JP3476208B2 - Dyes for color filters - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye suitably used for a color filter, especially 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. Has been made. 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 each propose a method of producing a color filter by forming a pattern with a photoresist to which a pigment or a dye is added as a pigment. However, the former method is not very suitable for the production of a color filter for CCD, which requires high resolution, because the pigment itself is particles of about 1 μm. Further, the latter method has a problem in the stability of the coloring pattern.

Moreover, these methods have another major problem. That is, a normal dye is present as a foreign substance in an alkali developable resist.
That is, unlike the case of semiconductor use, in the case of color filter use, it is desirable that the film thickness is 1 μm or less. Therefore, a large amount of dye should be added to a resist composition containing an alkali-soluble resin and an organic solvent. I won't.
However, if the dye is originally soluble in an organic solvent,
In most cases, since it is insoluble in an alkaline developing solution (aqueous solution), it is impossible to obtain a photoresist having high resolution by adding a large amount of dye.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems and provide a dye for resist addition for color filters, which is excellent in various properties such as resolution and stability of a colored pattern. is there.

[0005]

Means for Solving the Problems] The present invention can be represented by the general formula ^{_{(I) D- (SO 3 -}} ) m X m (I) ( wherein, D is represents a dye matrix, m is an integer of 1 or more Where X is the formula (Ia) or (Ib) And Q _{1 to} Q ₆ each independently represent a hydrogen atom, an aralkyl group, a heterocyclic group, or an aliphatic or aromatic organic compound residue. However, Q ₁
At least one of Q ₄ to Q ₄ represents a group having 5 or more carbon atoms. Amine salts Der acid dye represented by) it is, and Yes
Machine solvent and alkaline aqueous solution-soluble color filter resist additive dye, the general formula (II) D - [(SO 2 NHQ 7) p (SO 2 NHQ 8) q] (II) ( wherein, D is the Q ₇ to Q ₈ represents the same meaning are each independently of the represents the number 1 or more organic compound residue carbon, p and q each represents an integer of 1 or more. However, p + q is 1
It is 6 or less. ) Sulfonamide compound der acid dye represented by is, and soluble in an organic solvent and an aqueous alkali solution
A color filter resist addition dye, novolac and the color filter resist addition dye is applied to a substrate for color filter resist and the color filter resist is dissolved in an organic solvent,
The present invention provides a method for producing a color filter, which comprises evaporating a solvent to form a resist film, exposing the resist film through a mask, and performing alkali development.

Specific examples of such dyes include amine salts of acid dyes represented by the following general formula (I),
And a sulfonamide compound of an acid dye represented by the following general formula (II).

[0007] ^{_{D- (SO 3 -) m X}} m (I) D [(SO 2 NHQ 7) p] [(SO 2 NHQ 8) q] (II)

In the formula, D represents a dye matrix, m represents an integer of 1 or more, and X represents the following formula (Ia) or (Ib).

[0009]

[Chemical 1]

Represents a cation represented by, where Q ₁
To Q ₆ each independently represent a hydrogen atom, an aralkyl group, a heterocyclic group or an aliphatic or aromatic organic compound residue, and at least one of Q _{1 to} Q ₄ is a group having 5 or more carbon atoms, That is, it represents an aralkyl group, an aromatic organic compound residue, or a heterocyclic group having 5 or more carbon atoms or an aliphatic organic compound residue, respectively. Q ₇ and Q ₈ are each independently
It represents an organic compound residue having 1 or more carbon atoms, preferably 5 or more carbon atoms, p and q each represent an integer of 1 or more, and p + q is 16 or less.

Examples of the aralkyl group, heterocyclic group, aliphatic organic compound residue and aromatic organic compound residue represented by Q _{1 to} Q ₆ in the formulas (Ia) and (Ib) include benzyl, phenethyl, Heterocyclic group exhibiting aromaticity, C1 or more aliphatic hydrocarbon residue, C2 or more aliphatic ester residue, C2 or more aliphatic ether residue, C6
The above-mentioned aromatic hydrocarbon residue, aromatic ether residue having 12 or more carbon atoms, aromatic ester residue having 8 or more carbon atoms and the like can be mentioned. In formula (Ia), at least one of Q _{1 to} Q ₄ is a group having 5 or more carbon atoms, that is, an aralkyl group,
It represents an aromatic organic compound residue, or a heterocyclic group having 5 or more carbon atoms or an aliphatic organic compound residue, respectively.

