene glycol methyl ether acetate, (reaction is molten Agent) 50 parts by weight input flask, while continuing nitrogen bubbling and stirring, while making it react 4 hours with 125 DEG C.In sampling It is tolerant, GPC measure is carried out, as a result peak top molecular weight is 10140, Mw/Mn 1.45.

Then, temperature in system is warming up to 210 DEG C, 2.0kPa will be decompressed in system, solvent is distilled off and takes out Block copolymer (I).Obtained block copolymer (I) is subjected to GPC measure, as a result peak top molecular weight is that 10990, Mw/Mn is 1.49.In addition, acid number is 74.0mgKOH/g, amine value 52.9mgKOH/g.

The manufacture of (Production Example 6) blue organic pigment 2

By C.I. pigment blue 15s：6 (trade names：FASTOGEN Blue EP-207, DIC system) it is 300 parts by weight, neutral anhydrous Saltcake (about 20 μm of average grain diameter, three field buttocks chemical industry (strain) system) 3000 parts by weight, diethylene glycol ((strain) day as solvent This catalyst system) 750 parts by weight make an addition to 5L kneaders ((strain) Moriyama systems, S5-2GH-S types), while the temperature with mixture Degree carries out temperature control as 50 DEG C of mode, is ground 9 hours while being kneaded.By warm water 30L of the mixing triturate at 40 DEG C In be stirred scattered, move to exert to adopt thereafter and filtered in funnel (Nutsche), repetition is washed to saltcake and removed completely, obtains To pigment water suspension paste.The pigment water suspension paste is dried 2 hours with 105 DEG C.The dried object (is found into science and engineering (strain) altogether with pulverizer System, micromill, Sample Mill SK-M2) crush, obtain the blue organic pigment 2 of 330 parts by weight.Obtained blueness The average grain diameter of the primary particle of organic pigment 2 is 40nm.The average grain diameter is to be measured, calculated by the shooting carried out using TEM Result.

The composition used in following test example, embodiment and comparative example is as described below.

(a) at least one kind of black organic pigment being selected from above-mentioned formula (1) and (2)

Black organic pigment 1：BASF AG's system, Lumogen Black FK4280

(b) the black organic pigment beyond above-mentioned (a)

Black organic pigment 2：BASF AG's system, Paliogen Black S0084

(c) coloured organic pigment

Organic red pigment 1：Dainippon Ink Chemicals's system, the 229-6438 of PERRINDO Maroon 179, pigment red179 (PR179)

Organic red pigment 2：Clariant company systems, PV Fast Red B, pigment red 149 (PR149)

Organic red pigment 3：Cynic company systems, Cinilex DPP Red SR2P, paratonere 254 (PR254)

Organic red pigment 4：BASF AG's system, Irgazine Red L3551HD, paratonere 255 (PR255)

Blue organic pigment 1：Dainippon Ink Chemicals's system, EP-210, pigment blue 15：6(PB15：6)

Blue organic pigment 2：Production Example 6

Blue organic pigment 3：BASF Co. Ltd. systems, Heliogen Blue D7490, pigment blue 16 (PB16)

Blue organic pigment 4：BASF Co. Ltd. systems, Paliogen Blue EH1900, pigment blue 60 (PB60)

Purple organic pigment：Dainippon Ink Chemicals's system, the 229-4050 of PERRINDO VIOLET 29, pigment violet 29 (PV29)

(d) dispersant

Resin type dispersant 1：Production Example 5

Resin type dispersant 2：BYK-Chemie Japan Co. Ltd. systems, Disperbyk LPN22102, acrylic acid series Resin, acid number 0mgKOH/g, amine value 32mgKOH/g

Resin type dispersant 3：Otsuka Chemical Co., Ltd's system, TERPLUS D2015, acrylic resin, acid number 30mgKOH/g, amine value 63mgKOH/g

Resin type dispersant 4：Otsuka Chemical Co., Ltd's system, TERPLUS MD1000, acrylic resin, acid number 30mgKOH/g, amine value 63mgKOH/g

(e) dispersing aid

Dispersion resin 1：Nippon Shokubai Co., Ltd's system, RD-Y-503, alkali-soluble acrylic resin

Dispersion resin 2：Osaka organic chemistry company system, SOP-005, alkali-soluble acrylic resin, acid number 29mgKOH/g, amine value 116mgKOH/g, weight average molecular weight 19000

(f) solvent

Propylene glycol methyl ether acetate (PMA)

(g) film forming component

Film forms resin：Nippon Shokubai Co., Ltd's system, RD-Y-507, acrylic resin

(embodiment 1~7, comparative example 1)

The preparation ＞ of ＜ black pigment compositions

Each composition is mixed in a manner of as the composition (for solid constituent benchmark beyond solvent) shown in table 1, uses ball mill Disperseed, obtain black pigment compositions.For the crushing medium of ball mill, it is using particle diameterZirconium pearl, Added by being measured relative to abrasive (mill base) in a manner of 100 parts by weight turn into 400 parts by weight.The medium is in decentralized processing After remove.In addition, the composition shown in table 1 is parts by weight.

