KR100481667B1 - Developer for dye dispersing photoresist - Google Patents

Abstract

The present invention relates to a photoresist developer, wherein the developer according to the present invention comprises (a) an alkali compound, (b) a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer or a polyoxypropylene-polyoxyethylene-poly One or more first surfactants selected from oxypropylene triblock copolymers and one or more second surfactants selected from etherified polyoxyethylene-polyoxypropylene block copolymers. The developer according to the present invention not only has a small bubble but also has a low developing residue and excellent productivity.

Description

Developer for dye dispersing photoresist

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist developer, and more particularly, to a developer for pigment dispersion photoresists used in the production of color filters for color liquid crystal displays.

Various methods have been proposed for manufacturing a color liquid crystal display (LCD), but recently, a black matrix is manufactured on a transparent substrate such as glass, and a color filter in which red, green, and blue pixels are formed thereon is used. After lamination, a method of forming a transparent electrode by sputtering a transparent conductive film such as indium tin oxide (ITO) thereon and then forming an alignment film thereon and aligning the liquid crystal is generally used.

Pigment dispersion method, dyeing method, dye dispersion method, printing method, electrodeposition method and the like are known as color filter manufacturing methods. Dye dispersion method and dyeing method are used for liquid crystal displays for televisions, but they are not widely used.

Pigment dispersion method has become mainstream for the liquid crystal display of general devices such as computers because of the high position of the color filter pixel, the precision of the film thickness, the long life, and the small number of pinholes. In the pigment dispersion method, a color filter is manufactured by spin coating a color photoresist in which an organic pigment or an inorganic pigment is dispersed to form a pattern of a specific pixel. Although the colored layer of the color filter manufactured by the conventional pigment dispersion method had only the red, green, and blue pixel, the black matrix layer which disperse | distributed carbon black etc. is also made using the color photoresist nowadays.

In Japanese Patent Laid-Open No. 11-249322, an alkali compound is used, in addition to inorganic alkali, an alkanolamine as a second component, and a nonionic surfactant in which polyoxyethylene and polyoxypropylene are added to an alkyl (aryl, alkylaryl) group. Therefore, a developing method without developing residue is disclosed, and in Japanese Patent Laid-Open No. 7-120935, a precise pattern can be formed by a method using an alkali compound and a polyoxyethylene derivative. In addition, Japanese Patent Application Laid-Open No. 9-171261 discloses that a precise pattern can be formed by using an alkali solution and a polyoxyethylene derivative using a hydroxide and a carbonate in parallel, and Japanese Patent Laid-Open No. 8-101511 uses a fatty acid alkanolamide. A developer is disclosed in Japanese Patent Application Laid-Open No. 11-305451, and a compound in which ethylene oxide and propylene oxide are added to fatty acid amine. We propose each as developer.

However, in order to improve the speed of the color filter manufacturing process, a developer having low bubbles is required because the production process is changed from a method of dipping in a developer to develop a photoresist and spraying the developer directly on the photoresist. When developing with the conventional composition of the proposed compound, there is a problem in that a large amount of bubbles are generated in the spraying process so that the production speed cannot be increased.

Therefore, the technical problem to be achieved by the present invention is to provide a developer having a high development speed because the amount of bubbles generated in the photoresist developing process using a spray method is small.

In order to solve the above object, the developer for pigment dispersion photoresist according to the present invention is (a) an alkali compound; (b) at least one first interface selected from polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of Formula 1 or polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer of Formula 2 Active agent; And (C ₂ H ₄ O) n (C ₃ H ₆ O) m (C ₂ H ₄ O) n (C ₃ H ₆ O) i (C ₂ H ₄ O) j (C ₃ H ₆ O) i (Wherein n, m, i and j are repeating unit numbers) (c) at least one second surfactant selected from etherified polyoxy ethylene-polyoxy propylene block copolymers having the structure of Formula 3 or Formula 4 below It includes. RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b H RO (C ₃ H ₆ O) _b (C ₂ H ₄ O) _a H

(Wherein R is an alkyl group, an aryl group, or an alkylaryl group, and in the case of an alkyl group, 1-20 carbon atoms, 6-30 carbon atoms in an aryl group, 7-30 carbon atoms in an alkylaryl group, and a is 5- 20 and b is 1-10)

