JPH01134356A - Resist developer - Google Patents

Abstract

PURPOSE:To improve the development of a resist by incorporating dichloro difluoroethane in the title developer. CONSTITUTION:The resist developer contains the dichlorodifluoroethane A as an effective component. The developer is preferably incorporated, as required, with one or more kinds of components selected from the group comprising hydrocarbons (such as n-heptane), alcohols (such as ethanol), ketones (such as acetone), chlorinated hydrocarbons (such as trichloroethane) and esters (such as methyl acetate) in addition to the component A. When the component A is used for the resist developer, the resist can be satisfactorily developed, even in case of using reduced amount of the trichloroethane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resist developer used for developing resist during the manufacture of printed circuit boards and semiconductors.

[Prior Art] When creating printed circuit boards or semiconductor circuits, there is a process of applying a resist, exposing it to light, developing the resist, and then etching it. ,1,1. -1-Chlorine-based resist developers such as ethane are used.

[Problems to be Solved by the Invention] The present invention proposes a new resist developer to replace the chlorine-based resist developer in order to reduce the amount of chlorine-based resist developer used, since the conventionally used chlorine-based resist developer is undesirable in terms of groundwater contamination. The purpose is to provide a drug for

[Means for solving the problems] The present invention has been made to achieve the above-mentioned objects,
A resist developer containing dichlorodifluoroethane as an active ingredient is provided.

Dichlorodifluoroethane, which is an active ingredient of the resist developer of the present invention, is an excellent solvent that is nonflammable and capable of good development. Dichlorodifluoroethane includes 1,2-dichloro-1,2-difluoroethane (hereinafter referred to as R132) and 1,1-dichloro-2,2-difluoroethane (hereinafter referred to as R132a).

1,2-dichloro-1,1-difluoroethane (hereinafter referred to as R
132b) and 1,1-dichloro-1,2-difluoroethane (hereinafter referred to as R132c), and these can be used alone or as a mixture of two or more of these.

The resist developer of the present invention can contain various other components depending on various purposes. For example, for better development, hydrocarbons, alcohols,
At least one kind selected from organic solvents such as ketones, chlorinated hydrocarbons, and esters can be contained. The content of these organic solvents in the resist developer is 0 to 50% by weight, preferably 10 to 40% by weight, and more preferably 20 to 30% by weight.

When the mixture of dichlorodifluoroethane and the organic solvent has an azeotropic composition, it is preferred to use the azeotropic composition.

The hydrocarbons are preferably linear or cyclic saturated or unsaturated hydrocarbons having 1 to 15 carbon atoms, such as n-pentane, isopentane, n-hexane, isohexane, 2-methylpentane, 2,2-dimethylbutane, 2.3-dimethylbutane, n-hebutane, isohebutane, 3-methylhexane, 2.4-dimethylpentane, n-octane, 2-
Methylhebutane, 3-methylhebutane, 4-methylhebutane, 2.2-dimethylhexane, 2.5-dimethylhexane, 3.3-dimethylhexane, 2-methyl-3-
Ethylpentane, 3-methyl-3-ethylpentane, 2
．． 3.3-trimethylpentane, 2.3.4-trimethylpentane, 2,2.3-trimethylpentane, isooctane, nonane, 2.2.5-trimethylhexane.

Decane, dodencane, 1-pentene, 2-pentene, 1
-hexene, 1-octene, 1-nonene, 1-decene,
It is selected from cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, tetralin, amylene, amylnaphthalene, and the like. More preferably n-
These include pentane, n-hexane, n-hebutane, and the like.

The alcohols are preferably linear or cyclic saturated or unsaturated alcohols having 1 to 17 carbon atoms, such as methanol, ethanol, n=propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, 5ec-amyl alcohol, l-ethyl-1-propatol, 2-methyl-1-butanol, isopendel alcohol, terL
-pendel alcohol, 3-methyl-2-butanol,
Neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptatool, 2
- heptatool, 3-heptatool, 1-octanol, 2-octanol, 2-ethyl-1-hexanol,
I-nonanol, 3.5.5-trimethyl-1-hexanol, 1-decanol,! -Undecanol, l-
Dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-
Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, a-terpineol, avinitinol, 2,5-dimethyl-4-heptatool, trimethylnonyl alcohol, tetradecyl alcohol, heptadecyl It is selected from alcohol, etc. More preferred are methanol, ethanol, isopropyl alcohol and the like.

