CN103149799A - Colored resin composition, color filter, liquid crystal display and organic el display device - Google Patents
Colored resin composition, color filter, liquid crystal display and organic el display device Download PDFInfo
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- CN103149799A CN103149799A CN2012105139416A CN201210513941A CN103149799A CN 103149799 A CN103149799 A CN 103149799A CN 2012105139416 A CN2012105139416 A CN 2012105139416A CN 201210513941 A CN201210513941 A CN 201210513941A CN 103149799 A CN103149799 A CN 103149799A
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Abstract
The invention provides a colored resin composition which is characterized in that the section of the obtained pixel is in the shape of a positive cone and is highly dissoluble in developing liquid. Conventionally, the colored resin composition and the developing liquid trade off and take turns and a balance therebetween is hard to achieve. The colored resin composition comprises (A) pigment, (B) solvent, (C) adhesive resin containing resin with specific unsaturated groups, and (D) polymeric monomer containing monomer with oxygroups.
Description
Technical field
The present invention relates to colored resin composition, color filter, liquid crystal indicator and organic EL display.
Background technology
In recent years, color filter not only is used for monitor in liquid crystal display cells (LCD) purposes, and the tendency that expands to for TV is arranged.Along with expansion and the trend in energy-saving epoch of this purposes, the colourity of color filter, contrast etc. there is the requirement of the color characteristics of height.In addition, on the color filter of image sensor (solid-state imager) purposes, need too the high color filters of color characteristics such as color spot minimizing, the raising of color decomposition ability, expect in addition its high-precision refinement.
As mentioned above, in recent years, in surging, colored resin composition tends to high pigment levels to the requirement of the high color reprodubility of color filter.But, when the colored resin composition of use high pigment levels forms colored pattern by photoetching process, see through or make under-exposed phenomenon remarkable its absorption because the pigment obstruction is ultraviolet, when being arranged, exposure can not obtain the tendency that property is solidified in sufficient deep.As a result, easily occur undercut (under cut) in developing procedure, become the colored pattern that cross sectional shape is inverted cone shape, when forming the conductive film of ITO etc., produce the problems such as broken string.
In order to address this problem, for example to disclose in patent documentation 1 and used the colored resin composition that contains specific polymerizable compound.
But, in patent documentation 1, there is following problem: elongated due to the dissolution time in developer solution, dissolution time is elongated, the problem that causes existing the yield in manufacturing easily to reduce.
On the other hand, in order to shorten dissolution time, for example disclose in patent documentation 2 and to have used the Photoepolymerizationinitiater initiater that contains the tertiary amine structure and the photocurable compound with 1 above acidic functionality and 3 above photo-curable functional groups.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2009-288313 communique
Patent documentation 2: Japanese Patent Laid-Open 2004-287230 communique
Summary of the invention
The problem that invention will solve
Yet, in the colored resin composition of record, opposite specifically in patent documentation 2, find: have the situation of the problems such as broken string that causes due to conical in shape.
That is to say, in above-mentioned various prior aries, in the colored resin composition of high pigment levels, the broken string that is caused by conical in shape suppresses, even cross sectional shape becomes along taper, improves with making the dissolubility in developer solution, is the relation of these disappear those long (trade-off), be difficult to take into account.
Therefore, for along taper and the high colored resin composition of the dissolubility in developer solution, the two those long relations that for this reason disappear were difficult to take into account problem of the present invention in the past for the cross sectional shape of pixel that a kind of gained is provided.
In addition, problem of the present invention have for providing the color filter that uses the pixel that above-mentioned colored resin composition forms, and high-quality liquid crystal indicator and organism EL display device.
Solve the means of problem
The inventor is through wholwe-hearted research, found that, if following colored resin composition, can solve above-mentioned problem, complete the present invention, in described colored resin composition, (C) adhesive resin contains the resin of specific unsaturated group, and (D) polymerizable monomer contains the monomer that contains the oxygen base.
Be that the present invention has following formation.
(1) a kind of colored resin composition, it is characterized in that, contain (A) pigment, (B) solvent, (C) adhesive resin and (D) polymerizable monomer, the resin (below be sometimes referred to as " resin that contains specific unsaturated group ") that should (C) adhesive resin contains unsaturated group, and (D) polymerizable monomer contains the monomer of oxygen base, the described resin that contains unsaturated group is to make at least following (C-1) and (C-3) addition (C-4) and (C-5) resin of gained on the multipolymer of copolymerization gained.
(C-1): the compound that has unsaturated link and epoxy radicals in a part
(C-3): have can with the compound of the unsaturated link of described (C-1) copolymerization
(C-4): unsaturated carboxylic acid
(C-5): multi-anhydride.
(2) colored resin composition of record in described (1), is characterized in that, described multipolymer is to make (C-1), (C-3) and following (C-2) copolymerization and the multipolymer that obtains.
(C-2); Have at least a kind of skeleton selecting and the compound of unsaturated link in a part from the group who is formed by tricyclodecane skeleton and bicyclopentadiene skeleton.
(3) colored resin composition of record in described (1) and (2), is characterized in that, the acid number of the described monomer that contains the oxygen base is more than 10mg-KOH/g, below 150mg-KOH/g.
(4) colored resin composition of any one record in described (1)～(3), is characterized in that, (C-4) unsaturated carboxylic acid is methacrylic acid.
(5) colored resin composition of any one record in described (1)～(4), it is characterized in that, the content M of the monomer solid constituent in the content P of the polymer solids composition in colored resin composition and colored resin composition than P/M ratio, more than 0.5, below 4.5.
(6) colored resin composition of any one record in described (1)～(5), is characterized in that, contains described (A) pigment that 28 % by weight are above, 45 % by weight are following that accounts for all solids composition.
(7) colored resin composition of any one record in described (1)～(6), is characterized in that, described (A) pigment contains the zinc bromide phthalocyanine color.
(8) colored resin composition of any one record in described (1)～(7), is characterized in that, further contains (E) photopolymerization and cause composition and thermal polymerization and cause at least a among composition.
(9) a kind of color filter, is characterized in that, contains the pixel of the colored resin composition formation of using any one record in described (1)～(8).
(10) a kind of liquid crystal indicator, is characterized in that, contains the color filter of described (9) record.
(11) a kind of organic EL display, is characterized in that, contains the color filter of described (9) record.
The effect of invention
The pixel of using colored resin composition of the present invention to form, its cross sectional shape is along cone, form ITO etc. lead the Electricity film time be difficult to produce the problem such as broken string, and because the dissolution time in developer solution is short, the yield in the manufacturing that is therefore caused by dissolution time is difficult to reduction.
That is to say, colored resin composition of the present invention can take into account in the past take this disappear that those long relations are that exist, the cross sectional shape of pixel that obtain is for along these two situations of the height of the dissolubility in taper and developer solution.
In addition, the liquid crystal indicator and the organic EL display that contain the color filter that uses the pixel that colored resin composition of the present invention forms and contain this color filter are high-quality.
Description of drawings
[Fig. 1] is the cross section skeleton diagram that shows an example of the organic EL with color filter of the present invention.
[Fig. 2] is the representational microphotograph of the cross sectional shape of the pixel after developing.
Symbol description
100 organic ELs
20 pixels
30 organic protection layers
40 inorganic oxide films
500 organic luminorphors
51 hole injection layers
54 electron injecting layers
Embodiment
Below, explain embodiments of the present invention, but following record being an example of embodiments of the present invention, the present invention is not limited to these contents.
Also have, in the present invention, " (methyl) propenyl ", " (methyl) acrylate " etc. refer to " propenyl and/or methylpropenyl ", " acrylate and/or methacrylate " etc., and for example " (methyl) acrylic acid " refers to " acrylic acid and/or methacrylic acid ".
In addition, " total solids composition " refers to all the components of the colored resin composition of the present invention except the aftermentioned solvent composition.
In the present invention, " look material " has the meaning of " dyestuff " and " pigment " two aspects.
Further, " aromatic ring " has " aromatic hydrocarbon ring " to reach the meaning of " heteroaromatic " two aspects.
In addition, terms such as " C.I. naphthol greens " refers to pigment index (C.I.).
＜colored resin composition 〉
Colored resin composition of the present invention contains (A) pigment, (B) solvent, (C) adhesive resin and (D) polymerizable monomer, should have the resin that contains specific unsaturated group by (C) adhesive resin, and (D) polymerizable monomer has the monomer that contains the oxygen base.In addition, as required, contain (E) photopolymerization and cause composition and/or thermal polymerization initiation composition and other any composition.
At first, describe (C) adhesive resin in detail.
[(C) adhesive resin]
In colored resin composition of the present invention, (C) adhesive resin contains the resin of unsaturated group, and the described resin that contains unsaturated group is to make at least following (C-1) and (C-3) copolymerization and make (C-4) and (C-5) addition and the resin that obtains on the multipolymer that obtains.
(C-1): the compound that has unsaturated link and epoxy radicals in a part
(C-3): have can with the compound of the unsaturated link of described (C-1) copolymerization
(C-4): unsaturated carboxylic acid
(C-5): multi-anhydride
As the compound that has unsaturated link and epoxy radicals in described (C-1) a part, have for example specifically, (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxycyclohexyl ester, (methyl) acrylic acid methyl ethylene oxidic ester.Preferred (methyl) glycidyl acrylate.These can distinguish use separately, also can make up two or more uses.
As have can with the compound (C-3) of the unsaturated link of described (C-1) copolymerization, concrete example has, and the nothing of the unsaturated carboxylic acid that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate and (methyl) acrylic-amino ethyl ester are such replaces or the substituted alkyl ester;
(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid ring heptyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid menthyl ester, (methyl) acrylic acid cyclopentene ester, (methyl) acrylic acid cyclohexenyl group ester, (methyl) acrylic acid cycloheptene ester, (methyl) acrylic acid cyclooctene ester, (methyl) acrylic acid pentadiene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid pinane base (pinanyl) ester, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid norbornene ester, the carboxylate of the ester ring type base that contains unsaturated carboxylic acid that (methyl) acrylic acid pyrene ester is such,
Single saturated carboxylic acid carboxylate of the glycols that (methyl) acrylic acid oligomeric diol mono alkyl ester is such;
The carboxylate of the aromatic rings that contains unsaturated carboxylic acid that (methyl) benzyl acrylate ester, (methyl) acrylic acid phenoxy group ester are such;
The aromatic ethenyl compound that styrene, α-methyl styrene and vinyltoluene are such;
The vinyl esters of carboxylic acids that vinyl acetate and propionate are such;
The vinyl cyanide based compound that (methyl) vinyl cyanide and α-chloro-acrylonitrile are such; The maleic anhydride contracting group with imine moiety that N-phenyl maleic anhydride contracting imines is such etc.