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Wherein polypropylene oxide acts as a lipophilic group and polyethylene oxide acts as a hydrophilic group. In the ethylene oxide-propylene oxide triblock copolymer represented by the above formula, the number of repeating units of ethylene oxide or propylene oxide attached to both sides is the same. In the above formula, the total molecular weight of the first surfactant is preferably 1,000 to 30,000 and the molecular weight of the polypropylene oxide is preferably 950 to 4,000. When used as a developer, the amount of bubble generation occurs as the fraction of polypropylene oxide in the whole molecule increases. The polymer is commercialized under the trade names Pluronic, Poloxamer, etc. from BASF, ICI, and the like. As a specific product name, BASF's ethylene oxide-propylene oxide-ethylene oxide type is L10, L31, L35, F38, L42, L43, L44, L61, L62, L63, L64, P65, F68, L72, P75, F77, L81 , P84, P85, F87, F88, L92, F98, L101, P103, P104, P105, F018, L121, L122, P123, F127, etc.As a propylene oxide-ethylene oxide-propylene oxide type, 10R5, 10R8, 12R3, 17R1, 17R2, 17R4, 17R8, 25R1, 25R2, 25R4, 25R5, 31R1, 31R2, 31R4 and the like. In Chemical Formulas 3 and 4, R is both an alkyl group, an aryl group, an alkylaryl group, and in the case of an alkyl group, It is generally 1 to 20 carbon atoms, 6 to 30 carbon atoms for the aryl group, 7 to 30 carbon atoms for the alkylaryl group, more preferably 6 to 16 carbon atoms for the alkyl group, 12 to 27 carbon atoms for the aryl group In the case of a dog and an alkylaryl group, it is 12-27 carbon atoms. As for ethylene oxide repeating unit a, 5-20 are common, More preferably, it is 7-15, and propylene oxide repeating unit b is 1-10 normally, More preferably, it is about 1-5. If a is less than 5, it is difficult to dissolve in water, but if it is more than 20, the penetration force worsens and the development time is increased. When b is more than 10, it is difficult to dissolve in water.

As the alkali compound, both an inorganic alkali compound and an organic alkali compound can be used, and specifically, an inorganic alkali compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, potassium carbonate and sodium carbonate or ammonia water, monoethanolamine , An organic alkali compound selected from the group consisting of diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine and tetramethylammonium hydroxide can be used. The alkali compound is generally used to adjust the pH to about 9-13 using a mixture of at least one compound mentioned above. More preferably, when the pH is 10 to 12.5 and the pH is 9 or less, developing residues may occur. When the pH is 13 or more, a part or the whole of the pixel may be peeled off.

      Moreover, the density | concentration of the said 1st surfactant is 0.03-0.5 weight%, Preferably it is 0.05-0.3 weight%. If the concentration of the surfactant is less than 0.03% by weight, developing residues are formed. When the concentration of the surfactant is more than 0.5% by weight, bubbles are generated to decrease the developing speed.

In the developer according to the present invention, even when the first surfactant is used alone, development of a sufficiently small color photoresist is possible, but when used in combination with the second surfactant, there is less development residue and the pattern of the pixel is precise. In the developer using the second surfactant in combination, the total concentration of the surfactant is 0.03 to 0.5%, and the ratio of the second surfactant in the total surfactant is 90% or less, more preferably 70% or less. When the ratio of the second surfactant is 90% or more, bubbles are generated to decrease the working speed.

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Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1

