JPH0651115A - Dyestuff for color filter - Google Patents

Abstract

PURPOSE:To easily produce a color filter excellent in refinedness, stability in colored pattern, etc., by using a specified dyestuff for the color filter. CONSTITUTION:This dyestuff for the color filter is the amine salt of acid dye or a sulfonamide compd. of acid dye and is soluble in org. solvent or aq. alkali. The amine salt of acid dye shown by formula I is exemplified as the dyestuff. In formula I, D is host dyestuff, X is (R1') (R2' (R3') (R4')N<+> or a group shown by formula II, and R1',...R4' are independently hydrogen atom, aralkyls, hetrocyclic rings or aliphatic or aromatic org. compd. residues. In formula II, R5' and R6' are independently hydrogen atom, aralkyls, heterocyclic rings or aliphatic or aromatic compd. residues.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter, and more particularly to a dye used in a color filter for a solid-state image pickup device.

[0002]

2. Description of the Related Art A color filter, particularly a color filter for a solid-state image pickup device such as a charge coupled device (CCD) or a liquid crystal display device (LCD), is generally formed by first forming a pattern with a photoresist and then dyeing it. It is made by the method. However, this method has problems such as complexity of the dyeing process and difficulty in process control. Therefore, for example, JP-A-4-163552 and JP-A-4-128703 propose methods of forming a color filter by forming a pattern with a photoresist to which pigments such as pigments and dyes are added. . However, the former method is not suitable for producing a CCD color filter that requires high resolution because the pigment itself contains particles of about 1 μm. In addition, the latter method has a problem in the stability of the coloring pattern. And, these methods have more serious problems. That is, a normal dye is present as a foreign substance in an alkali developable resist. That is, unlike the case of semiconductor production, in the case of color filter production, it is desirable that the film thickness is 1 μm or less. Therefore, a large amount of dye must be added to a resist composition containing an alkali-soluble resin and an organic solvent. I have to. However, originally, if the dye is soluble in an organic solvent, in most cases, it is insoluble in the alkaline developer (aqueous solution). Therefore, it is actually possible to add a large amount of the dye and obtain a photoresist having high resolution. It cannot be done.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a dye for a color filter which is excellent in various properties such as resolution and stability of a coloring pattern.

[0004]

The present invention is a dye for a color filter which is an amine salt of an acid dye or a sulfonamide compound of an acid dye and which is soluble in an organic solvent and an alkaline aqueous solution.

[0005] As such a dye, for example, the general formula ^{_{(I) D- (SO 3 -}} ) m X m (I) wherein, D is a dye matrix, X is _{(R 1 ') (R 2} ' )
(R ₃ ') (R ₄ ') N + or the following formula

[0006]

[Chemical 1]

(Where R_Five'And R₆'Each independently hydrogen
Atoms, aralkyl groups, heterocyclic groups or aliphatic or aromatic groups
Represents an aromatic organic compound residue. ) Is a group represented by m
Each represents an integer of 1 or more. R₁'~ R_Four' Each is independent
Hydrogen atom, aralkyl group, heterocyclic group or aliphatic
Or, it represents an aromatic organic compound residue. ] Acid
Salt of organic dye, and general formula (II) D_y[(SO₂NHR₇')_q] [(SO₂NHR₈')_{q '}] [(SO₂NHR₉') _{q ''} ] (II) [wherein D_yIs the dye matrix, R₇'~ R₉'Independently
Hydrogen atom, having 1 or more carbon atoms (preferably having 5 or more carbon atoms)
Of) organic compound residue,_q~_{q ''}Is an integer greater than or equal to 1
, Respectively. However,_q+_{q '}+_{q ''}≤16
It ] The acid sulfone amide compound represented by
You can