These can distinguish use separately, maybe both can be used in combination.
In addition, intensity aspect consideration for the pixel that improves gained, multipolymer in the present invention (make at least (C-1) and (C-3) copolymerization and the multipolymer that obtains) preferably makes (C-1), (C-3) and (C-2) copolymerization and the multipolymer that obtains, and described (C-2) has at least a kind of skeleton of from the group who is formed by tricyclodecane skeleton and bicyclopentadiene skeleton selection and the compound of unsaturated link in a part.
As (C-2), concrete example has, the compound of (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, following formula (1) expression.These can distinguish use separately, maybe both can be used in combination.
(in formula (I), R
1Expression hydrogen atom or methyl.)
As described unsaturated carboxylic acid (C-4), specifically, preferred acrylic acid or methacrylic acid.Acrylic acid and methacrylic acid can be distinguished separately and use, or both are used in combination.In addition, except these acrylic or methacrylic acid, also can use other acid.As other acid, specifically, also may be used at least a kind of carboxylic acid that butenoic acid, itaconic acid, maleic acid, fumaric acid etc. are selected from other unsaturated carboxylic acid.In addition, also may be used the monomer that contains hydroxyl and carboxyl in same a part as α-(hydroxymethyl) acrylic acid.
As described multi-anhydride (C-5), use with alkali-developable in order to give adhesive resin.Particularly, the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic acid acid anhydride are arranged for example; The multi-anhydride of trimellitic anhydride, PMA, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride etc.Preferred tetrabydrophthalic anhydride or succinic anhydride.These can distinguish use separately, or are used in combination of two or more.
Of the present invention making (C-1)～(C-3) copolymerization and in the multipolymer that obtains, the ratio of the constituent of introducing respectively from (C-1)～(C-3), with respect to the total molal quantity of the constituent that consists of described multipolymer, in mole fraction, preferably in following scope.
Component units from (C-1) introducing: 2～98 % by mole
Component units from (C-2) introducing: 2～90 % by mole
Component units from (C-3) introducing: 2～65 % by mole
In addition, the ratio of preferred described constituent is in following scope.
Component units from (C-1) introducing: 40～80 % by mole
Component units from (C-2) introducing: 5～40 % by mole
Component units from (C-3) introducing: 5～30 % by mole
In addition, further, reach (C-5) in described multipolymer addition (C-4), pay dissolubility and the light/Thermocurable of resin in developer solution.
(C-4) addition amount, epoxy radicals 1.0 equivalents in the resin that obtains with respect to making (C-1)～(C-3) polymerization are 0.5～1.0 equivalent, preferred 0.7～1.0 equivalent.
If ratio of components (C-4) in above-mentioned scope, obtains sufficient photo-curable or Thermocurable, sensitivity or reliability are excellent, and be therefore preferred.
(C-5) addition amount with respect to the amount that makes the hydroxyl that (C-4) when reaction generate, in the mole fraction base, is 50～100%, preferred 60～100%.
(C-5) ratio of components is in above-mentioned scope the time, and the dissolubility in alkaline developer is excellent, is difficult for having residue to occur, and is therefore preferred.
Contain in the resin of specific unsaturated group, the weight-average molecular weight of the polystyrene conversion of measuring with GPC, usually more than 4,000, preferred 4, more than 500, more preferably more than 5,000, in addition, usually 100, below 000, preferred below 20,000, more preferably below 15,000.
In the time of in above-mentioned scope, be not prone to film during development and reduce, and during development, the removal of non-pixel portion is good, therefore preferred.
The molecular weight distribution (weight-average molecular weight Mw/ number-average molecular weight Mn) that contains the resin of specific unsaturated group, preferred 1.5～6.0, more preferably 2.0～4.0.Molecular weight distribution (weight-average molecular weight Mw/ number-average molecular weight Mn) is 1.5～6.0 o'clock, and developability is excellent, and is therefore preferred.
(other resins)
Colored resin composition of the present invention except the resin that contains specific unsaturated group, also can contain other adhesive resins.Such as the macromolecular compound that uses the middle records such as each communiques such as Japanese patent laid-open 7-207211 communique, Japanese Patent Laid-Open 8-259876 communique, Japanese Patent Laid-Open 10-300922 communique, Japanese Patent Laid-Open 11-140144 communique, Japanese Patent Laid-Open 11-174224 communique, Japanese Patent Laid-Open 2000-56118 communique, Japanese Patent Laid-Open 2003-233179 communique.
(content)
The content of (C) adhesive resin that uses in colored resin composition of the present invention, all solids composition with respect in colored resin composition is generally 5～90 % by weight, the scope of preferred 10～70 % by weight.
Preferably when above-mentioned scope, the dissolubility in developer solution is abundant, be not prone to the development residue on the substrate of non-pixel portion, and the film that is not prone to the pixel portion of exposure when developing section reduces, and the removal of non-pixel portion is good, thereby preferred.
In addition, in the present invention, as the contained all resins of (C) adhesive resin, be preferably the resin that contains specific unsaturated group, that is to say, preferably contain the resin that contains specific unsaturated group in above-mentioned scope.
[(D) polymerizable monomer]
In colored resin composition of the present invention, (D) polymerizable monomer contains the monomer of oxygen base.
(D) polymerizable monomer be can polymerization low molecular compound, preferably have at least the two keys of an ethene can addition polymerization compound (below, be sometimes referred to as " ethene compound ").
That is, the monomer that contains the oxygen base in the present invention be can polymerization low molecular compound, as long as and contain the aerobic base, preferably contain the ethene compound of aerobic base.
Other compositions that contain in colored resin composition are considering with the good this point of intermiscibility of the resin that contains specific unsaturated group that especially preferred oxygen base is carboxyl.
That is to say, the monomer that contains the oxygen base preferably contains the low molecular compound of carboxyl and the two keys of ethene.
As the monomer that contains the oxygen base, the carboxylate of aliphatic polyhydroxy compound and unsaturated carboxylic acid is for example arranged for example.
Following compound is arranged for example: with the unreacted hydroxyl dibasic acid anhydride modification of aliphatic polyhydroxy compound, import the compound of carboxyl, import sulfonic compound etc. by the photo-curable functional group that will have more than 3 with the concentrated sulphuric acid or oleum modification in addition.
As this photo-curable functional group, be preferably acryloyl group, particularly preferably aliphatic polyhydroxy compound is pentaerythrite and/or person's dipentaerythritol.
In addition, consider the preferred carboxyl of oxygen base of importing from the good this point of alkali-developable.
The particularly preferred monomer that contains the oxygen base, the pentaerythrite of the acidic groups that has in 1 molecule more than 1 and the photo-curable functional group more than 3 is arranged for example or in dipentaerythritol addition acrylic acid and succinic anhydride or phthalic anhydride, trimellitic anhydride and the material that obtains, in dipentaerythritol addition acrylic acid and succinic anhydride or phthalic anhydride, trimellitic anhydride and the material that obtains.
Wherein, consider from the balance this point that easily obtains dissolubility developer solution and photo-curable, the acid anhydride acid of addition is succinic anhydride or phthalic anhydride preferably.
As the monomer that contains the oxygen base, the compound of preferred following formula (2) expression (below, be sometimes referred to as the compound (below, be sometimes referred to as " compound (3) ") of " compound (2) " or following formula (3) expression.
(about compound (2))
(in above-mentioned formula (2), X
1Represent Direct Bonding, can have substituent alkyl, can have substituent heterocyclic radical or can have substituent aromatic cyclic hydrocarbon group.
R
2Expression hydrogen atom or can have the alkyl of substituent carbon number 1～4.
R
11And R
12The alkyl that each represents independently hydrogen atom or can have substituent carbon number 1～4.But, R
11And R
12Also bonding forms ring mutually.
In addition, contain a plurality of-CR in a part
11R
12-time, can be identical or also can be different.
The integer of 1 expression 1～12, n represents 0～12 integer, m represents 1～3 integer.)
(about X
1)
X
1Represent Direct Bonding, can have substituent alkyl, can have substituent heterocyclic radical or can have substituent aromatic cyclic hydrocarbon group.
X
1In alkyl, can be any one in straight chain shape, chain or ring-type, have for example its carbon number be generally 1 or more, in addition common below 8, preferred alkyl below 5.
As concrete example, methylene, ethylidene, positive propylidene, 2-propylidene, positive butylidene, isobutylene, uncle's butylidene, cyclohexylene etc. are arranged for example.
X
1In heterocyclic radical, so long as at least one that contains nitrogen-atoms, sulphur atom and oxygen atom get final product as heteroatomic ring, mean aromatic series cyclic group and non-aromatic cyclic group the two.
As X
1In heterocyclic radical, can be monocycle, also can be condensed ring, be 3～10 and be not particularly limited as long as form the carbon number of ring.In addition, the atomic time of the formation ring beyond heterocyclic radical contains a plurality of carbon, these atoms can be identical, also can be different.
as this heterocycle, for example have for example, furan nucleus, the coumarone ring, thiphene ring, the benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole rings, indole ring, the carbazole ring, the pyrrolo-imidazole ring, the pyrrolo-pyrazole ring, the pyrrolopyrrole ring, the Thienopyrroles ring, the thienothiophene ring, chaff (furo) and pyrrole ring, chaff and furans (furo furan) ring, the thienofuran ring, the benzoisoxazole ring, the benzisothiazole ring, the benzimidazole ring, pyridine ring, the pyrazine ring, the pyridazine ring, pyrimidine ring, triazine ring, the quinoline ring, the isoquinoline ring, cinnolines (cinnoline) ring, quinoxaline ring, the phenanthridines ring, perimidine (perimidine) ring, the quinazoline ring, quinazolinone (quinazolinone), azulene (azulene) ring, thiazole ring, oxazole ring, Thiadiazole, the phthalimide ring, piperidine ring, pyrrolidine ring, the imidazolidine ring, the pyrazolidine ring, piperazine ring, the morpholine ring, the dihydroindole ring, the isoindoline ring, piperidine ring etc.