As an organic pigment, 40g of pigment red 224 and 177 was used for the color index name in the case of red, respectively. 40 g of acrylic acid / methacrylic acid / 2-hydroxy ethyl methacrylate / benzyl methacrylate copolymer (copolymerization ratio = 10/10/10/70, number average molecular weight 10,000) as an alkali-soluble resin, dipenta as a polyfunctional monomer 20 g of erythol hexaacrylate, 5 g of 2,2-bis (2,4 dichlorophenyl) -4,4,5,5-tetraphenyl-1,2-diimidazole and 4,4, -bis (as photopolymerization initiator) 5 g of diethylamino) benzophenone, 20 g of 2-benzyl-2-dimethylamineno-1- (4-morpholinophenyl) butan-1-one, and 10 g of gamma-methacryloxypropylmethyldimethoxysilane as catalysts 1000 g of a photoresist liquid composition was prepared by mixing with a solvent and ethylene glycol ethyl ether acetate. The pigment concentration was about 44% of the total solids. Next, in order to prevent elution of sodium ions on the surface, the photoresist liquid composition was spun-coated and applied on a soda glass substrate coated with a silicon dioxide film. The coated substrate was baked at about 80 ° C. for 10 minutes to obtain a 2.0 μm film. After baking the board | substrate to room temperature, the ultraviolet-ray containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed by the exposure amount of 10 mJ / cm <^2> using a mercury lamp, using a photomask between substrates. On the other hand, a developer was prepared containing 0.1 g of potassium hydroxide as the alkali compound and 0.1 g of 17R4 (manufactured by BASF Corporation) as the first surfactant and having a pH of 12.0. The exposed substrate was developed by spraying 600 g of the developer, and then washed with distilled water to form a pixel. The development speed was controlled by adjusting the bubble so that it did not overflow, and the sharpness of the phenomenon was observed by observing the pixel with an electron microscope after the pixel was formed.

The development speed is expressed as the speed for developing one color filter, and the smaller the value, the faster the development speed.

Example 2

A developing solution was prepared in the same manner as in Example 1 except that 0.1 g of 10R8 (manufactured by BASF Corporation) was used as the first surfactant.

Example 3

A developer was prepared in the same manner as in Example 1 except that 0.1 g of 31R2 (manufactured by BASF Corporation) was used as the first surfactant.

Example 4

A developer was prepared in the same manner as in Example 1, except that 0.1 g of L31 (manufactured by BASF Corporation) was used as the first surfactant.

Example 5

A developer was prepared in the same manner as in Example 1 except that 0.1 g of L44 (manufactured by BASF Corporation) was used as the first surfactant.

Example 6

A developer was prepared in the same manner as in Example 1 except that 0.1 g of P103 (manufactured by BASF Corporation) was used as the first surfactant.

Example 7

A developer was prepared in the same manner as in Example 1 except that the concentration of 17R4 (manufactured by BASF Corporation), which is the first surfactant used in Example 1, was changed to 0.05 g.

Example 8

A developer was prepared in the same manner as in Example 1, except that the concentration of 17R4 (manufactured by BASF Corporation), which is the first surfactant used in Example 1, was changed to 0.2 g.

Example 9

A developer was prepared in the same manner as in Example 1 except that sodium hydroxide was used as the alkali compound.

Example 10

A developer was prepared in the same manner as in Example 1 except that 0.07 g of 17R4 (manufactured by BASF Corporation) was included as the first surfactant and 0.03 g of NP-E10 (manufactured by Korean Polyol) was included as the second surfactant.

Example 11

A developer was prepared in the same manner as in Example 10, except that 0.04 g of 17R4 (manufactured by BASF Corporation) and 0.06 g of NP-E10 were included as the second surfactant.

Example 12

A developer was prepared in the same manner as in Example 10, except that 0.03 g of NP-E10P2 (manufactured by Korean Polyol) was included as the second surfactant.

Example 13

A developer was prepared in the same manner as in Example 10, except that 0.03 g of OP-E10 (manufactured by Korean Polyol) was included as the second surfactant.

Example 14

 A developer was prepared in the same manner as in Example 10 except that 0.03 g of LA-E7 (manufactured by Korean Polyol) was included as the second surfactant.

Comparative Example 1

A developer was prepared in the same manner as in Example 10, except that the concentration was changed by using the amount of NP-E10, which is the second surfactant, as 0.1 g without using the first surfactant.

Comparative Example 2

A developer was prepared in the same manner as in Example 13, except that the concentration of the OP-E10, which is the second surfactant, was changed to 0.1 g without using the first surfactant.

Comparative Example 3

A developer was prepared in the same manner as in Example 14, except that the concentration was changed by using the amount of LA-E7, which is the second surfactant, in 0.1 g without using the first surfactant.