Specific examples of the cation represented by X in the general formula (I) include those represented by the following formulas (i) to (iv).

(C _n H _{2n + 1} NH ₃ ) ⁺ (i) (C _s H _{2s + 1} OC _t H _2t NH ₃ ) ⁺ (ii) [(C _n H _{2n + 1} ) (C ₆ H ₅ CH ₂ ) ₂ NH] ⁺ (iii) (C _n H _{2n + 1} ) Py ⁺ (iv)

In the formula, n is 1 or more, preferably 5 to 20.
, S and t each represent an integer of 1 or more, s is preferably 5 or more, s + t is preferably 5 to 20, Py is pyridine in which a nitrogen atom is connected to C _n H _{2n + 1.} Represents a ring or a methylpyridine ring.

In the general formula (II), Q ₇ and Q ₈
The organic compound residue having 1 or more carbon atoms represented by
For example, an aliphatic hydrocarbon residue having 1 or more carbon atoms, 2 carbon atoms
The above-mentioned aliphatic ester residue, aliphatic ether residue having 2 or more carbon atoms and the like can be mentioned. Specific examples of Q ₇ and Q ₈ include groups represented by the following formulas (v) and (vi).

C _n H _{2n + 1} − (v) C _s H _{2s + 1} OC _t H _2t − (vi)

In the formula, n, s and t have the same meanings as described above.

As the dye matrix represented by D in the general formulas (I) and (II), those having a desired spectrum and performance as a color filter may be appropriately selected. For example, an acid dye having a phthalocyanine skeleton is preferably used as the cyan dye matrix. The amine salt of the acidic dye represented by the general formula (I) can be produced by reacting the acidic dye having a sulfonic acid group with the amine corresponding to X in the general formula (I). Further, the sulfonamide compound of the acidic dye represented by the general formula (II) corresponds to -NHQ ₇ and -NHQ ₈ in the general formula (II) after converting the sulfonic acid group of the acidic dye into a sulfonyl chloride by a conventional method. Then, it can be produced by reacting with the respective amines represented by NH ₂ Q ₇ and NH ₂ Q ₈ .

The dye of the present invention can be applied to an alkali-developable resist containing an alkali-soluble resin. As such a resist, an alkali-soluble resin and a quinonediazide compound are dissolved in an organic solvent, and in some cases, a positive resist which may further contain other components such as a cross-linking agent, and an alkali-soluble resin, a cross-linking agent. A negative resist in which the agent and the photo-acid generator are dissolved in an organic solvent can be used.

The alkali-soluble resin may be any alkali-soluble resin that has been conventionally used in alkali-development type positive or negative resists, and specifically, a resin having a phenolic hydroxyl group, for example, a phenol resin. And novolac resin. The novolak resin is usually obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols used for producing the novolac resin include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol C, and bisphenol A. These phenols may be used alone or in combination of two or more. As aldehydes,
Examples thereof include aliphatic or aromatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like. The molecular weight distribution of the alkali-soluble resin may be adjusted by means such as fractionation, if necessary. In addition, low molecular weight phenols such as bisphenol A and bisphenol C may be added as a part of the alkali-soluble resin.

The quinonediazide compound used in the positive resist may also be one conventionally known as a photosensitizer for an alkali development type positive resist. Specifically, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4-sulfonic acid ester, o-naphthoquinonediazide-4-sulfonic acid amide, etc. Can be mentioned. For example, JP-A-2-84
The quinonediazide sulfonic acid ester of a phenolic compound described as the general formula (I) in JP-A-650 and JP-A-3-185447 can be used as the photosensitive quinonediazide compound.