As X
1In aromatic cyclic hydrocarbon group, it can be monocycle, it can be also condensed ring, form the carbon number of ring so long as 5～18 just be not particularly limited, for example, have for example contain 1 free atomicity, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene ring, benzo pyrene ring, thick dinaphthyl (chrysene) ring, 9, the group of 10-benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc.
In addition, about the free atomicity in the present invention, according to the record of " on organic chemistry biological chemical name method " (Pingshan Mountain is good for three, the Pingshan Mountain and male translations, 11-12 page for Nan Jiangtang, distribution on May 20th, 1992).
Consider X at the easy aspect such as synthetic
1Optimization aromatic hydrocarbon ring, particularly preferably phenyl ring.
As X
1In alkyl, heterocyclic radical and the aromatic cyclic hydrocarbon group substituting group that can have, following (replacing basic group W) for example arranged for example.
(replacing basic group W)
fluorine atom, the chlorine atom, the thiazolinyl of carbon number 2～8, the alkoxy of carbon number 1～8, phenyl, 2, 4, the 6-trimethylphenyl, tolyl, naphthyl, cyano group, acetoxyl group, the alkyl carboxyl of carbon number 2～9, the sulfonic acid amides base, the sulfone alkylamidoalkyl of carbon number 2～9, the alkyl-carbonyl of carbon number 2～9, phenethyl, hydroxyethyl, the acetyl group amide group, the dialkyl amido ethyl of the alkyl linked rear formation of carbon number 1～4, trifluoromethyl, the trialkylsilkl of carbon number 1～8, nitro, the alkyl thio-base of carbon number 1～8.
(about R
1)
R
1Expression hydrogen atom or can have the alkyl of substituent carbon number 1～4.
Easily occuring on the cross-linking reaction this point, particularly preferably hydrogen atom or methyl.
As R
1The substituting group that middle alkyl can have has above-mentioned (replacing basic group W) material for example.
(about R
11And R
12)
R
11And R
12Represent that independently of one another hydrogen atom maybe can have the alkyl of substituent carbon number 1～4.In addition, R
11And R
12Bonding forms ring each other.
In addition, contain a plurality of-CR in a part
11R
12-time, R
11And R
12Can be identical separately, also can be separately different, on easy synthetic compound this point, preferred contained a plurality of-CR
11R
12-be identical.
(about 1 and n)
The integer of 1 expression 1～12, n represents 0～12 integer.
On easy synthetic this point, 1 is preferred 1～5, and more preferably 1～2.
In addition, on easy synthetic this point, n is preferred 2～5, and more preferably 2.
In addition, contain a plurality of 1 and during n in a part, separately respectively can be identical, also can be different.
(about m)
M represents 1～3 integer.
Wherein, on the good this point of curing of the dissolubility in alkaline developer and the pixel that obtains, m preferred 1 or 2, and more preferably 1.
(molecular weight)
The molecular weight of compound (2) is usually more than 400, and is preferred more than 500, and usually below 2000, preferred below 1800.
If in above-mentioned scope, easily make compound, therefore preferred on this point.
(about compound (3))
(in above-mentioned formula (3), R
4And R
5, R
31And R
32, R
41And R
42, R
51And R
52, also have R
61And R
62Represent that independently of one another hydrogen atom maybe can have the alkyl of substituent carbon number 1～4.
But, R
31And R
32, R
41And R
42, R
51And R
52, also have R
61And R
62Mutual bonding forms ring independently of one another.
In addition, in a part contained a plurality of-CR
31R
32-, CR
41R
42-,-CR
51R
52-,-CR
61R
62-, R
4And R
5Can be identical separately, also can be different separately.
A and b represent 1～3 integer independently of one another,
1
3And 1
6Represent independently of one another 1～12 integer,
n
3And n
6Represent independently of one another 0～12 integer.)
(about R
4And R
5, R
31And R
32, R
41And R
42, R
51And R
52, and R
61And R
62)
R
4And R
5With the R in described compound (2)
2Implication is identical.Preferred form too.
R
31And R
32, R
41And R
42, R
51And R
52, and R
61And R
62With the R in compound (2)
11And R
12Implication is identical.Preferred form too.
(about 1
3～1
6And n
3～n
6)
1
3～1
6Identical with the implication of 1 in compound (2).Preferred form too.
In addition, n
3～n
6Identical with the n implication in compound (2).Preferred form too.
(about a and b)
A and b represent 1～3 integer independently of one another.
A and b preferred 1～2, especially preferred 1.
In addition, a and b can be identical, also can be different.
(molecular weight)
The molecular weight of the compound in the present invention (3) is usually more than 400, and is preferred more than 500, and usually below 1000, preferred below 800.
If in above-mentioned scope, easily synthetic compound, therefore preferred in this.
Below show the preferred concrete example of the monomer that contains the oxygen base, but the present invention is not limited to these.
(concrete example)
These monomers can be used alone, but are difficult to obtain single compound on making, therefore also can use the potpourri more than 2 kinds.
The acid number when monomer that contains the oxygen base is potpourri is more than being generally 10mg-KOH/g, more than preferred 15mg-KOH/g, more preferably more than 20mg-KOH/g, in addition, be generally below 150mg-KOH/g, below preferred 110mg-KOH/g, more preferably below 100mg-KOH/g.
If in above-mentioned scope, easily obtain dissolubility and photo-curable balance in developer solution, so preferred.
(other monomers)
Can contain other monomers outside the monomer of oxygen base in (D) polymerizable monomer of colored resin composition of the present invention.
As other monomers, so long as the low molecular compound of energy polymerization just is not particularly limited, for example, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate etc. are arranged for example.
(content)
The content of (D) polymerizable monomer in colored resin composition of the present invention is in all solids composition, usually more than 1 % by weight, more than preferred 5 % by weight, more preferably more than 8 % by weight, in addition, usually below 80 % by weight, below preferred 70 % by weight, more preferably below 50 % by weight, particularly preferably below 40 % by weight.
In addition, the content of the monomer that contains the oxygen base in colored resin composition of the present invention is in whole (D) polymerizable monomers, usually more than 10 % by weight, preferably more than 30 % by weight.
In addition, the full dose of preferred (D) polymerizable monomer is the monomer that contains the oxygen base, and the upper limit is below 100 % by weight.
(P/M ratio)
P/M ratio in colored resin composition of the present invention, preferred more than 1.0 usually more than 0.5, and usually below 5.0, preferred below 4.5.
If in above-mentioned scope, easily obtain the balance of alkali development dissolubility and curing property, cross sectional shape, so preferred.
In addition, P is the content of the polymkeric substance in colored resin composition, and M is the content of the monomer in colored resin composition.
[(A) pigment]
Colored resin composition of the present invention as (A) pigment, can use the versicolor pigment such as red pigment, viridine green, yellow uitramarine, violet pigment, orange pigment, brown usually.
As the chemical constitution of various pigment, have for example that azo system, quinacridone, phthalocyanine system, benzimidazolone system, isoindolone are that, dioxazine (dioxazine) is, an organic pigment such as indanthrene Xi, perylene system.Beyond these, various inorganic pigments etc. also can utilize.
In above-mentioned pigment, especially when using phthualocyanine pigment, pigment concentration easily uprises, and is difficult to be adjusted at the dissolution time in alkaline developer, therefore easily obtains effect of the present invention.When especially using the metal halide phthalocyanine color, this tendency is strong, significantly obtains effect of the present invention.
Common metal phthalocyanine has 16 hydrogen atoms in 1 molecule, these hydrogen atoms are the metal halide phthalocyanines after being replaced by bromine atoms or chlorine atom, and what the present invention preferably used is bromination metal phthalocyanine color.
Wherein, on average contain the bromination metal phthalocyanine of the bromine atoms more than 13 in 1 molecule, show high transmitance, be fit to form the green pixel of color filter, so preferred.Further, contain not chloride in 13～16 bromine atoms and 1 molecule in preferred 1 molecule or contain average zinc bromide phthalocyanine below 3, on average contain in 14～16 bromine atoms and 1 molecule not chloride atom in especially preferred 1 molecule or contain average bromination metal phthalocyanine below 2.As the bromination metal phthalocyanine, preferable examples has copper bromide phthalocyanine and zinc bromide phthalocyanine.As the copper bromide phthalocyanine, preferred C.I. pigment green 36.In addition, as the zinc bromide phthalocyanine, preferred C.I. naphthol green 58.
In addition, if the concrete example of other viridine green represent with the face item number, can enumerate C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,45,48,50,51,54,55 etc.
Further, the concrete example of the pigment outside the viridine green that uses in the present invention is represented with the face item number, but be not limited to these examples.
at first, as red pigment, can enumerate C.I. paratonere 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 etc.Wherein, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242,254 etc., more preferably C.I. paratonere 177,209,224,242,254 etc.
As blue pigment, such as enumerating C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79 etc.
as yellow uitramarine, C.I. pigment yellow 1 is arranged for example, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and following＜pigment Y in the definition pigment (hereinafter referred to as " pigment Y ").
＜pigment Y 〉
Embed the formed compound of other compounds in 1: 1 complex compound of the nickel of the azo barbituric acid that represents with following structural formula or its dynamic isomer.
In addition, as described other compound, the compound shown in following formula (I-1) etc. is arranged for example.
Wherein, preferred C.I. pigment yellow 83,117,129,138,139,154,155,180,185 and pigment Y etc., more preferably C.I. pigment yellow 13 8,139 and pigment Y etc.
As violet pigment, C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50 etc. are arranged for example.Wherein, preferred C.I. pigment violet 19,23 etc., more preferably C.I. pigment Violet 23 etc.
As orange pigment, C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79 etc. is arranged for example.Wherein, preferred C.I. pigment orange 38,71 etc.
In addition, the resin black matrix that colored resin composition as described later forms color filter can be prepared, at this moment, black pigment can be used.In addition, black pigment can use separately, also can be with red, green, and the blue pigment that waits mixes use.In addition, can be inorganic pigment, can be also organic pigment.