The aralkyl group, heterocyclic group or aliphatic or aromatic organic compound residue represented by R ₁ 'to R ₆ ' is, for example, benzyl or phenethyl group, heterocyclic group showing aromaticity, carbon number 1 The above aliphatic hydrocarbon groups, aliphatic ester residues having 2 or more carbon atoms, aliphatic ether groups having 2 or more carbon atoms, aromatic hydrocarbon groups having 6 or more carbon atoms, aromatic ether groups having 12 or more carbon atoms, or Examples thereof include aromatic ester residues having 8 or more carbon atoms. At least one of R ₁ ′ to R ₆ ′ is preferably an aralkyl or heterocyclic group having 5 or more carbon atoms, or an aliphatic or aromatic organic compound residue. Specific examples of X in the general formula (I), the following formula _{(C n H 2n + 1 NH} 3) + (i) wherein, n represents 1 or more (preferably 5 or more, 20 or less)
It is an integer. ] _{(C s H 2s + 1 OC} t H 2t NH 3) + (ii) wherein, s and t are each 1 or more (preferably 5 or more,
It is an integer (less than or equal to 20), and preferably s + t ≧ 5. ] [(Wherein, n is the same meaning as _{above.) (C n H 2n +} 1) (C 6 H 5 CH 2) 2 NH ] _{+ (iii) (C n H} 2n + 1) P y ( iv) (wherein, n is as defined above, P _y is. representing a pyridinium _{group) (C n H 2n + 1} ) P y '(v) ( wherein, n has the same meaning as above , P _y 'represents a methylpyridinium group).

The organic compound residue having 1 or more carbon atoms represented by R ₇ 'to R ₉ ' is, for example, an aliphatic hydrocarbon group having 1 or more carbon atoms, an aliphatic ester residue having 2 or more carbon atoms, or a carbon number. Examples thereof include two or more aliphatic ether groups. R ₇ '
Examples of the to R ₉ ', (wherein, n is the same meaning as above.) The formula _{C n H 2n + 1 (vi} ) C s H 2s + 1 OC t H 2t (vii) ( wherein In the above, s and t have the same meanings as described above.) And the like.

The dye matrix represented by D and D _y may be appropriately selected from those having a desired spectrum and performance as a color filter, and as the cyan color, a matrix of an acid dye having a phthalocyanine skeleton is preferably used. That is, the dye represented by the general formula (I) or (II) is composed of the above acid dye or its derivative and an amine corresponding to X in the general formula (I) or NH ₂ R ₇ ′ to NH ₂ R ₉ ′. Each of the amines shown can be prepared by reacting. Examples of organic solvents for photoresists include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate,
Examples thereof include propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, ethyl pyruvate, dimethyl sulfoxide, dioxane or dimethylformamide. These organic solvents may be used alone or in combination of two or more. The dye of the present invention can be applied to an alkali-developable resist containing an alkali-soluble resin. These resists include alkali-soluble resins,
A positive resist containing a quinonediazide compound and an organic solvent (which may optionally contain a crosslinking agent), or a negative resist containing an alkali-soluble resin, a photoacid generator, a crosslinking agent and an organic solvent can be mentioned.

Examples of the alkali-soluble resin include resins having a phenolic hydroxyl group, such as phenol resin or novolac resin. Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol C or bisphenol A. These phenols may be used alone or in combination of two or more. Examples of the aldehydes include aliphatic or aromatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or benzaldehyde. If necessary, the resin having a phenolic hydroxyl group may be adjusted in molecular weight distribution by means such as fractionation. Further, phenols such as bisphenol A or bisphenol C may be added to the resin having a phenolic hydroxyl group.

Examples of the cross-linking agent include the following formula:-(CH ₂ ) _p OR (wherein R represents a hydrogen atom or a lower alkyl group, _p
Represents an integer of 1 to 4. And a melamine having a group represented by the formula (1). As the compound having a group represented by the above formula, for example, the following formula

[0013]

[Chemical 2]

[In the formula, Z represents —NR ₁ R ₂ or a phenyl group. R _{1 to} R ₆ are each a hydrogen atom, — (CH ₂ ) _p OH, provided that at least one of them represents — (CH ₂ ) _p OH or — (CH ₂ ) _p OR _7.
Or - represents a (CH _{2) p} OR _7. R ₇ represents a lower alkyl group. _p represents an integer of 1 to 4. ] The compound shown by the following, or the following formula

[0015]

[Chemical 3]

[0016]

[Chemical 4]

Examples thereof include compounds represented by: The alkyl group represented by R and R _{1 to} R ₇ includes a methyl, ethyl, n-propyl or n-butyl group, and the preferred alkyl group includes a methyl or ethyl group. The compounds (crosslinking agents) represented by formulas (i) to (ii) are
It can be produced by condensing p-cresol or t-butylphenol with formaldehyde under basic conditions. The compounds represented by formulas (iii) to (vi) (crosslinking agents) are known compounds described in JP-A-1-293339. Preferable compounds having a group represented by the formula:-(CH ₂ ) _p OR include, for example, hexamethoxymethylolated melamine, hexamethoxyethylolated melamine, hexamethoxypropyrolated melamine and the like.

