JPS61254906A - Photosensitive and heat resistant colored paste for color filter - Google Patents

Abstract

PURPOSE:To obtain a photosensitive and heat resistant colored paste for a color filter suitable for direct patterning and giving a distinct contrast between photosensitive and nonphotosensitive parts by mixing an org. pigment insoluble in solvents with a photosensitive polyimide precursor in a specified ratio. CONSTITUTION:A photosensitive and heat resistant colored paste for a color filter is obtd. by mixing 10-300g org. pigment insoluble in org. solvents with 100g photosensitive polyimide precursor. For example, pyromellitic acid dianhydride is added to a soln. of diaminodiphenyl ether and polymerized by heating to prepare polyamic acid, and an amino compound having an azido group is bonded to the polyamic acid as a photosensitivity providing group. After a sensitizer is added, he resulting liq. mixture is kneaded with an org. pigment. The obtd. paste can be heat treated at >=300 deg.C, can be directly patterned without using a photoresist mask, and can form a pattern having sharp edges.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive heat-resistant coloring paste for color filters.

[Prior art]

Conventionally, as a heat-resistant coloring paste for color filters, for example, as shown in Japanese Patent Application Laid-Open No. 58-46325, 9.
It is known that a pigment is added to a normal non-photosensitive polyimide face.

To make a color filter using a pigmented paste on a normal non-photosensitive polyimide surface, a photoresist pattern is formed using a positive or negative type photoresist on the pigmented colored polyimide layer. Using this as a mask, the polyimide layer must be etched in a pattern using a positive resist developer in the case of a positive resist, and hydrazine or ethylenediamine as an etching agent in the case of a negative resist, and the photoresist must be peeled off. This method requires two extra steps: forming a photoresist film and peeling it off.
(Blue) Required to form each filter, making the process long and complicated.

In addition, this method has the disadvantage that the two-colored polyimide layer as a whole has the same solubility in the etching agent, and the boundary between the dissolved area and the remaining area tends to be unclear.

[Problem that the invention seeks to solve]

An object of the present invention is to eliminate the above-mentioned drawbacks, and to provide a photosensitive heat-resistant coloring paste for Color 7 filters, which has a short and simple process for making a color filter, and has a clear boundary between the melted part and the remaining part. be.

[Means for solving problems]

The present invention has a primary configuration to achieve the above object.

That is, 1. the present invention comprises a solvent and an organic pigment insoluble in the solvent.
10. In the photosensitive heat-resistant coloring paste for color filters comprising a photosensitive polyimide precursor (II) and a photosensitive polyimide precursor (II), the organic pigment [I] is a photosensitive polyimide precursor (II).
This is a photosensitive heat-resistant coloring paste for color filters, characterized in that it is mixed at a ratio of 10 to 600 g to 0 g.

The photosensitive polyimide precursor (II) in the present invention is:
(General formula % formula %) (However, R1 is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R2 is a divalent organic group having at least 2 or more carbon atoms, R3 is hydrogen, Represents an alkali metal ion or ammonium ion. n is 1 or 2. COOR, is bonded at the ortho or beri position with respect to the amide group. Was the photosensitive group attached via a chemical bond?

Alternatively, it refers to a mixture of photosensitive compounds.

Polymer having the structural unit CM in the present invention (hereinafter referred to as
What is a polyimide polymer precursor?

It has a structure represented by the above general formula, and can be turned into a polymer (hereinafter referred to as a polyimide polymer) having an imide ring or other cyclic structure by heating or a suitable catalyst.

In the above structural unit CIII), R1 is a trivalent or tetravalent organic group having at least two or more carbon atoms. In terms of heat resistance of polyimide polymers.

R4 preferably has a structure in which the bond to the carbonyl group of the polymer main chain is directly formed through an aromatic ring or an aromatic heterocycle. Therefore, as R1.

Contains an aromatic ring or aromatic heterocycle, and has 6 to 3 carbon atoms
A trivalent or tetravalent group of 0 is preferred.

More preferable specific examples of R1 include:

H3CF5 (In the formula, the bond represents a bond with the carbonyl group of the polymer main chain, and the carboxyl group is located at the ortho position to the bond, but this bond is not shown in the above structural formula).

Examples include, but are not limited to, the following.

Further, in the polyimide polymer precursor, R1 may be composed of only one of these types.

A copolymer composed of two or more types may also be used.

What is particularly desirable as R1?

(However, the definition of the bond in the formula is the same as above).

In the above structural unit [■], R2 is a divalent organic group having at least two or more carbon atoms, but from the viewpoint of heat resistance when made into a polyimide polymer, the bond with the amide group of the polymer main chain is is preferably formed directly from an aromatic ring or an aromatic heterocycle. Therefore, R1 contains an aromatic ring or an aromatic heterocycle and has 6 carbon atoms.
-30 divalent groups are preferred.