In addition, the effect of the present invention that is easy to get calmly aspect considers, the pigment in the present invention is C.I. (color index) paratonere 58 particularly preferably.
In addition, as the inorganic pigment that can use in the present invention, barium sulphate, lead sulfate, titanium dioxide, yellow lead, iron oxide red, chromium oxide etc. are arranged for example.
In addition, above-mentioned various pigment also can multiple and use.For example, in order to adjust colourity, as (A) pigment, and with red pigment and yellow uitramarine, perhaps also with viridine green and yellow uitramarine.
In addition, (A) pigment that the present invention relates to, its average primary particle diameter usually below 100nm, below preferred 80nm, more preferably 20nm above, below 70nm.Because the present invention is effective especially when containing the composition of highly micronized pigment, therefore particularly preferably contain the situation of the pigment that average primary particle diameter 20nm is above, 60nm is following.
Average primary particle diameter by (A) pigment of using is in above-mentioned scope, the good depolarized characteristic that can be maintained, realize that high-contrast and transmitance and dispersion stabilization are good, also excellent colored resin composition of thermotolerance and photostability.
In addition, the primary particle size of pigment can be obtained in the following method.
At first, use the ultrasound wave dispersed color in chloroform, drop on the grid that posts collodion membrane, make its drying, observe with seeing through electron microscope (TEM), obtain the primary particle picture of pigment.But in the situation of organic pigment, the particle diameter of each pigment particles as the area circle equivalent diameter that is converted into diameter of a circle of the same area, is obtained respectively particle diameter to a plurality of (common 200～300 left and right) pigment particles.With the value of the primary particle size that obtains, the calculating formula by following formula calculates number mean value.Obtain mean grain size.
The particle diameter of each pigment particles: X
1, X
2, X
3, X
4..., X
i... X
m
(A) pigment that obtains like this can use separately, but in the scope of harmless effect of the present invention, can mix the pigment more than a kind or 2 kinds.
The content of (A) pigment in colored resin composition of the present invention is with respect to the total solids composition, usually below 60 % by weight, below preferred 50 % by weight, more preferably below 45 % by weight, and usually more than 10 % by weight, more than preferred 20 % by weight, more preferably more than 28 % by weight.
Content by making (A) pigment is in above-mentioned scope, not only make thickness can not become excessive with respect to color depth, clearance control when liquid crystal groove (liquid crystal cell) is changed etc. does not have bad influence, and obtain sufficient image formative, but also keep the disperse state of pigment, be difficult for producing cohesion or precipitation, result can be eliminated the problems such as thickening or luminance contrast reduction.
[(B) solvent]
(B) solvent has the function that makes each composition dissolving of containing in colored resin composition or dispersion, adjusting viscosity.As this (B) solvent, so long as each composition dissolving of formation colored resin composition or the thing of dispersion are got final product, preferred boiling point is at the solvent of 100～200 ℃ of scopes, and more preferably boiling point is the solvent of 120～170 ℃.
As such solvent, following substances is arranged for example.
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-single uncle's butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxy amylalcohol, dihydroxypropane single-ether, DPE, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, the glycol monoalkyl ethers that Tripropylene glycol monomethyl Ether is such;
Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, the such glycol dialkyl ether of dibutyl ethylene glycol ether;
The ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxyl butylacetic acid ester, 3-methoxyl butylacetic acid ester, methoxyl amyl group acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, dipropylene glycol monomethyl ether acetic acid esters, 3-methyl-such glycol alkyl ether acetate esters of 3-methoxyl butylacetic acid ester;
Diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, the such ethers of two hexyl ethers;
The ketone of acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisobutyl acetone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone and so on;
The monobasic of ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerine and so on or polyalcohols;
The aliphatic hydrocarbon of n-pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene, dodecane and so on;
Cyclohexane, methylcyclohexane, methylcyclohexene, the such ester ring type hydro carbons of dicyclohexyl;
Such aromatic hydrocarbon based of benzene,toluene,xylene, isopropyl benzene;
amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, the ethylene glycol ethyl ethers acid esters, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, ethyl caprilate, butyl stearate, ethyl benzoate, propionic acid 3-ethoxy methyl esters, propionic acid 3-ethoxy ethyl ester, propionic acid 3-methoxyl methyl esters, propionic acid 3-methoxyl ethyl ester, propionic acid 3-methoxyl propyl ester, propionic acid 3-methoxyl butyl ester, the chain that gamma-butyrolacton is such or cyclic ester class,
3-methoxypropionic acid, the such alkoxy carboxylic acids of 3-ethoxy-propionic acid;
Butyl chloride, the such halogenated hydrocarbon of amyl chloride;
The ether ketone that the methoxy pentanone is such;
Acetonitrile, the such nitrile of benzonitrile.
These solvents can be used alone, also can two or more and use.
In above-mentioned solvent, consider preferred diol monoalkyl ethers from the favorable dispersibility this point of above-mentioned (A) dyestuff.Wherein, especially the dissolubility this point of the various constituents from colored resin composition, particularly preferably propylene glycol monomethyl ether.
In addition, the higher this point of solubleness of the constituent, composition good from the balance of the coating of colored resin composition and surface tension etc. is further more preferably mixed and is used the glycol alkyl ether acetate esters as solvent.
In addition,, storage stability suitable from the viscosity of colored resin composition good aspect is considered, the use amount of glycol monoalkyl ethers, and in whole (B) solvents, preferred 5～50 quality %, more preferably 5～30 quality %.
In addition, consider from the viewpoint that the slot coated mode corresponding with nearest and large substrate etc. adapts, preferred and with the solvent with the boiling point more than 150 ℃.At this moment, the content of this high boiling solvent is whole with respect to (B) solvent, preferred 3～50 % by weight, more preferably 5～40 % by weight, particularly preferably 5～30 % by weight.
If in above-mentioned scope, separate out at the gap nozzle tip because of pigment etc. and solidify the foreign matter defective that causes and be difficult to occur, and rate of drying is suitable, so beat (tact) in color filter described later manufacturing process, the drying under reduced pressure operation is bad or the pin vestige of prebake conditions etc. is difficult to occur.
Moreover the solvent of boiling point more than 150 ℃ can be the glycol alkyl ether acetate esters, can be also the glycol alkyl ether class in addition, and at this moment, also it doesn't matter not contain in addition the solvent of boiling point more than 150 ℃.
In colored resin composition of the present invention, the content of (B) solvent is not particularly limited, usually below 99 % by weight, in addition usually more than 75 % by weight, more than preferred 80 % by weight, more preferably more than 82 % by weight.
If in above-mentioned scope, the viscosity that adapts with coating is arranged, be suitable for forming coated film, see preferably from this point.
[spreading agent]
If spreading agent in the present invention is can dispersed color, keep stable, unrestricted to its kind.For example, can use the spreading agents such as kation system, negative ion system, nonionic system or both sexes, the preferred polymers spreading agent.Specifically, can enumerate the alkylammonium salt of modified acroleic acid based copolymer, acrylic acid series copolymer, polyurethane, polyester, high-molecular copolymer or phosphate ester salt, cationic comb type graft polymer etc.In these spreading agents, preferred modified acroleic acid based copolymer, polyurethane, cationic comb type graft polymer.Especially preferred modified acroleic acid based copolymer, the modified acroleic acid based copolymer that is wherein especially preferably consisted of by segmented copolymer, its amine value is that 80mg-KOH/g is above, 150mg-KOH/g following (effectively solid constituent converts), and described segmented copolymer is made of the A block with solvophilic and B block with functional group of nitrogen atom.More preferably 100～140mg-KOH/g.
In the time of in above-mentioned scope, abundant to the absorption affinity of surface of pigments, dispersion stabilization is good.
Wherein, (methyl) acrylic acid series segmented copolymer of putting down in writing in preferred Japanese Patent Laid-Open 2009-025813 communique.
The acrylic acid series segmented copolymer can efficient disperse (A) pigment admirably.Infer that its reason is, by controlling molecules align, dispersant adsorption becomes obstacle when pigment mechanism is few.
In addition, in the present invention, AB block and/or ABA segmented copolymer that the acrylic acid series segmented copolymer is preferably formed by A block and B block.
The B block that consists of described acrylic acid series segmented copolymer has amino, and amino preferably is expressed as-NR
71R
72(wherein, R
71And R
72Respectively independently the expression can have substituent ring-type or chain alkyl, can have substituent aryl or can have substituent aralkyl.), the part-structure as containing this material preferably represents with following formula.
(wherein, R
71And R
72With above-mentioned R
71And R
72Implication is identical, R
73The alkylidene of carbon number more than 1, R
74Expression hydrogen atom or methyl.)
Wherein, R
71And R
72Preferable methyl, R
73Preferred methylene or ethylidene, R
74Preferable methyl.As such compound, the represented part-structure of following formula is arranged for example.
Can contain the part-structure that contains amino as above more than 2 kinds in 1 B block.At this moment, can contain with any form of random copolymerization or block copolymerization the amino part-structure that contains more than 2 kinds in this B block.Simultaneously, in the scope of harmless effect of the present invention, in the B block can some do not contain amino part-structure, as such part-structure, have for example from the part-structure of (methyl) acrylic ester monomer etc.
On the other hand, in the present invention, the A block of spreading agent has solvophilic, so long as by consisting of with the monomer of the monomer copolymerization that consists of above-mentioned B block, just be not particularly limited.
As the A block, for example, it is that monomer, vinyl acetate are that monomer, glycidol ether are the polymer architecture after the comonomer copolymerization such as monomer that the styrenic monomers of making, (methyl) acrylic ester monomer, (methyl) acrylates are arranged for example.
Spreading agent in the present invention is AB block or the ABA block copolymerization type macromolecular compound that is made of A block as above and B block.Preferred AB segmented copolymer wherein.Such segmented copolymer is for example by the preparation of living polymerization method.
The living polymerization method has living anion polymerization method, anion living polymerization method, radical living polymerization method.Particularly, for example just like the method for putting down in writing in Japanese Patent Laid-Open 2007-270147 communique.
