JP2000310861A - Developer composition for photosensitive resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a developer composition capable of forming a precise pattern without causing the swelling, undercutting and peeling of a photoset part or leaving residue on development in an unexposed part and having no problem of environmental disruption and safety by using a liquid composition to which water has a specified solubility at 20 deg.C and water in an amount below the solubility. SOLUTION: The developer composition contains a liquid composition to which water has 3-30 wt.% solubility at 20 deg.C and water in an amount below the solubility. In the case of <3 wt.% solubility, the amount of water which can be added is stuall, the problem of safety is caused, the composition is not throughly removed by washing after development and residue is liable to stick to a pattern. In the case of >30 wt.%, the solvent power of a liquid compound is high and the swelling, undercutting and peeling of a photoset pattern are caused. The liquid composition is one or more compounds of the formula, wherein R1 and R2 are each H, 1-10C alkyl or the like, R3-R6 are each H or 1-3C alkyl and (n) is an integer of 1-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resist developer composition.

[0002]

2. Description of the Related Art Conventionally, in the fields of printed wiring board manufacturing, metal precision processing, and structure formation, etching, plating,
In the step of forming a pattern for the purpose of forming a protective film or the like, as a developing solution used for removing an unexposed portion of the photosensitive resist, an aqueous solution of sodium carbonate,
No. 175372, an alkaline developer such as a developer composition, a chlorine-based organic solvent based developer such as 1,1,1-trichloroethane, toluene, xylene, butyl cellosolve, N-methyl-2-pyrrolidone; 5-2162
No. 42, JP-A-6-19484
7, a developer composition described in JP-A-8-171213
And an organic solvent-based developer using an organic solvent such as the developer composition described in Japanese Patent Application Laid-Open No. H11-163,086.

[0003]

The conventional developing solution for a photosensitive resist has the following problems.

[0004] An alkali-based developer does not contain an alkali-soluble group such as a carboxyl group or has a small content in a photosensitive resist that requires particularly high chemical resistance and heat resistance. There is a problem that the resin cannot be used because the conductive resin cannot be dissolved.

In a chlorine-based organic solvent-based developer, 1,1,1,
Although 1-trichloroethane has excellent developability, it has environmental problems such as ozone layer destruction and groundwater contamination.

[0006] Organic solvent-based developers are flammable and therefore have a risk of ignition explosion. In addition, it has a strong dissolving power, and has problems such as swelling, undercut, and peeling of the photocured pattern, and particularly has a problem in forming a precise pattern. In addition, there is a problem that a developing solution containing a dissolved substance cannot be sufficiently removed at the time of washing with water and a residue remains.

An object of the present invention is to solve these problems and to form a precise pattern without generating swelling, undercut, peeling, and development residue in an unexposed portion of a photocured portion, thereby destructing the environment and reducing safety. An object of the present invention is to provide a developer having no problem.

[0008]

The object of the present invention is to provide a developer composition comprising a liquid composition having a water solubility of 3 to 30% by weight at 20 degrees Celsius with respect to the liquid composition and water having a solubility lower than the solubility. Can be solved.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The solubility of water in a liquid composition is a concentration at which the amount of water dissolved in a liquid composition becomes saturated and water is no longer dissolved. Although the solubility varies depending on the temperature, in the present invention, the temperature that defines the solubility of water in the liquid composition is set to 20 degrees Celsius because the temperature generally used for comparing the solubility of the composition is 20 degrees Celsius.
It is not intended to limit the production temperature, use temperature, etc. of the present developer composition.

[0010] The solubility of water at 20 ° C in the liquid composition used in the developer composition of the present invention is 3 to 30% by weight, preferably 5 to 25% by weight, particularly preferably 10 to 20% by weight. . If the solubility of water is less than 3 weight, the amount of water that can be added is small, which is a safety problem. In addition, there is a problem that the residue cannot be sufficiently removed by washing with water after development and the residue adheres to the pattern. If the solubility of water exceeds 30% by weight, the dissolving power of the liquid compound is so strong that problems such as swelling, undercut and peeling of the photocured pattern occur. In addition, since the liquid composition itself has a strong water-absorbing power, there is a problem in that the water penetrates into a photo-cured pattern at the time of washing, causing swelling, peeling, and undercut. That is, by controlling the solubility of water in the developer composition of the present invention, swelling, peeling, undercut, and the like of residues and patterns due to washing with water can be suppressed.

The developer composition of the present invention is used by mixing water. The mixing of water has a safety advantage in preventing the risk of flammable explosions. The water content is below its solubility. When water exceeding the solubility is added, the liquid composition and water are separated from each other, so that a developer composition having a uniform composition is not obtained, and the developability is not stable.

The developer composition of the present invention can be purified by distillation and reused. By distilling and purifying and reusing, it is unnecessary to dispose of the developer composition after development, which is environmentally convenient. Existing distillation methods such as atmospheric distillation and vacuum distillation are used for the distillation.