Preferred specific examples of R2 include:

CH.

(In the formula, the bond represents a bond with an amide group in the main chain). Further, these may have a nuclear substituent such as an amine group, an amide group, a carboxyl group, or a sulfonamide group within a range that does not adversely affect the side heating properties of the polyimide polymer. Particularly preferred examples of those having these nuclear substituents include CONH2 and NH2.

In the polymer having the structural unit CI[[], R2. may be composed of only one type among these, or may be a copolymer composed of two or more types.

Furthermore, in order to improve the adhesiveness of the polyimide polymer, it is also possible to copolymerize an aliphatic group having a siloxane structure as R2 within a range that does not reduce the heat resistance. A preferred example is CH3CH.

Examples include.

Structural unit ([As a specific example of a polymer whose main component is 3.

Pyromellitic dianhydride and 4,4'-diaminodiphenyl ether.

Pyromellitic dianhydride and 3.3? 4.4/-benzophenone tetracarboxylic acid and 4.4'-diaminodiphenyl ether.

3, 3? 4.4/-benzophenone tetracarboxylic dianhydride and 4.4'-diaminodiphenyl ether.

5,5j 4.4'-hyphenyltetracarboxylic dianhydride 4.4/-diaminodiphenyl ether.

3,3j 4.4'-h722tetracarboxylic dianhydride and 3.3j 4.4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether.

Pyromellitic dianhydride and 3. terdiaminodiphenylsulfone pyromellitic dianhydride and'), 5', 4.4
'-benzophenone tetracarboxylic dianhydride and 3.5
'-(also c4.4'-)diaminodiphenylsulfone.

3, 3? 4.4'-benzophenonetetracarboxylic dianhydride and 3. ter (or 4.4/-)diaminodiphenylsulfone.

3.! l? 4.4/-biphenyltetracarboxylic dianhydride and 5.5/- (or 4.4/-) diaminodiphenylsulfone.

5, 354.4/-biphenyltetracarboxylic dianhydride and 3.3? 4.4/-benzophenone tetracarboxylic anhydride and 3.37 (or 4.4/-) diaminodiphenylsulfone.

Pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and bis(3-aminopropylene)tetramethyldisiloxane.

Pyromellitic dianhydride and 6,3ζ4,4/-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

3, 3? 4.4/-benzophenonetetracarboxylic dianhydride and 4.4'-diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

3, 3? 4. aI-biphenyltetracarboxylic dianhydride and 4,41-diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

3, 3? 4.4/-biphenyltetracarboxylic dianhydride and 3.3? 4.4/-benzophenonetetracarboxylic anhydride and 4,4'-diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3,3'-(or 4,4/
-) diaminodiphenylsulfone and bis(3-aminopropyl)tetramethyldisiloxane.

Pyromellitic dianhydride and 3+ 3j 4.4t-
Benzophenone tetracarboxylic dianhydride and 3,3/-
(or 4,4/)diaminodiphenylsulfonoyohibisc'5-aminopropyl)tetramethyldisiloxane.

3, 3? 4.4/-benzophenonetetracarboxylic dianhydride and 6. (or 4,4/-)diaminodiphenylsulfone and bis(3-aminopropyl)tetramethyldisiloxane.

3.3, 4,4'-biphenyltetracarboxylic dianhydride, 3,3/- (or 4,4/-) diaminodiphenylsulfone, and bis(3-aminopropyl)tetramethyldisiloxane.

3, 3? 4.4/-biphenyltetracarboxylic dianhydride and 3.3? 4. Polyamic acid synthesized from 4/-benzophenone tetracarboxylic dianhydride, 3,3/- (or 4,4/-) diaminodiphenylsulfone, bis(5-aminopropyl)tetramethyldisiloxane, etc. is preferred. used.

The polymer having the structural unit CII) as a main component may consist only of the structural unit (III), or may be a copolymer with other structural units. The type and amount of structural units used in copolymerization are desirably selected within a range that does not significantly impair the heat resistance of the polyimide polymer obtained by the final heat treatment. These are typical examples, but are not limited to these.

The most typical photosensitive group bonded to the polyimide polymer precursor via a chemical bond is a group having a carbon-carbon double bond that can be trimerized or polymerized by light, such as vinyl group, acrylic group, methacrylic group, etc. Examples include groups having a group, an allyl group, and a methallyl group. These photosensitive groups are ester bonds.

It can be bonded to a polyimide polymer precursor via an amide bond, an imide bond, or the like. As a method for introducing a photosensitive group through an ester bond, well-known methods such as the method shown in US Pat. No. 3,957,512 can be applied.