In addition, the amine value of spreading agent (effectively solid constituent converts) represents with the weight of the KOH of the alkali number a great deal of of the solid constituent of removing the solvent in the spreading agent sample with every 1g, measures by the following method.With 0.5～1.5g of the beaker accurate weighing spreading agent sample of 100mL, with the acetic acid dissolving of 50mL.Use has the automatic titration device of pH electrode, to the HCLO of this solution with 0.1mol/L
4Acetic acid solution carries out acid-base titration.Titration pH point of inflexion on a curve as titration end-point, is obtained the amine value value by following formula.
Amine value [mg-KOH/g]=(561 * V)/(W * S)
(wherein, W: the spreading agent sample amount of weighing [g], V: at the titer [mL] of titration end-point, S: the solid component concentration of spreading agent sample [wt%].)
Simultaneously, the acid number of this segmented copolymer, because of as the basic acidic groups of this acid number have or not and kind different, but a preferred low side is usually below 50mg-KOH/g, preferred below 40, more preferably below 30.
The average primary particle diameter of pigment hour, specific surface area increases, the dispersant adsorption quantitative change of per unit area is few, and is larger than other dispersant effect by the spreading agent that described multipolymer forms at this moment, so be fit to use.
Spreading agent in the present invention is with respect to (A) pigment full dose in colored resin composition, more than preferred 5 % by weight, more preferably more than 10 % by weight, in addition usually below 200 % by weight, more preferably below 100 % by weight.
Colored resin composition of the present invention is as long as harmless effect of the present invention just can comprise other spreading agent.As other spreading agent, for example, the spreading agent of putting down in writing in Japanese Patent Laid-Open 2006-343648 communique is arranged for example.
[dispersing aid]
Colored resin composition of the present invention can further contain dispersing aid.Here said dispersing aid can be pigment derivative, as pigment derivative, can use the various compounds of records such as Japanese Patent Laid-Open 2001-220520 communique, Japanese Patent Laid-Open 2001-271004 communique, Japanese Patent Laid-Open 2002-179976 communique, Japanese Patent Laid-Open 2007-113000 communique and Japanese Patent Laid-Open 2007-186681 communique etc.
In addition, the content of the dispersing aid in colored resin composition of the present invention is with respect to the full dose of (A) pigment, usually more than 0.1 % by weight, again usually below 30 % by weight, preferably below 20 % by weight, more preferably below 10 % by weight, further below preferred 5 % by weight.
In the time of in above-mentioned scope, effectively obtain the effect as dispersing aid, dispersiveness and dispersion stabilization are good, so preferred.
[dispersion resin]
Colored resin composition of the present invention, can contain from described (C) adhesive resin select resin part or all as following dispersion resin.
Particularly, in " compound method of colored resin composition " described later, by containing (C) adhesive resin together with the composition of described spreading agent etc., should (C) adhesive resin to help the dispersion stabilization of (A) pigment with the multiplying each other effect of spreading agent.As a result, might reduce the addition of spreading agent, so preferred, and developability improves, and there is no the remaining last dissolved matter that has in the non-pixel portion of substrate, and the being adjacent to property raising of pixel to substrate is owing to obtaining such effect, so preferred.
(C) adhesive resin that so, will use in the dispersion treatment operation is called dispersion resin.Dispersion resin with respect to the pigment full dose in dispersible pigment dispersion, preferably uses about 0～200 % by weight.More preferably use about 10～100 % by weight.
As dispersion resin, can use described various (C) adhesive resin.
More than the preferred 0.5mg-KOH/g of the acid number of dispersion resin, more preferably more than 1mg-KOH/g, most preferably more than 5mg-KOH/g, again, below preferred 300mg-KOH/g, more preferably below 200mg-KOH/g, most preferably below 150mg-KOH/g.By acid number being controlled at above-mentioned scope, alkali-developable becomes well, also becomes in synthetic first-class and easily processes.
And, the weight-average molecular weight of the polystyrene conversion of measuring with GPC of dispersion resin, preferred more than 1000, more preferably more than 1500, most preferably more than 2000, preferred below 200000 again, more preferably below 50000, most preferably below 30000.By molecular weight being controlled at above-mentioned scope, alkali-developable becomes well, again, can prevent that also dispersion stabilization from descending.
[(E) photopolymerization causes composition and thermal polymerization initiation composition]
Based on the purpose that makes curing of coating, colored resin composition of the present invention preferably contains (E) photopolymerization to be caused composition and thermal polymerization and causes at least a in composition.Just, the method for curing can be for using these initiating agents method in addition.
Particularly preferably be, when colored resin composition of the present invention contains the resin with the two keys of ethene as (C) composition, with as (D) composition when containing the ethene compound, contain the thermal polymerization initiation composition that photopolymerization causes composition and/or produces the polymerization activity free radical by heat, described photopolymerization causes composition and has following functions: directly absorb light, or decomposition reaction or dehydrogenation reaction are occured by photoactivate, produce the polymerization activity free radical.In addition, (E) composition that causes composition as photopolymerization in the present invention refers to, in Photoepolymerizationinitiater initiater (following also at random be called " (E1) composition ") and with the potpourri of the addition agents such as polymerization accelerator (following also at random be called " (E2) composition "), sensitization pigment (following also at random be called " (E3) composition ").
[(E) photopolymerization causes composition]
(E) of the present invention photopolymerization causes composition, normally as (E1) Photoepolymerizationinitiater initiater and (E2) polymerization accelerator that adds as required and (E3) potpourri of the addition agent such as sensitization pigment use, to have direct absorption light or by photoactivate, decomposition reaction or dehydrogenation reaction occur, and produce the composition of the function of polymerization activity free radical.
As (E1) Photoepolymerizationinitiater initiater that consists of photopolymerization and cause composition, for example, two luxuriant titanium derivatives of record in Japanese Patent Laid-Open is arranged for example clear No. 59-152396, clear No. 61-151197 each communique of Japanese Patent Laid-Open etc.; Six aryl united imidazole derivative classes of record in No. 10-300922, Japanese patent laid-open, No. 11-174224, Japanese patent laid-open, No. 2000-56118 each communique of Japanese Patent Laid-Open etc.; Free radical activity agent, the alpha-aminoalkyl benzophenone derivatives class of the N-aryl of the halogenation first base oxadiazole derivative class of record, halogenation methyl-s-pyrrolotriazine derivatives class, N-phenylglycine-alpha-amido acids, N-aryl-alpha-amido hydrochlorate, N-aryl-α-aminoacidesters class etc. in Japanese patent laid-open 10-39503 communique etc.; In Japanese Patent Laid-Open 2000-80068 communiques etc., the oxime ester of record is derivant class etc.
Particularly, for example, the international Photoepolymerizationinitiater initiater that the 2009/107734th trumpeter's volume etc. puts down in writing etc. that disclose is arranged for example.
In these Photoepolymerizationinitiater initiaters, more preferably alpha-amido alkane acyl benzene derivative class, oxime ester are derivant class, united imidazole derivative class, acetophenone derivs class and thioxanthone derivates class.
In addition; be the derivant class as the oxime ester; the compound of 1,2-octane diketone 1-(4-(phenyl sulfo-) phenyl)-2-(o-benzoyl oxime), ethyl ketone 1-(9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl) 1-(adjacent acetyl group oxime) and following manner (XI) expression etc. is arranged for example.
(in formula (XI), R
101Expression hydrogen atom, the alkyl of carbon number 1～20, the thiazolinyl of carbon number 2～25, the heteroaryl of carbon number 3～20 or the heteroaryl alkyl of carbon number 4～25, any in these groups all can have substituting group.Perhaps, R
101Also can with X or Z bonding, form ring.
R
102Expression carbon number 2～20 alkanoyl, the thiazolinyl of carbon number 3～25, the cycloalkanes acyl group of carbon number 4～8, the aroyl (ア リ one ロ イ Le base) of carbon number 7～20, the alkoxy carbonyl of carbon number 2～10, the aryloxy carbonyl of carbon number 7～20, the heteroaryl of carbon number 2～20, the 4-hetaroylpyrazol of carbon number 3～20 or the alkyl amino-carbonyl of carbon number 2～20, no matter anyly in these groups all can contain substituting group.
X represents to contain divalent aromatic cyclic hydrocarbon group and/or the aromatic heterocycle that substituting group, the cyclic condensation more than 2 form.
Z represents to have substituent aromatic series cyclic group.)
In addition, in the compound of described formula (XI) expression, preferred X be for can have the compound of substituent carbazole ring, the compound of the following formula of specifically can giving an example (XII) expression etc., the wherein compound of following formula (XIII) expression particularly preferably.
(in formula, R
101, R
102And Z is identical with implication in described formula (XI).R
103～R
109Represent independently of one another hydrogen atom or any substituting group.)
(in formula, R
101aMean the alkyl of carbon number 1～3 or the group of following formula (XIIIa) expression).
(in formula, R
103And R
104Represent that independently of one another hydrogen atom, phenyl or N-acetyl group-N-acetoxyl group is amino.
* represent the bonding position.
R
102aThe alkanoyl of expression carbon number 2～4, X
aThe expression nitrogen-atoms can by 1～4 alkyl replace 3, the 6-carbazyl.Z
aThe phenyl that expression can be replaced by alkyl or the naphthyl that can be replaced by the morpholino base.)
Other also there are styrax alkyl ether, anthraquinone derivative class; The 2-methyl-(4 '-the methyl thio-phenyl)-2-morpholino-acetophenone derivs class, 2-ethyl thioxanthones, 2 such as 1-acetone, the thioxanthone derivates classes such as 4-diethyl thioxanthone, benzoic acid ester derivant class, acridine derivatives class, azophenlyene derivant class, anthracyclinone derivatives class etc.
In these Photoepolymerizationinitiater initiaters, more preferably alpha-aminoalkyl benzophenone derivatives class, thioxanthone derivates class, oxime ester are the derivant class.Particularly preferably the oxime ester is the derivant class.
As (E2) polymerization accelerator that uses as required, can enumerate as, N, the N such as N-dimethylamino ethyl benzoate, N-dialkyl amido benzoic acid alkyl esters; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle; The sulfhydryl compound classes such as the multifunctional sulfhydryl compound of aliphatics etc.
These (E1) Photoepolymerizationinitiater initiaters and (E2) polymerization accelerator can use separately respectively a kind, also can be more than 2 kinds and use.
