JP2006220961A - High concentration developer undiluted solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable developer undiluted solution containing a basic substance and a surfactant in a high concentration and easily prepared without adversely affecting developing performance. <P>SOLUTION: The undiluted solution is an alkali developer stock solution for a radiation sensitive composition, the solution comprising an alkali compound, a surfactant, and a solubilizing agent in water. The solubilizing agent comprises a compound expressed by formula of R-(COOH)<SB>n</SB>, wherein R represents a 1-30C straight or branched and saturated or unsaturated aliphatic group, a 3-30C alicyclic group or a 6-30C aromatic group, and R can be substituted or not substituted and can contain one or more hetero atoms in the carbon chain of R, and n is a number of 1 to 6. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

    The present invention is for developing a resist applied on a substrate when manufacturing color filters, integrated circuits, printed circuit boards, and flat panel displays for electro-optical display devices of precision electronic devices such as liquid crystal displays, CMOS, and CCD. The present invention relates to an alkaline developer composition. Specifically, the present invention relates to a composition for highly concentrating an alkali developer used for developing an alkali-soluble photosensitive film.

    Conventionally, in the fields of liquid crystal displays, color filters for electro-optical display devices of precision electronic equipment such as CMOS and CCD, integrated circuits, printed circuit boards, flat panel displays, etc., alkali-soluble photosensitive films are developed with alkali to form images. There is a way to do. Such an alkali-soluble photosensitive film is developed by a method such as immersion development, rocking development, spray development, or paddle development. An alkaline developer is used for this development. Conventionally, as such an alkaline developer, generally an inorganic alkali compound (carbonate, silicate, phosphate, caustic soda, caustic potash, etc.) or an organic alkali compound (TMAH etc.) is optionally used with a surfactant ( A developer containing other components such as nonionic and anionic) is used. Developers that are used in large quantities are expensive to transport and complicated in order management, and therefore high concentration of the developer has been required.

    However, when the concentration of the developer is simply increased by increasing the alkali concentration of the developer stock solution, there is a problem that the concentration of the alkaline substance becomes very high and the surfactant becomes insoluble. Thus, it becomes difficult for the developing solution which became difficult to melt | dissolve to isolate | separate a surfactant and aqueous alkali solution easily and to exhibit a developing solution capability. In order to solve such problems and concentrate the developer, the use of a solubilizing agent is considered as one of the solution means.

    However, many of the solubilizers have poor compatibility with the resist, and there is a problem that the performance of the developer is remarkably lowered by adding them. For example, ground contamination such as pigment residue, scum such as resist insoluble, uneven development such as film residue, over-development such as pattern peeling, etc., resulting in problems such as poor pattern accuracy and adhesion, taper shape, etc. obtain. Further, there is a problem that the developer becomes non-uniform during transportation (separation or turbidity occurs) as the developer temperature increases during transportation, which also hinders the use of the highly concentrated solution.

    For this reason, in the prior art, various solubilizers have been studied in order to highly concentrate the developer stock solution, and attempts have been made to solve the problem by using specific types of solubilizers.

    For example, Japanese Patent Laid-Open No. 6-282080 (Patent Document 1) discloses an alkali compound, dipolar ionic organic compound, anionic surfactant, and cationic interface in which a 0.1 wt% aqueous solution exhibits a pH of 10 or more. An alkaline developer for a radiation-sensitive composition in which a surfactant selected from the group consisting of an active agent and a nonionic surfactant is dissolved in water, and this developer as a high-concentration alkaline developer It is described. However, in the concentrate for 5-fold dilution, the concentration of the alkali compound is at most 0.5% by weight, and the surfactant concentration is at most 1%.

    In JP-A-7-319170 (Patent Document 2), a metal ion-free organic base and a weight average molecular weight of 100 to 1000 are selected from among a polyethylene oxide compound, a polypropylene oxide compound and an ethylene oxide / propylene oxide compound. A resist developer stock solution containing at least one selected from the above is disclosed. A developer stock solution containing a base concentration (TMAH) of 20.1% by weight is described, but the surfactant concentration is as low as 2% by weight.