The cross-linking agent used for the negative type resist and optionally used for the positive type resist may be any one as long as it can cross-link and cure the above-mentioned resin.
II)

-(CH ₂ ) _u OR (III)

(Wherein R represents a hydrogen atom or a lower alkyl group, and u represents an integer of 1 to 4), and compounds such as melamine. Formula (II
Specific examples of the compound having a group represented by I) include di- or triamino-s- represented by the following formula (IV).
Examples thereof include triazine compounds and compounds represented by the following formulas (V) to (X).

[0025]

[Chemical 2]

In the formula, Z represents a group —NR ₁ R ₂ or a phenyl group, one of R _{1 to} R ₆ represents a group — (CH ₂ ) _u OR, and the rest are each independently a hydrogen atom or group - (CH _{2) u} O
Represents R, where R and u have the meanings given above.

[0027]

[Chemical 3]

The lower alkyl group represented by R in the formulas (III) and (IV) includes, for example, methyl, ethyl, propyl, butyl and the like, among which methyl or ethyl is preferable. Each of the compounds represented by formula (V) and formula (VI) can be produced by condensing p-cresol or pt-butylphenol with formaldehyde under basic conditions. In addition, formula (VII) ~
Each compound represented by (X) is described in, for example, JP-A-1-
It is described in Japanese Patent No. 293339. Examples of preferable compounds having a group represented by the formula (III) include, for example,
Hexamethoxymethylol melamine, hexamethoxyethylol melamine, hexamethoxypropyrol melamine and the like can be mentioned.

The photo-acid generator used in the negative resist may be a compound which directly or indirectly generates an acid by the action of light, and is not particularly limited. Trihalomethyltriazine compounds described in Japanese Patent No. 163552, Japanese Patent Publication No. 1-5777
The disulfone compound described in Japanese Patent Laid-Open No.
Examples thereof include compounds containing a sulfonic acid ester group described in JP-A-293339, compounds represented by the following respective formulas, onium salts, and the like.

R ₈ —SO ₂ —SO ₂ —R ₉ —SO ₂ —SO ₂ —R ₁₀ CF ₃ —SO ₂ O— (CH ₂ ) _v —Y CF ₃ —SO ₂ O— [C (Y ₁ ) _{(Y 2)] w -C (} O) -Y 3 CF 3 -SO 2 O-N (Y 4) -C (O) -Y 5 CF 3 -SO 2 O-N = C (Y 6) (Y ₇ )

In the formula, R ₈ and R ₁₀ each independently represent an optionally substituted aryl, aralkyl, alkyl, cycloalkyl or heterocyclic group, and R ₉ represents an optionally substituted arylene group. Represents; Y represents an optionally substituted aryl group, and v is 0
Or Y ₁ and Y ₂ each independently represent an optionally substituted alkyl, alkoxy or aryl group, Y ₃ represents an optionally substituted aryl group, and w is 1 or 2 Y ₄ represents an optionally substituted alkyl group, Y ₅ represents an optionally substituted aryl group; Y ₆ represents a hydrogen atom or an optionally substituted alkyl or aryl group, Y ₇ represents an optionally substituted aryl group.

[0032]

[Chemical 4]

Further, the organic solvent used for the positive and negative resists may be any one which can dissolve the above-mentioned components including the dye of the present invention, for example, 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, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, ethyl pyruvate, dimethyl sulfoxide, dioxane , Dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more.

In both the positive and negative resists, the alkali-soluble resin is usually used in an organic solvent in an amount of 2-5.
It is dissolved at a concentration of about 0% by weight. The quinonediazide compound in the positive resist is usually used in the above resin solution,
It is used so as to have a concentration of about 2 to 20% by weight. The cross-linking agent contained in the negative type resist and optionally contained in the positive type resist is usually used in each case so as to have a concentration of about 2 to 20% by weight in the above resin solution. . The photo-acid generator contained in the negative resist is usually used in the above resin solution so as to have a concentration of about 2 to 20% by weight. Further, the dye according to the present invention, whether it is a positive resist or a negative resist, is usually used in the above resin solution so as to have a concentration of about 0.1 to 20% by weight.

By coating such a resist on a substrate, evaporating the solvent to form a resist film, exposing the resist film through a mask, and performing alkali development, a colored pattern to be a color filter can be obtained. For the exposure at this time, for example, ultraviolet rays from a mercury lamp, deep ultraviolet rays, electron beams, X-rays, etc. are used.