An amine compound having 9 dichromate, bisazide, or vinyl group as a photosensitive compound that can photosensitize a polyimide polymer precursor by mixing.

Examples include amino compounds having an azide group.

A method of photosensitizing a polyimide polymer precursor by mixing dichromate is described by Kevwin and Coldrick (
Polymer Fjng &, Sci 11, 4
26.1971).

For example, bisazide.

Typical examples include aromatic bisazide compounds such as H3.

The amount added is 0.1 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the polyimide polymer precursor.

Preferably, the amount is 0.5 parts by weight or more and 50 parts by weight or less. Outside this range, the developability and storage stability of the phenol will be adversely affected.

An example of an amino compound having a vinyl group is:

General formula (where R4 is hydrogen or a phenyl group, R5 is hydrogen or a lower alkyl group having 1 to 6 carbon atoms, R4 is a substituted or unsubstituted hydrocarbon group having 2 to 12 carbon atoms, R2H is a substituted or unsubstituted hydrocarbon group) each represents an alkyl group having 1 to 6 carbon atoms).

represents an alkyl group).

General formula [C] R1゜ (CH song C-CH+N-H.

2 n (Here, R1° represents hydrogen or a methyl group.

n+7wm! 1, 1l-1 to 3. ) or their quaternized salts.

As a specific example.

(Here, R7 is an unsubstituted or substituted carbon number 1 to 6 (CH
,).

CH, mouth CH-OH, NH.

CH.

CH-〇　-CHNH 2!2 (CH, m CH-CH,), NH etc.

The amount added should be 0.1 times or more and 2 times or less, preferably 0.5 times or more and 1.5 times or less, the equivalent weight of all carboxyl groups in the polyimide polymer precursor. or have a negative impact on the heat resistance of the final product.

Examples of amine compounds having an azide group include:

General formula (where X is -N or -3ON, Y is an alkyl 3!3 lene group, and R4, Rli, R6 represent hydrogen or an alkyl group having 5 or less carbon atoms).

(Here, x is -N or -502N3 e R4l
R5 and R4 represent hydrogen or an alkyl group having 5 or less carbon atoms) (here, X is -N, or -3o, N3.R4
, R5, R6 are hydrogen or an alkyl group having 5 or less carbon atoms,
R7 represents one group selected from).

(Here, X represents -N, , -3o□N, , R4, R□ represents hydrogen or an alkyl group having 5 or less carbon atoms).

in particular.

H5 is preferred.

The amount added is desirably 0.05 times or more and 5 times or less, preferably 0.4 times or more and 3 times or less, of the equivalent weight of all carboxyl groups in the polyimide polymer precursor.

If it deviates from this range, it will cause a decrease in photosensitivity, a decrease in developability, and a decrease in the heat resistance of the final product.

Among the above methods, a method in which a polyimide polymer precursor is mixed with a compound having an amine group and a photosensitive group is particularly suitable as a method for photosensitizing a polyimide polymer precursor.

The organic pigment [technique] in the present invention is applied to a light Mihara substrate and heat-treated at 600°C for 10 minutes.

A product with excellent heat resistance that does not cause decomposition, foaming, or significant discoloration. The particle size of the pigment is preferably 1 micron or less.

As an example of the organic pigment (I), for example, as R (red), Co1or Index Ha 73905 P
igment Red209, 46500 Pigm
ent Violet 19 and the luquinacridone pigment G (green) is Co1orIn-dex N
u 74160 Pigment area 36
, 74260 PigmsntGreen 7 Phthalocyanine green pigment B (blue) is as follows:
Co1or Index m 74160Pigme
nt Blue 15-3, Co1or Ind
ex & 74160Pigment Blue 15
--It becomes difficult to uniformly disperse the phthalocyanine and pigment shown in 4, and the film forming ability is impaired.

In the present invention, the solvent does not dissolve the organic pigment.

The photosensitive polyimide precursor may be one that dissolves, but from the viewpoint of polymer solubility, it should be 50% or more.

Preferably, 70% or more is composed of a polar solvent. A polar solvent has a solubility parameter (δ) of 95
Preferred examples of the polar solvent mentioned above include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl 2-pyrrolidone, hexamethylphosphoramide, and mixtures thereof.

In addition to the two constituent elements consisting of CI) and (II) above, a surfactant may be used as necessary to the extent that the performance as a color filter and #4 thermal properties are not significantly impaired.

A small amount of an adhesion improver etc. may be added. As a surfactant, @Florard v c-430 = (manufactured by 3M) As an adhesion improver, "5H6020" (manufactured by Toshi Silicone) "KBE-90": 5'' (manufactured by Shin-Etsu Silicone ■) etc. are mentioned as a typical example.