Japanese Patent Application Laid-Open No. 11-288103 (Patent Document 3) also discloses a developer containing a weakly basic substance and a nonionic surfactant and a concentrated stock solution thereof. However, the basic substance content is only 5% by weight, and the surfactant concentration is about 7% by weight. In addition, as a nonionic surfactant, three types of nonionic surfactants must be used in combination with respect to the HLB value, and the blending ratio thereof must be strictly controlled within the specified range. It is complicated.
JP-A-6-282080 JP 7-319170 A JP 11-288103 A

    Accordingly, one of the problems of the present invention is that not only does the development performance not be affected, but also contains a basic substance and a surfactant at a higher concentration than that achieved in the prior art, and a simple formulation. It is to provide a stable developer stock solution that can be prepared by The term “stable” as used herein means, for example, the property that the developer stock solution does not cause separation or turbidity due to an increase in ambient temperature during storage and transportation, and maintains its uniform state over a long period of time. Is done.

  The present inventors have conducted intensive studies in view of the above problems, and have found that the above problems can be solved by using an organic compound containing a certain carboxyl group as a solubilizer.

Therefore, the present invention provides an alkaline developer stock solution for a radiation-sensitive composition comprising an alkaline compound, a surfactant and a solubilizer in water, wherein the solubilizer has the following formula:
R- (COOH) _n
[Wherein, R represents a linear or branched, saturated or unsaturated aliphatic group having 1 to 30 carbon atoms, an alicyclic group having 3 to 30 carbon atoms, or 6 to 30 carbon atoms. Wherein R may be unsubstituted or substituted, the carbon chain of R may contain one or more heteroatoms, and n Is a number from 1 to 6]
The developer stock solution is characterized in that it comprises a compound represented by formula (1) or a salt thereof.

  Furthermore, the present invention also provides a developer that can be directly used for developing a radiation-sensitive composition obtained by diluting such a developer stock solution with water.

  Furthermore, the present invention also provides a method of using the developer for developing a resist in manufacturing a color filter for an electro-optical display device, an integrated circuit, a printed circuit board, or a flat panel display.

The solubilizer used in the present invention is a compound represented by the formula R- (COOH) _n or a salt thereof. Wherein R is a linear or branched, saturated or unsaturated aliphatic group having 1-30 carbon atoms, preferably 3-20, each optionally substituted with one or more substituents. Group, an alicyclic group having 3 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aromatic group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, wherein the substituent is a carbon atom 1 to 20, preferably 1 to 10 linear or branched saturated or unsaturated aliphatic group, 4 to 20 carbon atoms, preferably 4 to 10 alicyclic group, 6 to 20 carbon atoms Preferably selected from 6 to 10 aromatic groups, hydroxy groups, amino groups and ether groups, and in R is selected from heteroatoms, especially nitrogen, oxygen, phosphorus, sulfur and silicon One or more atoms may be included. n is a number from 1 to 6, preferably from 1 to 3, in particular 1 or 2. Examples of the salt of the above compound include metal salts such as alkali metal salts (especially sodium and potassium salts) and alkaline earth metal salts (particularly magnesium and calcium salts), and ammonium salts. In this case, the term “ammonium salt” includes not only NH ₄ salt but also substituted ammonium salt substituted with 1 to 3 lower alkyl groups such as methyl group or ethyl group, or tetramethyl or tetraethylammonium salt. Tetraammonium salts and the like are also included. In applications where the presence of metal ions is avoided as much as possible, such as in the manufacture of integrated circuits, the above compounds are preferably used in the free acid form or in the ammonium salt form.

  Preferred compounds represented by the above formula include, for example, saturated aliphatic mono- or polycarboxylic acids or unsaturated aliphatic mono- or polycarboxylic acids each having 1 to 30 carbon atoms, and the number of carbon atoms. Examples thereof include 6 to 20 aromatic carboxylic acids, further amino acids, and salts thereof. Particularly preferred are saturated aliphatic mono- or dicarboxylic acids or unsaturated aliphatic mono- having 1 to 20 carbon atoms or Dicarboxylic acids and their salts.