The photoacid generator is not particularly limited as long as it can generate an acid directly or indirectly by light. For example, a trihalomethyltriazine compound described in JP-A-4-163552, disulfone compounds described in 1-57777 JP, the _{formula, R 8 -SO 2 -SO 2 -R} 9 -SO 2 -SO 2 -R 10 ( wherein, R ₈ and R ₁₀ are each independently A compound represented by optionally substituted aryl, aralkyl, alkyl, cycloalkyl or heterocyclic group, and R ₉ represents optionally substituted aryl), JP-A-1-2933.
Photoacid generator containing a sulfonic acid ester group as described in 39 JP, the formula _{CF 3 -SO 2 O- (CH 2} ) n '-Y ( wherein, Y is an optionally substituted aryl group 'compounds, the formula CF ₃ -SO ₂ O- _{[C (Y 1) (Y 2} ) ] _m represented by represents 0 or 1.)' -C (O) -Y 3 ( wherein n, the Y ₁ and Y ₂ are each independently an optionally substituted alkyl, alkoxy or aryl group, and Y ₃
Is an optionally substituted aryl group, m ′ is 1 or 2
Are respectively represented. ), A compound represented by the formula: CF ₃ —SO ₂ O—N (Y ₄ ) —C (O) —Y ₅ (wherein Y ₄ represents an optionally substituted alkyl group, and
₅ represents an aryl group which may be substituted, respectively. ), A compound represented by the formula: CF ₃ —SO ₂ O—N═C (Y ₆ ) (Y ₇ ) (wherein Y ₆ represents a hydrogen atom or an optionally substituted alkyl or aryl group, Y ₇ Each represents an optionally substituted aryl group), a compound represented by the following formula:

[0019]

[Chemical 5]

Examples include onium salts represented by:

Examples of the quinonediazide compound include o
-Naphthoquinone diazide-5-sulfonic acid ester or sulfonic acid amide, or o-naphthoquinone diazide-
4-sulfonic acid ester, sulfonic acid amide, etc. are mentioned. These esters or amides are represented by the general formula (I) in JP-A-2-84650 and JP-A-3-49437.
It can be produced by a known method using the phenol compound described in 1.

The alkali-soluble resin is usually dissolved in an organic solvent in a proportion of about 2 to 50% by weight. The amount of the quinonediazide compound, the cross-linking agent, the photo-acid generator and the dye used is usually
2-20, 2-2 for alkali-soluble resin solution, respectively
It is added in a proportion of 0, 2 to 20 and 0.1 to 20% by weight.
For the exposure, for example, ultraviolet rays such as a mercury lamp, deep ultraviolet rays, electron beams or X-rays are used.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Reference Examples. In the examples and reference examples, parts represent parts by weight. The common conditions in the following reference examples are as follows. Regarding the method for producing the resist and the color filter (coloring pattern), a silicon wafer is spin-coated with a resist composition containing a dye, an organic solvent and an alkali-soluble resin, and a quinonediazide compound (or a crosslinking agent and a photo-acid generator), After the solvent was evaporated by heating, exposure was performed through a mask to decompose the quinonediazide compound (or photoacid generator). Then, after heating, development was performed to obtain a colored pattern. Exposure is Hitachi's i-line exposure stepper HITACHI LD-5010-i (NA = 0.
40) Or Nikon g-line exposure stepper NSR1505 G3C
(NA = 0.42). As the developing solution, SOPD manufactured by Sumitomo Chemical Co., Ltd. was used.

Example 1 Copper phthalocyanine sulfonic acid (CI Acid Blue 249
) An aqueous solution containing 2 parts, and a mixture of this and an equivalent amount of dibenzyldodecylamine and 2-heptanone were stirred. After completion of stirring, liquid separation was performed to obtain an organic layer.

Example 2 An organic layer was obtained in the same manner as in Example 1 except that dodecylamine was used instead of dibenzyldodecylamine.