The results of the composition and evaluation of the developer are shown in Table 1 below.

division Alkali compounds pH First surfactant Secondary surfactant water Developing speed (seconds / long) Pattern sharpness Kinds Kinds Content (g) Kinds Content (g) Example 1 KOH 12.0 17R4 0.1 - - 100 60 4 Example 2 KOH 12.0 10R8 0.1 100 60 4 Example 3 KOH 12.0 31R2 0.1 100 60 5 Example 4 KOH 12.0 L31 0.1 - - 100 65 5 Example 5 KOH 12.0 L44 0.1 - - 100 70 4 Example 6 KOH 12.0 P103 0.1 - - 100 75 4 Example 7 KOH 12.0 17R4 0.05 - - 100 60 4 Example 8 KOH 12.0 17R4 0.2 - - 100 60 4 Example 9 NaOH 12.0 17R4 0.1 - - 100 60 4 Example 10 KOH 12.0 17R4 0.07 NP-E10 0.03 100 90 5 Example 11 KOH 12.0 17R4 0.04 NP-E10 0.06 100 110 5 Example 12 KOH 12.0 17R4 0.07 NP-E10P2 0.03 100 80 5 Example 13 KOH 12.0 17R4 0.07 OP-E10 0.03 100 80 5 Example 14 KOH 12.0 17R4 0.07 LA-E7 0.03 100 80 5 Comparative Example 1 KOH 12.0 NP-E10 0.1 100 200 4 Comparative Example 2 KOH 12.0 OP-E10 0.1 100 180 4 Comparative Example 3 KOH 12.0 LA-E7 0.1 100 250 4

In the above description, 17R4, 10R8, 31R2, L31, L44 and P103 are ethylene oxide-propylene oxide triblock copolymers produced by BASF Corporation, NP-E10 is a product obtained by adding 10 moles of ethylene oxide to nonylphenol, and NP-E10P2. Is a product in which 10 mol of ethylene oxide and 2 mol of propylene oxide are added. On the other hand, OP, LA refers to octylphenol, lauryl alcohol.

The pattern clarity is 5: very good, 4: good, 3: normal, 2: poor, 1: very bad.

As described above, the photoresist developer according to the present invention not only has a high alkali penetration rate and a low development residue in the production of a color filter, but also has excellent pattern clarity. In addition, since the generation of bubbles in the spray developing process is less, the development speed is faster, it is possible to improve the productivity.

Claims (7)

(a) alkali compounds; (b) One type selected from polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of formula (1) or polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer of formula (2) The above first surfactant; And (C ₂ H ₄ O) n (C ₃ H ₆ O) m (C ₂ H ₄ O) n .............. (1) (C ₃ H ₆ O) i (C ₂ H ₄ O) j (C ₃ H ₆ O) i .............. (2) (In the above, n, m, i, j is the number of repeat units) (c) For pigment dispersion photoresists comprising at least one second surfactant selected from etherified polyoxyethylene-polyoxypropylene block copolymers having the structure of formula (3) or formula (4) developer. RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b H ... (3) RO (C ₃ H ₆ O) _b (C ₂ H ₄ O) _a H ... (4) (Wherein R is an alkyl group, an aryl group, or an alkylaryl group, and in the case of an alkyl group, 1-20 carbon atoms, 6-30 carbon atoms in an aryl group, 7-30 carbon atoms in an alkylaryl group, and a is 5- 20 and b is 1-10) The developer of claim 1, wherein the total molecular weight of the first surfactant is 1,000 to 30,000, and the molecular weight of the polypropylene oxide is 950 to 4,000.  The developer according to claim 1, wherein the alkali compound is an inorganic alkali compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, potassium carbonate and sodium carbonate. The organic alkali compound according to claim 1, wherein the alkali compound is selected from the group consisting of ammonia water, monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine and tetramethylammonium hydroxide. A developer for pigment dispersion photoresist, characterized in that. The developer for pigment dispersion photoresist according to claim 1, wherein the concentration of the first surfactant is 0.03 to 0.5% by weight. delete The developer according to claim 1, wherein the total concentration of the surfactant in the developer composition is 0.03 to 0.5% by weight, and the ratio of the second surfactant in the surfactant is 90% or less.