    Specific examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, Saturated aliphatic monocarboxylic acids such as lactic acid, oxalic acid, malonic acid, succinic acid, sebacic acid, citric acid and other saturated aliphatic polycarboxylic acids, methacrylic acid, sorbic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid , Unsaturated aliphatic monocarboxylic acids such as arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid, unsaturated aliphatic polycarboxylic acids such as fumaric acid, maleic acid and aconitic acid, aromatics such as benzoic acid, phthalic acid and terephthalic acid Carboxylic acids as well as amino acids are mentioned. These can be used alone or in combination of two or more.

  Among them, caprylic acid, isobutyric acid, sebacic acid or oleic acid or a mixture of two or more thereof and / or a salt thereof are used.

The solubilizer is usually used in the developer stock solution in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the developer stock solution. If it is less than 0.1% by weight, the solubilizing effect is not sufficiently exhibited. On the other hand, if it exceeds 30% by weight, there is a risk of developing problems.
As the inorganic alkali compound used in the present invention, any one commonly used in the art can be used, and there is no particular limitation. Specific examples include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, Alkali metal phosphates such as ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, alkali metal silicates such as lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, Examples thereof include alkali metal carbonates such as potassium carbonate, alkali metal borates such as lithium borate, sodium borate and potassium borate, and ammonia.

    Similarly, the organic alkali compound is not particularly limited, and any conventional organic alkali compound can be used. Specific examples include tetramethylammonium hydroxide.

    It is also possible to use a combination of two or more inorganic or organic alkali compounds.

    Of these, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, disodium hydrogen phosphate and dipotassium hydrogen phosphate are preferably used as the inorganic alkali compound, and tetramethylammonium hydroxide is used as the organic alkali compound. Is done.

    The alkali compound is generally used in the developer stock solution in an amount of 0.005 to 30% by weight, preferably 3 to 20% by weight, particularly preferably 8 to 20% by weight, based on the total weight of the developer stock solution. The In particular, when high concentration is desired, the developer stock solution of the present invention, as demonstrated in the Examples, can have an adverse effect on the developing performance, that is, the alkaline compound successfully even in an amount of 10% by weight or more. And without losing the liquid stability of the stock solution. If it is less than 0.005% by weight, the dilution efficiency is inferior. On the other hand, if it exceeds 30% by weight, inconveniences such as a decrease in temperature stability may occur.

  In the present invention, in particular, a nonionic surfactant or an anionic surfactant or any combination thereof is used as the surfactant.

    As the nonionic surfactant, any of those conventionally used in the art can be used, and there is no particular limitation, but specific examples include polyoxyethylene (propylene) alkyl ether, polyoxy Examples include ethylene (propylene) alkylphenyl ether, polyoxyethylene (propylene) alkyl naphthyl ether, sorbitan fatty acid ester, polyoxyethylene (propylene) fatty acid acid ester, polyoxyethylene (propylene) alkylamine, alkyl alkanolamide and the like. These may be used singly or in combination of two or more.

  Similarly, the anionic surfactant is not particularly limited. Specifically, for example, alkyl sulfates such as sodium lauryl alcohol sulfate, sodium lauryl sulfate, and ammonium lauryl sulfate, and alkyl such as sodium dodecylbenzenesulfonate. Examples include aryl sulfonates and higher alcohol sulfates such as sodium oleyl alcohol sulfate, but are not limited thereto, and these may be used alone or in combination of two or more.

  Among these, Preferably, polyoxyethylene (propylene) alkyl ether and polyoxyethylene (propylene) alkylphenyl ether are used as nonionic surfactants, and sodium lauryl alcohol sulfate and lauryl are used as anionic surfactants. Sodium sulfate, naphthalene sulfonate and alkyl naphthalene sulfonate are used.

  The surfactant is generally used in the developer stock solution in an amount of 0.001 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 8 to 30% by weight, based on the total weight of the developer stock solution. Is done. In particular, where high concentration is desired, the developer stock solution of the present invention can successfully contain a surfactant, especially in an amount of 10% by weight or more, as demonstrated in the examples. If the amount is less than 0.001% by weight, the effect of addition is difficult to be exhibited.

    In one particularly advantageous embodiment of the present invention, the developer stock solution of the present invention may comprise an alkali compound and a surfactant in a total amount of more than 20% by weight, particularly more than 25% by weight.

  The developer stock solution or developer of the present invention is an additive component conventionally used in a resist developer, for example, various known surfactants, lubricants, stabilizers, as long as the object of the present invention is not impaired. A dissolution aid or the like may be added as appropriate.