[0036]

EXAMPLES Next, the present invention will be described more specifically by way of examples and application examples. In these examples, parts represent parts by weight. In addition, in the following application examples, the conditions common to the production of the colored pattern (color filter) are as follows. That is, a silicon wafer was spin-coated with a resist composition in which an alkali-soluble resin, a dye, and other components were dissolved in an organic solvent, the solvent was evaporated by heating, and then exposure was performed through a mask. After the exposure, if necessary, it was heated and then developed to obtain a colored pattern. The exposure is an i-line exposure stepper HITACHI manufactured by Hitachi, Ltd.
LD-5010-i (NA = 0.40) or g-line exposure stepper NSR1505 G3C (NA = 0.42) manufactured by Nikon Corporation was used. For the development, a developer SOPD manufactured by Sumitomo Chemical Co., Ltd. was used.

Example 1 To an aqueous solution containing 2 parts of CI Acid Blue 249 which is copper phthalocyanine sulfonic acid, an equivalent amount of a mixture of dibenzyldodecylamine and 2-heptanone was added and stirred. After that, liquid separation was performed to obtain a 2-heptanone solution containing a dye in which CI Acid Blue 249 became a dibenzyldodecylamine salt.

Example 2 The same operation as in Example 1 was carried out except that dodecylamine was used in place of dibenzyldodecylamine, and CI Acid Blue 249 contained a dye in the form of a dodecylamine salt.
A heptanone solution was obtained.

Application Example 1 A cresol novolak resin (polystyrene-converted weight average molecular weight 4,300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5) was used as 3. 4 copies, below

[0040]

[Chemical 5]

An o-naphthoquinonediazide-5-sulfonic acid ester (having an average of two hydroxyl groups esterified) prepared from the phenol compound represented by
Part and each of the 2-containing dyes obtained in Examples 1 and 2.
20 parts of the heptanone solution was mixed to obtain a positive resist composition. Each positive resist composition thus obtained 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 cyan positive type pattern having a resolution of 1 μm.

Example 3 2 parts of CI Acid Blue 249, which is copper phthalocyanine sulfonic acid, was sulfonyl chlorided by a conventional method and then reacted with dodecylamine to give CI Acid Blue.
A dodecyl amidated product of 249 was obtained.

Example 4 The same operation as in Example 3 was carried out except that 3-decyloxypropylamine was used instead of dodecylamine to obtain a 3-decyloxypropyl amidation product of CI Acid Blue 249.

Application Example 2 0.8 parts of each sulfonamide compound obtained in Examples 3 and 4 and 3.4 parts of the same cresol novolac resin used in Application Example 1 were used in Application Example 1. The same o-naphthoquinonediazide-5-sulfonic acid ester as 1.8
Parts, 6 parts of ethyl cellosolve acetate and 15 parts of ethyl lactate were mixed to obtain a positive resist composition. Each positive resist composition thus obtained 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 cyan positive type pattern having a resolution of 1 μm.

Example 5 To an aqueous solution containing 2 parts of aminol fast brilliant pink RL which is an acid dye manufactured by Hoechst Co., a mixture of dibenzyldodecylamine and 2-heptanone in an equivalent amount was added and stirred. After that, liquid separation was performed to obtain a 2-heptanone solution containing a dye in which Aminol Fast Brilliant Pink RL became a dibenzyldodecylamine salt.

Example 6 Example 5 except that 2 parts of Suminol Milling Yellow MR, a yellow acid dye manufactured by Sumitomo Chemical Co., Ltd., was used.
The same procedure was followed as in (2) to obtain a 2-heptanone solution containing a dye in which Suminol Milling Yellow MR became a dibenzyldodecylamine salt.

Application Example 3 The procedure of Application Example 1 was repeated except that the 2-heptanone solutions containing the dyes obtained in Examples 5 and 6 were used.
A positive pattern of magenta and yellow colors having a resolution of μm was obtained.