The solubility of water at 20 degrees Celsius is 3 to 3
Examples of the liquid composition having 0% by weight include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 2-methyl-1-butanol, ethylene glycol monohexyl ether, ethylene glycol monobenzyl ether, Cyclohexanol, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, -Methyl-3-methoxybutyl acetate, butyl lactate and the like. These compounds are used alone or in a mixture at an arbitrary ratio. Further, a liquid compound having a solubility of less than 3% by weight or a compound having a solubility of more than 30% by weight may be mixed and used so as to have a solubility of 3 to 30% by weight.

The developer composition of the present invention is preferably one or more compounds represented by the general formula (1). R1 and R2 in (1) are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a phenyl group, an alkylphenyl group, an acyl group or a phenacyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Group, phenyl group, or acetyl group. Alkyl groups having more than 10 carbon atoms cannot be used due to high hydrophobicity and low solubility of the photosensitive resist. R3, R4, R5 and R6 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. When the number of carbon atoms exceeds 3, the solubility of the photosensitive resist becomes small and it cannot be used. n is an integer of 1 to 10, preferably 1 to 4. When n exceeds 10, the viscosity of the liquid composition increases, and the solubility of the photosensitive resist decreases.

Specific examples of the compound represented by the general formula (1) include ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, diethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and propylene glycol. Monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol diacetate, propylene glycol diacetate, etc. can give. Preferred are propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, ethylene glycol diacetate, and propylene glycol diacetate.

The developer composition for a photosensitive resist of the present invention can be used for commercially available photosensitive resists. As a photosensitive resist, for example, Nopco Cure F-1 manufactured by San Nopco, Inc.
040m, Nopcocure F702, Nopcocure F-1
520, and liquid resists such as Nopcocure L-1020 and Nopcocure L-7020.

As the method using the developing solution of the present invention, an existing method such as a spray method, an ultrasonic method, and an immersion rocking method can be used. The development temperature is not particularly limited, but is generally between room temperature and 50 degrees Celsius. After the development, the next step is performed after washing with water.

[0018]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Developer compositions were prepared at the compounding ratios shown in Table 1, and the developability was evaluated. Nopcocure F-, a dry film type photosensitive resist manufactured by San Nopco Co., Ltd.
Laminate 1040 on a copper clad laminate, line width / line interval = 5
The one exposed through a 0/50 μm photomask was used. The test pieces were developed using the developer compositions shown in Table 1 at a temperature of 30 ° C. and a pressure of 3 kg / cm ^{2 by} a spray method. After washing with water spray, drying in an oven at 80 ° C. for 30 minutes, observation of the pattern of the cured portion, undercut, and development residue of the unexposed portion were performed by observing with a microscope of 50 ×.

Table 1 shows the evaluation results of the developability, the solubility of water in the liquid composition, and the evaluation results of the flammability of the developer composition. The flammability was evaluated in accordance with the Fire Safety Law Dangerous Goods Evaluation Standards. Developability was determined based on the following criteria. ：: No peeling of pattern in cured part, no undercut, no development residue in unexposed part. Δ: Development residue is present. X: There are peeling of the pattern of the cured portion and undercut. The flammability was determined based on the following criteria. ○: Not flammable ×: Flammable

[0020]

[Table 1]

The developer composition shown in Example 1 was distilled at 120 ° C. under a reduced pressure of 5 mmHg after the evaluation of developability, and the recovery was 9%.
Purified product was obtained at 0%. When the developability was re-evaluated after adjusting the water content to a predetermined value of 10% by weight, the developability was equivalent to that before distillation.

[0022]

The developing solution composition of the present invention is a developing solution capable of forming a precise fine line pattern without swelling, undercut, peeling or developing residue of a photo-cured portion of the photosensitive resist and undeveloped portion. . In addition, the present invention can provide a developer having no inflammable explosive property and a developer having no ozone layer destruction or groundwater contamination, so that there is no safety or environmental problem. Therefore, the developer composition of the present invention is suitable as a developing solution for a plating resist, an etching resist, a solder resist, an interlayer insulating agent, and the like used in the production of a printed wiring board, a metal precision processing resist, and a structure forming resist. .

Claims (3)

[Claims] 1. A developer composition comprising: a liquid composition having a water solubility of 3 to 30% by weight at 20 ° C. with respect to the liquid composition; and water having a solubility equal to or lower than the solubility. 2. The developer composition according to claim 1, wherein the liquid composition is at least one compound represented by the general formula (1). Embedded image (However, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a phenyl group, an alkylphenyl group, an acyl group, a phenacyl group, R ³ , R ⁴ , R
⁵ and R ⁶ are hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 10. ) 3. A developing method, wherein the developer composition according to claim 1 or 2 is purified, distilled and reused after development.