  The developer stock solution of the present invention does not require any special means, and can be adjusted, for example, by adding the components together in water or in any order and mixing them using a suitable mixer or the like. Can do. In one of the preferred embodiments, first, the alkali compound and the solubilizer are poured into water together or in an arbitrary order, dissolved by stirring, then the stirring is stopped and left for a while to enter the solution. Remove dispersed air. By doing in this way, foaming when a surfactant is added later can be suppressed. In addition, since the temperature of the solution may increase due to the heat generated during the dissolution of the alkali compound and the solubilizing agent, when using a nonionic surfactant, the temperature of the solution is lowered after cooling. The temperature should be lower than the cloud point of the nonionic surfactant. Finally, a surfactant can be added and gently stirred with attention to foaming to obtain a uniform solution.

  The developer stock solution of the present invention can be used usually at a magnification of 5 to 200 times and usually diluted with water at the time of developing the resist. The pH value of the diluted developer is usually The range is 9 to 14. If necessary, the dilution water may contain an organic solvent.

  The developer of the present invention obtained by diluting the developer stock solution can be applied to a pattern forming resist comprising both a negative type and a positive type photosensitive resin composition. The photosensitive resin composition that is a target of the developer of the present invention is not particularly limited, and is generally used for the production of color filters, integrated circuits, and the like as long as it can be developed using an aqueous alkaline solution. It can be anything. This photosensitive composition is usually composed of a binder resin, a photosensitive compound and a solvent, and an organic or inorganic pigment is blended as needed. As the binder resin, for example, a novolak resin, an acrylic resin, a styrene resin, etc. are used, the photosensitive compound is a photopolymerization initiator, a photocrosslinking agent, etc., and the solvent is a ketone, cellosolve, or alcohol Etc. are used.

  There are no particular restrictions on the usage and conditions of the developer of the present invention. For example, any known method such as immersion development, rocking development, shower / spray development, paddle development, etc. Can be used for processing.

Action

    By adding the solubilizer defined in the present invention to the developer stock solution, the surfactant and alkali compound content can be significantly increased over the prior art, and such highly concentrated developer stock solution is: Under normal storage and transport temperature conditions (for example, 0 to 35 ° C. or higher), no separation phenomenon such as clouding due to nonionic surfactants and salting out of anionic surfactants occurs. .

    Further, the developer stock solution of the present invention maintains good solution stability in the state of the stock solution, but exhibits good development performance when diluted and used for development processing, and develops uneven development and pattern peeling. There will be no inconvenience. These characteristics are directly connected to the reduction of user purchases, transportation costs, and the number of orders, which is a huge advantage.

    In addition, in the present invention, the above effect can be achieved by simply adding a solubilizer defined in the present invention to a developer stock solution having a usual composition, and the preparation thereof is very simple. is there. This is also one of the great advantages of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these examples.

    The performance evaluation of the developers in the examples and comparative examples was performed by the following method.

    A color dispersion pigment dispersion resist was spin-coated on a non-alkali glass substrate (100 mm × 100 mm) for liquid crystal using a spin coater (manufactured by Actes, manual spinner ASC-4000) at 600 rpm for 20 seconds.

    Then, it prebaked at 80 degreeC for 2 minutes on a hot plate (the Neo hot plate HI-1000 made from Inoue Seieido), and obtained the dry coating film.

    Further, a 100 μm straight pattern for evaluation was formed using a high-pressure mercury lamp (manufactured by Mikasa, mask aligner MA-20) through a resolution mask for pattern evaluation. The exposure amount at this time was 150 mJ.

    Next, 4000 ml of a developer diluted at a predetermined dilution ratio for Examples 1 to 4 in Table 1 was prepared.