Example 7 Aminole Fast Brilliant Pink RL was prepared in the same manner as in Example 3 except that 2 parts of 3-aminoethyl Fast Brilliant Pink RL, an acid dye manufactured by Hoechst Co., and 3-decyloxypropylamine were used. To obtain 3-decyloxypropyl amidated compound.

Application Example 4 0.8 part of the sulfonamide compound obtained in Example 7 and 3. of the same cresol novolak resin as used in Application Example 1 were used.
5 parts, 1.8 parts of the same o-naphthoquinonediazide-5-sulfonic acid ester used in Application Example 1, 6 parts of ethyl cellosolve acetate and 15 parts of ethyl lactate were mixed to obtain a positive resist composition. Obtained. After spin-coating the positive resist composition on a silicon wafer, the organic solvent was evaporated. After exposing this silicon wafer, the exposed portion was removed by alkali development to obtain a magenta-color positive type pattern having a resolution of 1 μm.

Application Example 5 1 part of the 3-decyloxypropyl amidation product of CI Acid Blue 249 obtained in Example 4, 3 parts of the same cresol novolac resin used in Application Example 1 and hexamethoxymethylolated melamine were used. 0.3 part, the following formula

[0051]

[Chemical 6]

A negative resist composition was obtained by mixing 0.2 part of the photo-acid generator represented by the formula, 15 parts of 2-heptanone and 5 parts of dimethylformamide. After spin coating a silicon wafer with this negative resist composition, the organic solvent was evaporated. After exposing this silicon wafer,
Heat at 120 ° C for 3 minutes, then develop with alkali and
A cyan negative pattern having a resolution of μm was obtained.

[0053]

EFFECT OF THE INVENTION The dye for color filter resist addition of the present invention is soluble in an organic solvent and also in an alkali developing solution, so that when it is present in a large amount in a color filter manufacturing resist. However, it does not act as a foreign substance during development. So with this dye,
It is possible to easily manufacture a color filter excellent in various properties such as fineness and stability of a coloring pattern.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shigeki Yamamoto               3-1-1 Kasuga, Konohana-ku, Osaka City, Osaka Prefecture               No. 98 Sumitomo Chemical Co., Ltd.                (56) Reference JP-A-1-168775 (JP, A)                 JP 64-88505 (JP, A)

Claims (8)

(57) [Claims] 1. A general formula ^{_{(I) D- (SO 3 -}} ) m X m (I) ( wherein, D is represents a dye matrix, m represents an integer of 1 or more, X is formula (Ia) or (Ib) And Q _{1 to} Q ₆ each independently represent a hydrogen atom, an aralkyl group, a heterocyclic group, or an aliphatic or aromatic organic compound residue. However, Q ₁
At least one of Q ₄ to Q ₄ represents a group having 5 or more carbon atoms. Amine salts Der acid dye represented by) it is, and Yes
Dye for resist addition to color filters that is soluble in machine solvents and alkaline aqueous solutions . 2. General formula (II) D-[(SO ₂ NHQ ₇ ) _p (SO ₂ NHQ ₈ ) _q ] (II) (wherein D represents the same meaning as described above and Q _{7 to} Q ₈ are respectively Independently, it represents an organic compound residue having 1 or more carbon atoms, and p and q each represent an integer of 1 or more, provided that p + q is 1
It is 6 or less. ) Sulfonamide compound der acid dye represented by is, and soluble in an organic solvent and an aqueous alkali solution
Dye for resist addition for various color filters. 3. The colorant for resist addition for a color filter according to claim 1, wherein the acid dye is a dye having a phthalocyanine skeleton. 4. A color filter resist comprising a novolak and the color filter resist addition dye according to claim 1 dissolved in an organic solvent. 5. The color filter resist according to claim 4, wherein the quinonediazide compound is dissolved in an organic solvent. 6. The color filter resist according to claim 4, wherein the crosslinking agent and the photoacid generator are dissolved in an organic solvent. 7. The content of a color filter dye is 0.1.
The resist for color filters according to any one of claims 4 to 6, which is -20% by weight. 8. A resist film according to any one of claims 4 to 7 is applied onto a substrate and the solvent is evaporated to form a resist film.
A method for producing a color filter, which comprises exposing through a mask and developing with an alkali.