Simultaneously, as required, use (E3) sensitization pigment in order to improve induction sensitivity.the sensitization pigment uses suitable pigment according to the wavelength of image exposure light source, and for example, in Japanese patent laid-open is arranged for example No. 4-221958, No. 4-219756 each communique of Japanese patent laid-open etc., the xanthene of record is pigment, the coumarin series pigment with heterocycle of record in No. 3-239703, Japanese patent laid-open, No. 5-289335 each communique of Japanese patent laid-open etc., the 3-coumarin series pigment of the record such as No. 3-239703, Japanese patent laid-open, No. 5-289335 each communique of Japanese patent laid-open, in Japanese patent laid-open 6-19240 communiques etc., the methylene pyrrole of record is pigment, clear No. 47-2528 of Japanese Patent Laid-Open, clear No. 54-155292 of Japanese Patent Laid-Open, No. 45-37377, Jap.P. examined patent publication, clear No. 48-84183 of Japanese Patent Laid-Open, clear No. 52-112681 of Japanese Patent Laid-Open, clear No. 58-15503 of Japanese Patent Laid-Open, clear No. 60-88005 of Japanese Patent Laid-Open, clear No. 59-56403 of Japanese Patent Laid-Open, No. 2-69, Japanese patent laid-open, clear No. 57-168088 of Japanese Patent Laid-Open, No. 5-107761, Japanese patent laid-open, No. 5-210240, Japanese patent laid-open, the pigment with dialkyl amido benzene skeleton of putting down in writing in No. 4-288818 each communique of Japanese patent laid-open etc. etc.
(E3) the sensitization pigment also can use separately a kind, also can more than 2 kinds and use.
In colored resin composition of the present invention, these (E) photopolymerization cause the content of composition in the total solids composition, usually more than 0.1 % by weight, more than preferred 0.2 % by weight, further more than preferred 0.5 % by weight, in addition usually below 40 % by weight, preferably below 30 % by weight, further preferred scope below 20 % by weight.
When above-mentioned scope, good to the sensitivity of exposure light, the dissolubility of unexposed portion in developer solution is also good in addition, is difficult for bringing out poor visualization etc., and be therefore preferred.
((E) thermal polymerization causes composition)
Cause the object lesson of composition as (E) thermal polymerization that can contain in colored resin composition of the present invention, azo based compound, organic peroxide and hydrogen peroxide etc. are arranged for example.Among these, preferably use the azo based compound.More specifically, can use such as the international thermal polymerization initiation composition of putting down in writing in No. 2009/107734 grade that disclose.
These thermal polymerizations cause composition can use separately a kind, also can more than 2 kinds and use.
[(F) chain-transferring agent]
More easily obtaining on effect this point of the present invention, colored resin composition of the present invention preferably contains (F) chain-transferring agent.
(F) chain-transferring agent in the present invention refers to the free radical of accepting to produce, the compound that this free radical is passed to other compounds.
Colored resin composition of the present invention contains the compound of following formula (4) expression as (F) chain-transferring agent.
(in above-mentioned formula (4), p represents 2～4 integer.
R
3Represent hydrogen atom or can contain substituent alkyl.
X
2Expression Direct Bonding, primary～season level carbon atom, the heterocyclic radical of 2～4 valencys or the aromatic cyclic hydrocarbon group of 2～4 valencys.
What contain in a part is a plurality of
Can be identical, or also can be different.)
(about R
3)
R
3The expression hydrogen atom maybe can contain substituent alkyl.
As described alkyl, carbon number is generally 1～8, is particularly preferably 1 or 2.
As R
3, uprise on this point at the surface cure reactive high, the film that obtains of compound and set out, be preferably hydrogen atom.
In addition, as R
3In can tool contain the substituting group of alkyl, the material of record in (replacing basic group Z) is arranged as described for example.
(replacing basic group Z)
fluorine atom, the chlorine atom, the thiazolinyl of carbon number 2～8, the alkoxy of carbon number 1～8, phenyl, 2, 4, the 6-trimethylphenyl, tolyl, naphthyl, acetyl group oxygen base, the alkoxy carbonyl of carbon number 2～9, phenyloxycarbonyl, carbamyl, the alkyl-carbamoyl of carbon number 2～9, the phenyl amino formoxyl, sulfamoyl, the alkylsulfamoyl group of carbon number 1～8, the phenyl sulfamoyl base, the alkyl-carbonyl of carbon number 2～9, benzoyl, the alkyl sulphonyl of carbon number 1～8, trifluoromethane sulfonyl group, phenethyl, hydroxyethyl, acetyl-amino, the alkyl linked dialkyl amido ethyl that forms of carbon number 1～4, trifluoromethyl, the trialkylsilkl of carbon number 1～8, nitro, cyano group, carboxyl, the alkyl sulphur aminoacyl of carbon number 1～8.
(about X
2)
X
2Expression Direct Bonding, the second month in a season～quaternary carbon atom, the aromatic cyclic hydrocarbon group of 2～4 valencys or the heterocyclic radical of 2～4 valencys.
As X
2In aromatic cyclic hydrocarbon group and heterocyclic radical, described (about compound (2)) are arranged for example (about X
1) in the group put down in writing.Optimal way too.
X
2In, in the good this point of storage stability of compound (4), the preferred second month in a season～quaternary carbon atom, particularly preferably quaternary carbon atom.
In addition, X
2In carbon atom, heterocyclic radical and aromatic cyclic hydrocarbon group can have following structural formula (below; be sometimes referred to as " structure that contains the sulphur aminoacyl ") outside the substituting group of expression, the group of record in described (replace basic group Z) is arranged for example as this substituting group.
In the present invention, preferred only with the above-mentioned structure that contains the sulphur aminoacyl as substituting group, X
2In former, the heterocyclic radical of carbon and the progression of aromatic cyclic hydrocarbon group preferably identical with p.
(about p)
P represents 2～4 integer.
In compound (4), increase as the sulphur aminoacyl of reactive site, the reactivity of compound increases, on the abundant this point of the curing of the pixel that obtains, and particularly preferably 4.
Below show the concrete example of compound of the present invention (4), but the present invention is not limited to these.
【0091】
[concrete example]
have 2 compounds that contain the structure of sulphur aminoacyl: have for example 1, the 2-dithioglycol, 1, the 3-dimercaptopropane, 1, the 4-succinimide mercaptans, 2, the 3-succinimide mercaptans, 1, the 5-pentane disulfide thioalcohol, 1, the 6-ethanthiol, 1, hot two mercaptan of 8-, 1, 9-mercaptan in the ninth of the ten Heavenly Stems two, 2, 3-dimercapto-1-propyl alcohol, dithio-erythritol, 1, the 2-dimercaptobenzene, 1, the 2-benzene dimethanethiol, 1, the 3-dimercaptobenzene, 3, the 4-dimercapto toluene, 4-chloro-1, the 3-dimercaptobenzene, 2-hexyl amino-4, 6-dimercapto-1, 3, the 5-triazine, 2-diethylamino-4, 6-dimercapto-1, 3, the 5-triazine, 2-cyclohexyl amino-4, 6-dimercapto-1, 3, the 5-triazine, ethylene glycol bis (3-mercaptopropionic acid ester), 2, 5 dimercaptos-1, 3, the 4-thiadiazoles, 2, two (2-hydroxyl-3-sulfydryl propoxyl group the phenyl-propanes etc. of 2-,
Have 3 compounds that contain the structure of sulphur aminoacyl: trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris thioglycolic acid ester, 1,2 are arranged for example, 6-hexanetriol three sulfo-ethyl glycolates etc.,
Have 4 compounds that contain the structure of sulphur aminoacyl: pentaerythrite tetrathio ethyl glycolate, pentaerythrite four (3-mercaptopropionic acid ester) etc. are arranged for example.
(about content)
The content of (F) of the present invention chain-transferring agent is in the solid constituent of colored resin composition, usually more than 0.5 % by weight, more than preferred 1 % by weight, more preferably more than 1.5 % by weight, in addition usually below 10 % by weight, below preferred 8 % by weight, more preferably below 6 % by weight.
When above-mentioned scope, the curing of the colored resin composition that obtains is abundant, and, the excellent storage stability of colored resin composition, the brightness of the pixel that difficult impact obtains is so preferred.
In addition, colored resin composition of the present invention can contain the chain-transferring agent outside compound (4), at this moment, as long as the total content of the chain-transferring agent that contains is in above-mentioned scope.
Wherein, as chain-transferring agent, particularly preferably only contain compound (4), preferably contain compound (4) in above-mentioned scope.
[other any compositions]
Colored resin composition of the present invention can contain surfactant, organic carboxyl acid and/or organic carboxyl acid acid anhydride, Thermocurable compound, plastifier, thermal polymerization inhibitor, preserving stabilizer, surface protectant, adhere to improving agent, development modifying agent etc. except described each composition.As these any compositions, can use for example various compounds of Japanese Patent Laid-Open 2007-113000 communique record.
[compound method of colored resin composition]
In the present invention, colored resin composition can be by suitable method preparation, for example, by with described (A) pigment, have (C) adhesive resin that contains specific unsaturated group and have (D) polymerizable monomer of the monomer that contains the oxygen base and (B) solvent and any composition of using as required is mixed together to prepare.
In addition, preferably with (A) pigment in (B) solvent, at spreading agent and under the existence of the dispersing aid that adds as required, according to circumstances together with the part of (C) adhesive resin, for example, use paint mixer, sand mill, bowl mill, mill, stone mill, airslide disintegrating mill, the equilateral pulverizing of homogenizer limit to mix, disperse, the pigment preparation dispersion liquid.Following methods is arranged for example: by add in this dispersible pigment dispersion contain resin (C) adhesive resin of specific unsaturated group and have (D) polymerizable monomer of the monomer that contains the oxygen base, (E) photopolymerization of adding as required causes composition and/or thermal polymerization causes composition and other one-tenth grades, mix and prepare.
[application of colored resin composition]
Colored resin composition of the present invention is its whole constituent state of dissolving or disperse in solvent normally.Supply with such colored resin composition on substrate, form color filter or liquid crystal indicator, the component parts of organic EL display etc.
Below, as the application examples of colored resin composition of the present invention, to as the application of the pixel of color filter and use these liquid crystal indicator (panel) and organic EL display to describe.