Using the developer adjusted at a predetermined dilution ratio as described above, the substrate having the dried coating film obtained as described above was spray-developed (1.5 kg / kg) with a developing device (ADE-3000S, manufactured by Actes). cm) for 50 seconds, followed by spray water washing (1.5 kg / cm) in the same apparatus for 50 seconds. Next, it was dried with a nitrogen air gun.
Physical Properties Evaluation Test of Stock Solution 500 ml of an alkaline developer stock solution composed of each component as shown in Tables 1 and 2 was prepared as follows. A three-one motor FBL600M equipped with a turbine type as a stirring blade was used as a mixer. First, an alkali compound was added to water at room temperature and stirred for 5 minutes to dissolve. Next, in Examples 1 to 4 of the present invention, a solubilizer was added and dissolved by stirring for 5 minutes. Thereafter, the stirring was stopped, and the generated heat at which the alkali compound (and solubilizer) was dissolved was cooled to 30 ° C. or lower in a cold water bath at about 10 ° C. Finally, a surfactant was added and gently stirred to obtain a uniform solution. The developer stock solution thus obtained was allowed to stand at 25 ° C. and 35 ° C. overnight, and then the physical properties (dissolved state) of the stock solution were confirmed.
Development performance evaluation test The adhesion of the pattern was confirmed with an optical microscope.
2. The pattern accuracy was measured with a video microscope.
3. Surface observation with a scanning electron microscope (manufactured by Hitachi, S-3000N) and taper shape were confirmed.

    As is clear from the above results, it was demonstrated from the comparison with the blank test (Comparative Examples 1 to 4) that the solubilizer used according to the present invention greatly contributed to the stability of the system. That is, the developer stock solutions (Examples 1 to 4) of the present invention contain alkali compounds and surfactants at a high concentration exceeding 20% by weight in total, even under conditions of 25 ° C. and 35 ° C. No separation phenomenon (cloud point separation or salting out separation) occurred. In addition, when used for the development treatment of the radiation-sensitive composition, there were no inconveniences such as uneven development and pattern peeling, and good development results were obtained.

Claims (13)

An alkaline developer stock solution for a radiation-sensitive composition comprising an alkali compound, a surfactant and a solubilizer in water, wherein the solubilizer has the following formula
R- (COOH) _n
[Wherein, R represents a linear or branched, saturated or unsaturated aliphatic group having 1 to 30 carbon atoms, an alicyclic group having 3 to 30 carbon atoms, or 6 to 30 carbon atoms. Wherein R may be unsubstituted or substituted, the carbon chain of R may contain one or more heteroatoms, and n Is a number from 1 to 6]
The developer stock solution comprising the compound represented by the formula (1) or a salt thereof. The solubilizer is a saturated aliphatic mono- or polycarboxylic acid or unsaturated aliphatic mono- or polycarboxylic acid having 1 to 30 carbon atoms, an aromatic carboxylic acid having 6 to 20 carbon atoms, an amino acid, And a developer stock solution according to claim 1, which comprises one or more compounds selected from the group consisting of these salts. The solubilizer is one or two selected from the group consisting of saturated aliphatic mono- or dicarboxylic acids or unsaturated aliphatic mono- or dicarboxylic acids each having 1 to 20 carbon atoms, and salts thereof. The developer stock solution according to claim 1, comprising the above compound. 2. The developer stock solution according to claim 1, wherein the solubilizer comprises one or more selected from the group consisting of caprylic acid, isobutyric acid, sebacic acid, oleic acid, and salts thereof. The developer stock solution according to any one of claims 1 to 4, comprising a solubilizer in an amount of 0.1 to 30% by weight, based on the total weight of the developer stock solution. The developer stock solution according to any one of claims 1 to 5, wherein the surfactant is a nonionic surfactant. The developer stock solution according to claim 1, wherein the surfactant is a combination of a nonionic surfactant and an anionic surfactant. 8. The developer stock solution according to claim 1, comprising an alkali compound in an amount of 0.005 to 30% by weight based on the total weight of the developer stock solution. 9. The developer stock solution of claim 8, comprising an alkali compound in an amount of 8 to 20% by weight, based on the total polymerization of the developer stock solution. The developer stock solution according to claim 1, comprising a surfactant in an amount of 0.001 to 40% by weight, based on the total weight of the developer stock solution. 11. The developer stock solution of claim 10, comprising a surfactant in an amount of 8 to 30% by weight, based on the total weight of the developer stock solution. A developer prepared by diluting the developer stock solution of any one of claims 1 to 11 with water and having a pH value of 9 to 14. A method of using the developer according to claim 12 for developing a resist when producing a color filter for an electro-optical display device, an integrated circuit, a printed circuit board or a flat panel display.