＜ black coating films form the preparation ＞ of composition

Above-mentioned film is added in obtained each black pigment compositions and forms resin, is stirred, obtained with disperser Composition is formed to black coating film.For film forms the addition of resin, relative to contained in each black pigment compositions Total organic pigment (including pigment derivative) total 100 parts by weight, dispersant, dispersion resin and film is formed resin It is total to turn into 200 parts by weight.

The formation ＞ of ＜ films

Composition is formed using obtained each black coating film, to each composition, is revolved in a manner of thickness turns into 1 μm and 3 μm It is applied on glass plate.As prebake conditions, heated 2.5 minutes with 90 DEG C, as rear baking, heated 30 minutes with 230 DEG C, formed and applied Film.

The measure ＞ of ＜ optical concentrations (OD values)

Using the film for being adjusted to 3 μm of thickness and being formed, determine device (X-Rite361T) using OD and be measured.Measure The OD values of 3 films of thickness are changed centered on 1 μm, by gradient and section, value when the use of thickness being 1 μm is used as OD Value.Evaluation result is shown in table 1.

＜ solvent resistances ＞

The film that 1 μm of thickness will be adjusted to and formed is cut into 2 × 4cm size, at 1-Methyl-2-Pyrrolidone (NMP) After being impregnated 1 hour with 80 DEG C in 50g, the presence or absence of coloring of NMP liquid is confirmed by visual observation.Evaluation result is shown in table 1.In table 1, Using the situation of no coloring as " 〇 ", it will be observed that the situation of coloring represents as "×".

Table 1

(embodiment 8)

The preparation ＞ of ＜ black pigment compositions

Each composition is mixed in a manner of as the composition (for solid constituent benchmark beyond solvent) shown in table 2, uses ball mill Disperseed, on each pigment, obtain color compositions 1~3.For the crushing medium of ball mill, it is using particle diameterZirconium pearl, by relative to grinding the parts by weight of doses 100 turn into 400 parts by weight in a manner of add.The medium is scattered Removed after processing.In addition, the composition shown in table 2 is parts by weight.By 13.3g color compositions 1,1.25g color compositions 2nd, 2.55g color compositions 3 are mixed, and are stirred with disperser, are obtained black pigment compositions.

Table 2

＜ black coating films form the preparation ＞ of composition

Above-mentioned film is added in obtained black pigment compositions and forms resin 18.72g, is stirred with disperser Mix, obtain black coating film and form composition.

The formation of ＜ films and evaluation ＞

Operate similarly to Example 1, form the different film of thickness.Using obtained film, similarly to Example 1 Operation, evaluation OD values, solvent resistance.OD values are 1.24 (/ μm).In addition, the coloring without NMP.

From embodiment 1~8, the result of comparative example 1：For embodiment compared with comparative example, OD values are high, and in embodiment There is no NMP coloring.It may thus be appreciated that：As the embodiment, by using specific black organic pigment and at least two kinds of coloured have Machine pigment, OD values are high, i.e. the absorption of light is good in whole wavelength of visible region, and solvent resistance is also good. In addition, for each pigment used in embodiment 1~8, it is known that ultraviolet and infrared ray absorb and pressed down compared with visible ray System.And then from the contrast of embodiment 1~7 and embodiment 8, in the case of using defined dispersant, it is possible to reduce scattered Agent, the use of pigment derivative.

Claims (4)

1. A kind of 1. black pigment compositions, it is characterised in that：

   Containing at least two kinds of beyond at least one kind of black organic pigment in following formula (1) and (2), the black organic pigment Coloured organic pigment, dispersant and solvent,
2. 2. black pigment compositions as claimed in claim 1, it is characterised in that：

   It is organic that coloured organic pigment beyond the black organic pigment is selected from organic red pigment, blue organic pigment and purple Pigment.
3. 3. black pigment compositions as claimed in claim 2, it is characterised in that：

   The organic red pigment is at least one kind of in following (a) group, and the blue organic pigment is selected from following (b) It is at least one kind of in group, the purple organic pigment to be at least one kind of in following (c) group,

   (a) group：

   C.I. pigment red 149,179,254,255,

   (b) group：

   C.I. pigment blue 15,15：1、15：2、15：3、15：4、15：5、15：6th, 16,60,

   (c) group：

   C.I. pigment Violet 23,29.
4. 4. a kind of black coating film forms composition, it is characterised in that：

   Contain black pigment compositions according to any one of claims 1 to 3 and film forming component.