＜color filter 〉
Color filter of the present invention contains the pixel that is formed by colored resin composition of the present invention.
Below describe for the formation method of color filter of the present invention.
The pixel of color filter can be formed by various methods.Here so that be that example describes with the colored resin composition of optical polymerism with the situation that photoetching process forms, but manufacture method is not limited in this.
At first, on the surface of substrate, as required, form black matrix" (black matrix) to mark off the part that forms pixel, after coating colored resin composition of the present invention on this substrate, use prebake conditions to make the solvent evaporation and form and film.Then, this is filmed by after photomask exposure, use alkaline developer to develop, dissolve and remove the unexposed section of filming, then by rear baking, thereby can form the various pattern of pixels of redness, green, blueness, make color filter.
The substrate that uses during as the formation pixel, as long as transparent and have the intensity of appropriateness substrate, be not particularly limited, for example, polyester based resin, polyolefin-based resins, polycarbonate-based resin, acrylic resin, thermoplastic resin film-making, epoxy resin, heat-curing resin, various glass etc. are arranged for example.
In addition, these substrates can be according to expectation, suitably implements to be formed by the film that silane coupling agent agent or polyurethane series resin etc. carry out the pre-treatment of surface treatments such as processing, Corona discharge Treatment or ozone treatment etc.
When being coated on colored resin composition on substrate, rotary process, ring bar type rubbing method, flow coat method, slit rotary process (slit and spin method), die rubbing method method, print roll coating method, spraying process etc. are arranged for example.Wherein, preferred slit rotary process and die rubbing method method.
The thickness of coated film as dried thickness, is generally 0.2～20 μ m, preferred 0.5～10 μ m, particularly preferably 0.8～5.0 μ m.
In the time of in above-mentioned scope, easily adjust the gap in pattern development or liquid crystal groove chemical industry order, easily demonstrate in addition the color of expectation, so preferred.
The radioactive ray that use during as exposure, such as using visible light, ultraviolet ray, far ultraviolet, electron beam, X ray etc., optimal wavelength is at the radioactive ray of the scope of 190～450nm.
The radioactive ray light source used that uses in image exposure, use wavelength 190～450nm, be not particularly limited, the lamp source that xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp, carbon arc, fluorescent light etc. for example, are arranged for example; The LASER Light Source of argon laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser etc. etc.When using the specific wavelength irradiation, also can utilize optical filter.
The exposure of radioactive ray is preferred 10～10,000J/m
2
Simultaneously, as described alkaline developer, preference is as, the inorganic alkaline compound of NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium silicate, potassium silicate, sodium metasilicate, tertiary sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide etc.; Single-two-or three-monoethanolamine, list-two-or three-methyl amine, list-two-or three-ethylamine, list-or two-isopropylamine, n-butylamine, list-two-or the aqueous solution of the organic basic compound of three-isopropanolamine, aziridine, ethene diimine, Tetramethylammonium hydroxide (TMAH), choline etc. etc.
Can add in right amount in described alkaline developer such as the water-miscible organic solvent of isopropyl alcohol, phenmethylol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol, diacetone alcohol etc. or surfactant etc.In addition, alkali can be washed after developing usually.
As the development treatment method, can utilize any one method such as immersion development method, spray development method, brush development method, ultrasound wave development method.Lower 5～300 seconds of the preferred room temperature of development conditions (23 ℃).
The condition of development treatment is not particularly limited, and development temperature is usually more than 10 ℃, and is wherein preferred more than 15 ℃, and is more preferably more than 20 ℃, common below 50 ℃ in addition, wherein preferred below 45 ℃, more preferably the scope below 40 ℃.
As developing method, can utilize any one method of immersion development method, spray development method, brush development method, ultrasound wave development method etc.
When the color filter that as above method is produced is used for liquid crystal indicator, form the transparency electrode of ITO etc. on image with such state, a part as parts such as color monitor, liquid crystal indicators is used, but in order to improve surface smoothness or permanance, also can as required, the top coat (top coat) of polyamide, polyimide etc. be set on image.In addition, a part does not form transparency electrode sometimes yet in the purposes of plane orthotype type of drive (IPS pattern) etc.In addition, sometimes also form flange in vertical orientation type type of drive (MVA pattern).In addition, sometimes form rod structure (sensitization sept) by photoetching process and replace beading dispersal type sept.
＜liquid crystal indicator 〉
Liquid crystal indicator of the present invention uses above-mentioned color filter of the present invention to make.Style or structure to liquid crystal indicator of the present invention are not particularly limited, and can use color filter of the present invention to assemble according to common method.
For example, can use the method for record in " liquid crystal apparatus handbook " (daily magazine industry newspaper office, distribution on September 29th, 1989, JSPS the 142nd council's work) to form liquid crystal indicator of the present invention.
＜organic EL display 〉
When making has the organic EL display of color filter of the present invention; for example represent in Fig. 1; on transparent support substrate 10; be formed with by colored resin composition of the present invention on the blue color filter of pixel 20; across organic protection layer 30 and inorganic oxide film 40 lamination organic luminorphors 500, make thus multicolor organic element.
Lamination method as organic luminorphor 500, following method is arranged for example: form successively the method for transparent anode 50, hole injection layer 51, hole transporting layer 52, luminescent layer 53, electron injecting layer 54 and negative electrode 55 at the color filter upper surface, will stick at the organic luminorphor 500 that forms on other substrates method on inorganic oxide film 40 etc.The organic EL 100 of producing by as above method is also applicable to the organic EL of passive drive mode and the organic EL of active type of drive.
[embodiment]
Below, enumerate synthesis example, embodiment and comparative example the present invention is carried out more specific description, as long as but be no more than main idea of the present invention, just be not limited to following examples.
[1] (synthesizing of resin)
＜synthesis example 1: resin P-1's is synthetic 〉
As the separate type flask of reactive tank preparation with cooling tube, drop into propylene glycol methyl ether acetate 400 weight portions, after carrying out the nitrogen displacement, heat in oil bath while stirring, make the temperature of reactive tank be warming up to 90 ℃.
On the other hand, drop into dimethyl-2 in the monomer groove, 2 '-[oxygen two (methylene)] two-2-acrylate 30 weight portions, methacrylic acid 60 weight portions, cyclohexyl methacrylate 110 weight portions, caproic acid t-butyl peroxy-2-ethyl ester 5.2 weight portions, propylene glycol methyl ether acetate 40 weight portions, drop into n-dodecyl mercaptan 4.2 weight portions, propylene glycol methyl ether acetate 27 weight portions in the chain-transferring agent groove, the temperature stabilization of autoreaction groove begins to drip from monomer groove and chain-transferring agent groove at 85 ℃, initiated polymerization.Make temperature remain on 85 ℃, dripped in 135 minutes consuming time respectively, drip and finish to begin after 60 minutes to heat up, making reactive tank is 110 ℃.
Keep 110 ℃ after 3 hours, connect gas introduction tube at the separate type flask, the bubbling of beginning oxygen/nitrogen=5/95 (v/v) mixed gas.Then, drop into glycidyl methacrylate 39.6 weight portions, 2 in reactive tank, 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 0.4 weight portion, triethylamine 0.8 weight portion keep this state 110 ℃ of reactions 9 hours.
Be cooled to room temperature, the weight-average molecular weight 12000 of the polystyrene conversion of measuring through GPC obtains the resin P-1 of acid number 90mg-KOH/g.
＜synthesis example 2: resin P-2's is synthetic 〉
Nitrogen is carried out on propylene glycol methyl ether acetate 145 weight portion limits stir while replacing, be warming up to 120 ℃.In styrene 10 weight portions that wherein drip, glycidyl methacrylate 85.2 weight portions and mono acrylic ester FA-513M (Hitachi changes into society's system) 66 weight portions with tricyclodecane skeleton, follow 3 hours consuming time and drip 2.2 '-azo two-2-methylbutyronitrile 9.00 weight portions, further continue to stir 2 hours under 90 ℃.Then will change air displacement in reaction vessel into, drop into three-dimethylamino phenol, 0.7 weight portion and quinhydrones 0.12 weight portion in acrylic acid 43.2 weight portions, 100 ℃ of lower sustained responses 12 hours.Then, add tetrabydrophthalic anhydride (THPA) 68.5 weight portions, triethylamine 0.7 weight portion, reaction is 3.5 hours under 100 ℃, and adding propylene glycol methyl ether acetate to be adjusted to solid component concentration is 40%.The weight-average molecular weight Mw of the polystyrene conversion of measuring through GPC of the resin P-2 that as above obtains is approximately 5500, and acid number is 92mg-KOH/g.
＜synthesis example 3: resin P-3's is synthetic 〉
Nitrogen displacement limit is carried out on propylene glycol methyl ether acetate 145 weight portion limits stir, be warming up to 120 ℃.In styrene 10 weight portions that wherein drip, glycidyl methacrylate 85.2 weight portions and mono acrylic ester FA-513M (Hitachi changes into society's system) 66 weight portions with tricyclodecane skeleton, follow 3 hours consuming time and drip 2.2 '-azo two-2-methylbutyronitrile 8.47 weight portions, further continue to stir 2 hours under 100 ℃.Then, will change air displacement in reaction vessel into, drop into three-dimethylaminomethyl phenol, 0.7 weight portion and quinhydrones 0.12 weight portion in methacrylic acid 51.7 weight portions, continue to react 12 hours under 100 ℃.Then, add succinic anhydride 27.0 weight portions, triethylamine 0.7 weight portion, reaction is 3.5 hours under 100 ℃, and adding propylene glycol methyl ether acetate to be adjusted to solid component concentration is 40%.The weight-average molecular weight Mw of the polystyrene conversion of measuring through GPC of the resin P-3 that as above obtains is approximately 5500, and acid number is 80mg-KOH/g.