Reference Example 1 3.4 parts of cresol novolac resin (polystyrene-equivalent weight average molecular weight 4300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5)

[0027]

[Chemical 6]

O-naphthoquinonediazide-5-sulfonic acid ester prepared by using the phenolic compound represented by the formula (on average, two hydroxyl groups are esterified) 1.8
Part and each of the organic layers obtained in Examples 1 and 2 were mixed to obtain a positive resist composition. A silicon wafer was spin-coated with each of the positive resist compositions obtained above, and then the organic solvent was evaporated. After exposing this silicon wafer, the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 1 μm.

Example 3 Copper phthalocyanine sulfonic acid (CI Acid Blue 249
) 2 parts of sulfonyl chloride was converted by a conventional method and then reacted with dodecylamine according to Example 2 to obtain a sulfonamide compound.

Example 4 A sulfonamide compound was obtained in the same manner as in Example 3 except that 3-decyloxypropylamine was used in place of dodecylamine.

Reference Example 2 Each sulfonamide compound obtained in Examples 3 and 4 0.8
Part, cresol novolac resin used in Reference Example 1 3.4
Part, o-naphthoquinonediazide-5 used in Reference Example 1
A positive resist composition was obtained by mixing 1.8 parts of sulfonic acid ester, 6 parts of ethyl cellosolve acetate and 15 parts of ethyl lactate. After spin-coating each of the positive resist compositions obtained above on a silicon wafer,
The organic solvent was evaporated. After exposing this silicon wafer, the exposed portion was removed by alkali development to obtain 1 μm each.
A positive colored pattern having a resolution of m was obtained.

Example 5 Aminor Fast Brilliant Pink RL manufactured by Hoechst
(2 parts) An aqueous solution, and a mixture of this and an equivalent amount of dibenzyldodecylamine and 2-heptanone were stirred. After completion of stirring, liquid separation was performed to obtain an organic layer.

Example 6 An organic layer was obtained in the same manner as in Example 2 except that 2 parts of yellow acid dye [Suminol Milling Yellow MR manufactured by Sumitomo Chemical Co., Ltd.] was used.

Reference Example 3 The procedure of Reference Example 1 was repeated except that the organic layers obtained in Examples 5 and 6 were used to obtain positive type magenta and yellow color patterns having a resolution of 1 μm, respectively.

Example 7 A sulfonamide compound was obtained in the same manner as in Example 3 except that Aminol Fast Brilliant Pink RL (2 parts) and 3-decyloxypropylamine were used.

Reference Example 4 0.8 part of the sulfonamide compound obtained in Example 7, Reference Example 1
3.5 parts of the cresol novolac resin used in Example 1, 1.8 parts of o-naphthoquinonediazide-5-sulfonic acid ester used in Reference Example 1, 6 parts of ethyl cellosolve acetate and 15 parts of ethyl lactate were mixed to obtain a positive resist composition. . The positive resist composition obtained above was spin-coated on a silicon wafer, and then the organic solvent was evaporated. After exposing this silicon wafer, the exposed portion was removed by alkali development to obtain a positive type magenta color pattern having a resolution of 1 μm.

Reference Example 5 1 part of the sulfonamide compound obtained in Example 4, 3 parts of cresol novolac resin used in Reference Example 1, 0.3 part of hexamethoxymethylolated melamine, the following formula

[0038]

[Chemical 7]

A negative resist composition was obtained by mixing 0.2 part of the photoacid generator represented by the formula (2), 15 parts of 2-heptanone and 5 parts of dimethylformamide. A silicon wafer was spin-coated with this negative resist composition, and then the organic solvent was evaporated. After exposing this silicon wafer, 120 ℃ ・ 3
It was heated for a minute and then alkali-developed to obtain a negative type colored pattern (cyan color filter) having a resolution of 1 μm.

[0040]

EFFECT OF THE INVENTION By using the color filter dye of the present invention, it is possible to easily produce a color filter which is excellent in various properties such as fineness and stability of a coloring pattern.

Claims (2)

[Claims] 1. A dye for a color filter, which is an amine salt of an acid dye or a sulfonamide compound of an acid dye, and is soluble in an organic solvent and an aqueous alkaline solution. 2. The cyan dye for a color filter according to claim 1, wherein the acidic dye is a dye having a phthalocyanine skeleton.