Ketones include R-Co-R', R-CO,R
-CO-R' -r-CIIal C-R'', R-CO-R'', R-CO-R'' (where R, R', R'' are saturated or unsaturated carbon atoms having 1 to 9 carbon atoms) Acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl-0-butyl ketone, methyl butyl ketone, 2-heptanone, 4-
Heptanone, diisobutyl ketone 5 acetonylacetone, mesityl oxide, holone, methyl-n-amyl ketone, ethyl butyl ketone, methylhexyl ketone, cyclohexanone, butylcyclohexanone, isophorone,
It is selected from 2,4-bentanedione, diacetone alcohol, acetophenone, fenchen, and the like.

More preferred are acetone, methyl ethyl ketone and the like.

The chlorinated hydrocarbons are preferably saturated or unsaturated chlorinated hydrocarbons having 1 to 2 carbon atoms, such as methylene chloride, carbon tetrachloride, 1.1-dichloroethane, 1.2-dichloroethane, 1.1. I-trichloroethane, 1,1.2
-Trichloroethane, 1,1,1.2-tetrachloroethane, 1,1,2.2-tetrachloroethane, pentachloroethane, 1.1-dichloroethylene, 1.2-dichloroethylene, trichlorethylene , tetrachlorethylene, etc. More preferred are methylene chloride, 1,1,1-trichloroethane, trichlorethylene, tetrachlorethylene and the like.

As the esters, those represented by the following general formula are preferable: R, -COD-R,, R, -C-
R, -COO-R,.

■ OR.

C old ■4 (Here, R1, R2, R3, R,, R,, R, is 11 or old 1 or a hydrocarbon group having 1 to 19 carbon atoms and having a saturated or unsaturated bond.) Specifically, , methyl formate, ethyl formate, biruformate,
Butyl formate, isobutyl formate, pentyl formate, butyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, 5ec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, M 5ec-hexyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, 2 -Hydroxy-
Ethyl 2-methylpropionate, butyl stearate,
Pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl hexanate, ethyl abietate, benzyl abietate, bis-2-ethylhexyl adipate, γ-butyrolact, Diethyl oxalate, dibutyl oxalate, dibentyl oxalate, gedyl malonate, dimethyl maleate, gedyl maleate, dibutyl maleate, dibutyl tartrate, tribudyl citrate, dibutyl sebacate, bis-2-ethylhexyl sebacate,
Some are selected from dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis-2-ethylhexyl phthalate, dioctyl phthalate, and the like. More preferred are methyl acetate, ethyl acetate and the like.

The resist that can be developed according to the present invention is not limited in any way, and may include positive or negative light exposure resists, deep ultraviolet exposure resists, and X-ray or electron beam resists. Materials for resists for light exposure include quinone diazide based on phenol and cresol novolac resins, cyclized rubber based on cis-1,4-polyisoprene, and polycinnamic acid. Resists include polymethyl methacrylate, polymethyl isopropenyl ketone, etc.; electron beam and Coalescence and the like are known, but the resist developer of the present invention is effective for both.

The resist developing method is not limited in any way, and a conventional spray method, dipping and stirring, shaking, applying ultrasonic waves, etc. can be employed.

[Examples] Examples 1 to 9 A resist development test was conducted using the resist developers shown in Table 1 below. Photoresist film (Lam1n
A printed circuit board (copper-clad laminate) laminated with a printed circuit board (manufactured by Dynachem) was exposed to a certain circuit pattern, developed with a resist developer, and observed under a microscope to see if the circuit pattern was properly formed. The results are shown in Table 1.

Table 1 () shows the mixing ratio [total width %] O: Good development Δ: Slightly poor ×: Poor [Effects of the invention] As is clear from the examples, the resist developer of the present invention can It has an excellent developing effect.

Further, compared to conventional chlorine-based developers, it is advantageous in that it has less adverse effect on Plus Deck, etc. used in printed wiring boards.

Claims (2)

[Claims] (1) A resist developer containing dichlorodifluoroethane as an active ingredient. (2) Resist development according to claim 1, wherein the resist developer contains at least one selected from hydrocarbons, alcohols, ketones, chlorinated hydrocarbons, or esters. agent.