＜synthesis example 4: resin P-4's is synthetic 〉
Mono acrylic ester FA-513M (Hitachi changes into society's system) 93.6 weight portions, methacrylate 36.4 weight portions that will have tricyclodecane skeleton are dissolved in propylene glycol methyl ether acetate 150 weight portions, add azobis isobutyronitrile 1.25 weight portions under nitrogen environment, reaction is 7 hours under 80 ℃.Then stop the nitrogen bubbling, be warming up to 100 ℃, stirred 1 hour.Add etamon chloride 0.124g, stir, make it dissolving in 80 ℃, dripped in 1 hour consuming time further and be mixed with the solution of glycidyl methacrylate 23.4g, propylene glycol methyl ether acetate 23.90g, further adding propylene glycol methyl ether acetate to be adjusted to solid component concentration is 40%.The weight-average molecular weight Mw of the polystyrene conversion of measuring through GPC of the resin P-4 that as above obtains is approximately 8000, and acid number is 100mg-KOH/g.
＜synthesis example 5: resin P-5's is synthetic 〉
Make the methacrylic acid of resin P-4 become acrylic acid and similarly synthetic, the weight-average molecular weight that obtains the polystyrene conversion measured through GPC is approximately 8000, acid number is the resin P-5 of 100mg-KOH/g.
＜synthesis example 6: resin P-6's is synthetic 〉
In synthesis example 3, succinic anhydride 27.0 weight portions that replace resin P-3 with tetrahydrophthalic anhydride (THPA) 68.5 weight portions instead of, make it similarly to react, the weight-average molecular weight Mw that obtains the polystyrene conversion measured through GPC is approximately 5500, the about resin P-6 of 80mg-KOH/g of acid number.
＜synthesis example 7: resin P-7's is synthetic 〉
In synthesis example 2, tetrabydrophthalic anhydride (THPA) 68.5 weight portions that replace resin P-2 with succinic anhydride 27.0 weight portions, make it similarly to react, the weight-average molecular weight Mw that obtains the polystyrene conversion measured through GPC is approximately 5500, the about resin P-7 of 90mg-KOH/g of acid number.
[2] preparation of dispersible pigment dispersion
The synthetic resin P-1 in 3.25 weight portions that the solid constituent amount converts and above-mentioned synthesis example 1 of propylene glycol methyl ether acetate 74 weight portions, C.I. naphthol green 586.5 weight portions, pigment Y6.5 weight portion, dispersant containing acrylic LPN6919 (PVC Star グ ケ ミ one society's system) is mixed through 3.25 weight portions of solid constituent amount conversion, with stirring 3 hours in stirring machine, prepare the abrasive of solid component concentration 20 % by weight.These mixed liquor 100 weight portions and diameter 0.5mm zirconium oxide bead 300 weight portions are packed in rustless steel container, with disperseing 6 hours in paint mixer, make dispersible pigment dispersion.
[3] preparation of colored resin composition
Form in order to become shown in following table 1, be mixed in the dispersible pigment dispersion of preparation in described " preparation of [2] dispersible pigment dispersion " that adhesive resin, polymerizable monomer, photopolymerization cause composition and as the surfactant of other compositions and stir, adding solvent (propylene glycol methyl ether acetate) to be adjusted to solid component concentration is 20 % by weight, obtains colored resin composition.
In addition, pass through at last disposable syringe filter unit (the small-sized disposable Simple filter of Japanese: Horse type Off イ Le タ one, a kind of circle: Disposable syringe filter unit), remove foreign matter of 5 μ m.
Each compound in table 1 is as described below respectively.
M-520: carboxylic 5 functional acrylates, acid number 25mg-KOH/g, M-520 (society's system is synthesized in East Asia)
M-510: carboxylic 3 functional acrylates, acid number 95mg-KOH/g, M-510 (society's system is synthesized in East Asia)
Potpourri (the acid number: 35mg-KOH/g) of the compound that monomer mixture A:DPHA and following structural formula represent
CBX-1N:(2,2,2-, three acryloxy Methylethyl phthalic acids) acid number 85mg-KOH/g (Xin Zhong village chemical industry society system)
DPHA: dipentaerythritol acrylate (Japanese chemical drug society system)
OXE-02: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(adjacent acetyl group oxime) (BASF society system)
IrgaCure907:2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone (BASF society system)
PET-P: pentaerythrite-four (3-mercaptopropionic acid ester) (the chemical society system of forming sediment)
メ ガ Off ア Star Network F475: fluorine is surfactant (DIC society system)
[4]＜evaluation method 〉
The mensuration of the dissolution time of [4-1] colored resin composition
Have at evaporation on the glass substrate of chromium, with the colored resin composition of record in spin-coating method coating table 1, carry out the prebake conditions of 3 minutes in the heating plate of 80 ℃ respectively.The coating rotating speed is adjusted to color coordinates y=0.594 after rear baking.Use the potassium hydroxide aqueous solution of 0.04 % by weight, carry out spray development under 23 ℃ of developer temperaturs, pressure 0.25MPa, with the time that colored resin composition is dissolved in developer solution fully, substrate exposes of unexposed section, as the dissolution time of this colored resin composition.
Result is concluded in table 2.
The mensuration of [4-2] cross sectional shape
Use the color filter pattern mask, similarly the colored resin composition of record in table 1 is coated on glass substrate (AN100) with [4-1], carry out prebake conditions, then, use high-pressure mercury-vapor lamp with 60mj/em
2Expose.Then, use the potassium hydroxide aqueous solution of 0.04 % by weight, under 23 ℃ of developer temperaturs, 0.25MPa pressure, spray development 40 seconds.After development, rinse substrate with sufficient water, the air drying that is then cleaning.Then, carry out the rear baking of 30 minutes in the baking oven of 230 ℃.The thickness of colored resin composition is 2.0 μ m.Change the position of the pattern as above obtain, observe respectively separately cross sectional shape with the electron microscopes of 10000 times.
Result is concluded in table 2.
In addition, as described below about the evaluation of cross sectional shape, be respectively the shape of putting down in writing in Fig. 2.
◎: super suitable cone
Zero: along cone
△: substantially vertical
*: back taper
[5] result
Pixel as shown in table 2, as to use colored resin composition of the present invention to form, the dissolubility in developer solution is short, and cross sectional shape is along cone.
Therefore, the cross section of the pixel that the colored resin composition of the application of the invention forms be along cone, when forming the conductive film of ITO etc., is difficult for the problems such as generation broken string, and the dissolution time for developer solution is short, so the yield in the manufacturing that affects of dissolution time is high.
Namely, colored resin composition of the present invention is that the cross sectional shape of the pixel that obtains is for along cone and the composition short to the dissolution time of developer solution, the cross sectional shape of the pixel that obtains for along cone and short to the dissolution time of developer solution, is these those long relations that disappear in the past, is difficult to take into account.
Thus, the liquid crystal indicator and the OLED display that have the color filter that uses the pixel that colored resin composition of the present invention forms and have this color filter have high-quality.
Claims (11)
1. a colored resin composition, is characterized in that, contains (A) pigment, (B) solvent, (C) adhesive resin and (D) polymerizable monomer,
This (C) adhesive resin contains the resin of unsaturated group, the described resin that contains unsaturated group is to make at least following (C-1) and (C-3) copolymerization and the multipolymer addition (C-4) that obtains and the resin that (C-5) obtains
And (D) polymerizable monomer contains the monomer of oxygen base,
(C-1): have the compound of unsaturated link and epoxy radicals in a part,
(C-3): have can with the compound of the unsaturated link of described (C-1) copolymerization,
(C-4): unsaturated carboxylic acid,
(C-5): multi-anhydride.
2. colored resin composition according to claim 1, is characterized in that, described multipolymer is to make (C-1), (C-3) and following (C-2) copolymerization and the multipolymer that obtains,
(C-2): have at least a kind of skeleton selecting in the group that free tricyclodecane skeleton and bicyclopentadiene skeleton form and the compound of unsaturated link in a part.
3. colored resin composition according to claim 1, is characterized in that, the acid number of the described monomer that contains the oxygen base is more than 10mg-KOH/g, below 150mg-KOH/g.
4. colored resin composition according to claim 1, is characterized in that, (C-4) unsaturated carboxylic acid is methacrylic acid.
5. colored resin composition according to claim 1, is characterized in that, the ratio P/M of the content M of the monomer solid constituent in the content P of the polymer solids composition in colored resin composition and colored resin composition is than more than 0.5, below 4.5.
6. colored resin composition according to claim 1, is characterized in that, contains described (A) pigment that 28 % by weight are above, 45 % by weight are following that accounts for the total solids composition.
7. colored resin composition according to claim 1, is characterized in that, described (A) pigment contains the zinc bromide phthalocyanine color.
8. colored resin composition according to claim 1, is characterized in that, further contains at least 1 in (E) photopolymerization initiation composition and thermal polymerization initiation composition.
9. a color filter, is characterized in that, has the pixel of any one described colored resin composition formation of right to use requirement 1～8.
10. a liquid crystal indicator, is characterized in that, has color filter claimed in claim 9.
11. an organic EL display is characterized in that, has color filter claimed in claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-267814 | 2011-12-07 | ||
| JP2011267814 | 2011-12-07 |
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| CN103149799A true CN103149799A (en) | 2013-06-12 |
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|---|---|---|---|
| CN2012105139416A Pending CN103149799A (en) | 2011-12-07 | 2012-12-04 | Colored resin composition, color filter, liquid crystal display and organic el display device |
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| Country | Link |
|---|---|
| JP (2) | JP6107094B2 (en) |
| CN (1) | CN103149799A (en) |
| TW (1) | TW201331710A (en) |
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| CN103044248A (en) * | 2012-12-10 | 2013-04-17 | 深圳市惠乐光电有限公司 | Low-polymer cross-linking agent, preparation method thereof, insulation protection photoresist for manufacturing process of touch screen device and application thereof |
| CN105388547A (en) * | 2014-08-29 | 2016-03-09 | 三星电子株式会社 | Electronic device having color filter |
| CN109661855A (en) * | 2016-09-05 | 2019-04-19 | 三菱化学株式会社 | Organic electroluminescent device spaced walls, which are formed, uses photosensitive polymer combination, spaced walls, organic electroluminescent device, image display device and illumination |
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Also Published As
| Publication number | Publication date |
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| TW201331710A (en) | 2013-08-01 |
| JP6107094B2 (en) | 2017-04-05 |
| JP2017122927A (en) | 2017-07-13 |
| TWI563341B (en) | 2016-12-21 |
| JP2013140346A (en) | 2013-07-18 |
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