Next, as a method for producing the photosensitive heat-resistant coloring paste for color filters of the present invention, a method for forming a polymer such as 4,4'-diaminodiphenyl ether, for example, 4,4'-diaminodiphenyl ether, is added to a solvent heated to about 50°C with stirring. The components are added and dissolved.Next, a component for forming a polymer such as pyromellitic dianhydride is added to polymerize polyamic acid. For example, for the purpose of imparting photosensitivity to polymerized polyamic acid.

The amino compound is added, and Michler's ketone is added and mixed as a sensitizer to increase the photosensitivity. This is kneaded with an organic pigment using a triple roll under safe light to obtain the desired photosensitive side thermal coloring paste for color filters.

Note that the heat resistance in the photosensitive coloring paste for color filters of the present invention is 600"C or more, preferably 50
This means that heat treatment can be performed at 0°C for 20 minutes or more.

〔Effect of the invention〕

The photosensitive side thermal coloring paste for color filters of the present invention is
As described above, by employing a photosensitive polyimide precursor as a polymer solution and adding and mixing an organic pigment with excellent heat resistance thereto, excellent effects such as those of the first order can be obtained. That is, since the paste itself has photosensitivity, there is no need to pattern it using a photoresist as a mask, and patterning can be performed directly, making patterning very easy. Furthermore, since the contrast between the exposed and non-exposed areas is clear, a sharp edge pattern can be obtained.

Note that the effects of the present invention were evaluated based on the following criteria.

(1) Add 5 x photosensitive coloring paste for color filters prepared in the shape of the end face of the pattern.
Drop a small amount onto a 5 cm, 1 m thick glass plate using a spinner (I H-D S type manufactured by Mikasa) Terror 000
Coat at rpm x I minute and prebaked at 80°C for 1 hour.

Exposure and development, then 150℃, 20D'c, 300℃
Heat treatment was performed at 0°C for 30 minutes each. The film thickness was 1.1μ. About this sample 1Surface roughness meter (manufactured by Kosaka Laboratory, 5E)
-3E type) was investigated.

Next, the embodiments of the present invention will be fully explained based on Examples.

Example 1 110 g of diaminodiphenyl ether was dissolved in 278 g of N-methylpyrrolidone to prepare an amine solution. 120g of pyromellitic anhydride to 608g of dimethylacetamide
g and then 184 g of N-methylpyrrolidone.
was added and dissolved to obtain an acid solution. By adding an acid solution to an amine solution at 60°C and reacting for 6 hours,
A solution (A) of 60 poise was obtained at 0.

50 g of solution (A), 1.15 g of Mihira Ketone, 30
A solution of 10.2 g of diethylaminoethyl methacrylate dissolved in 10 g of dimethylacetamide was mixed together. The viscosity of this polymer solution was 12 voids/25°C.

The obtained Fes was placed in a 250 cc wide-mouthed polyethylene bottle, and 7 talocyanine blue powder 20ε was added thereto.
The mixture was thoroughly kneaded using three rolls to obtain a desired photosensitive heat-resistant colored paste for color filters.

Apply this paste on a glass plate with a spinner.

Prebaked at 80°C for 1 hour, and heated to 10CIPxID.

A mask with μ patterns lined up at 20g intervals is placed in close contact with the mask.
23. The sample was exposed for 2 minutes using a high-pressure mercury lamp from a distance of . After exposure, development was performed with a mixed solvent of dimethylformamide (5 parts) and methanol (2 parts) to obtain a relief pattern. This pattern was heated at 150°C, 200°C, and 300°C for 50 minutes each, and the pattern shape of the resulting sample was examined using a surface roughness meter. As a result, the end face shape was very sharp (blue), indicating that it was a filter. Ta.

Example 2 50 g of the polymer solution of Example 1, 1.15 Mihira Ketone
A solution of 2.34 g of 2-(N,N-dimethylamino)ethyl barazidobenzoate dissolved in 10 g of dimethylacetamide were mixed together.

The viscosity of this polymer solution was 12 voids/25°C.

The obtained face was taken into a 250 cc polyethylene wide-mouth container, and 20 g of 7 talocyanine green powder was added thereto.
The mixture was mixed and thoroughly kneaded with a triple roll to obtain a desired photosensitive heat-resistant coloring paste for color filters. This paste was coated, exposed, developed, and cured in the same manner as in Example 1, and the pattern shape was examined using a surface roughness meter. As a result, a G (green) filter with a very sharp end face shape was obtained.

Claims (1)

[Claims] (1) In a photosensitive heat-resistant coloring paste for color filters comprising a solvent, an organic pigment [I] insoluble in the solvent, and a photosensitive polyimide precursor [II], the organic pigment [I] is a photosensitive polyimide precursor [II]. II] 10-3 per 100g
A photosensitive heat-resistant coloring paste for color filters, characterized in that the paste is mixed at a ratio of 0.00g.