JPH02222469A - Resist remover - Google Patents

Abstract

PURPOSE:To provide the title remover excellent in resist-removing effect, having no adverse effect on plastics, etc., to be used in the production of printed circuit boards and semiconductors. containing as active component a specific unsaturated chlorofluorohydrocarbon. CONSTITUTION:The objective remover containing, as active component. a 3C- unsaturated chlorofluorohydrocarbon (pref. 1-chloro-2-fluoropropene, 2,3- dichloro-3,3-difluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3- trifluoropropene,-1,3-dichloro-1,3,3-trifluoropropene, 1,3-dichloro-2,3,3- trifluoropropene, 3,3-dichloro-1,1,3-trifluoropropene or 3,3-dichloro-2,3- difluoropropene) and furthermore, pref. containing hydrocarbon(s), alcohol(s), ketone(s), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resist stripping agent used in the manufacture of printed circuit boards and semiconductors.

[Prior Art] When producing a printed circuit board or a semiconductor circuit, there is a final step of removing the resist after etching. Conventionally, dichloromethane, tetrachloroethylene, 0-
Chlorinated solvents such as dichlorobenzene and phenol are used.

[Problems to be Solved by the Invention] The present invention aims to reduce the amount of chlorinated solvents and phenols used in place of these conventional solvents in order to reduce their usage, since they are undesirable in terms of toxicity and groundwater contamination. The purpose of this invention is to provide a new resist stripping agent.

[Means for Solving the Problems] The present invention has been made to achieve the above-mentioned objects, and
The present invention provides a resist stripping agent containing an unsaturated chlorinated fluorinated hydrocarbon having 3 carbon atoms as an active ingredient.

The unsaturated chlorinated fluorinated hydrocarbons of the present invention include l-chloro-2-fluoropropene (b, p, 59°C), 2
゜3-dichloro-3,3-difluoropropene (b,
p, 57°C), 1,1-dichloro-3,3,3-trifluoropropene (b.

p, 54°C), 1,2-dichloro-3,3,3-trifluoropropene (b, p, 53°C), 1,3-dichloro-1,3,3-trifluoropropene (b, 9. 57
℃), 1,3-dichloro-2,3゜3-trifluoropropene (b, p, 67℃), 3,3-dichloro-
1,1,3-trifluoropropene (b, p, 52
℃), 3,3-dichloro-2,3-difluoropropene (b, 9.54℃) and other hydrogen-containing unsaturated chlorinated fluorinated hydrocarbons, or a mixture of two or more thereof is preferred.

The resist stripping agent of the present invention can contain various other components depending on various purposes.

For example, hydrocarbons,
At least one kind selected from organic solvents such as alcohols, ketones, halogenated hydrocarbons, aromatics or esters can be contained. The content ratio of these organic solvents in the resist stripping agent is 0 to 50% by weight, preferably 10 to 40% by weight, and more preferably 20 to 30% by weight.
If an azeotropic composition exists in the mixture of the chlorinated fluorinated hydrocarbons of the present invention and the organic solvent, the use of the azeotropic composition is particularly preferred.

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, neohexane, 2,3-dimethylbutane, 3-methylpentane,
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-) dimethylpentane, 2.2.3-) dimethylpentane, isooctane, nonane, 2.2.5-) dimethylhexane, decane, dodecane, 1-pentene, 2-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, cyclopentane, methylcyclobencune, cyclohexane,
It is selected from methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, tetralin, amidino, amylnaphthalene, and the like. More preferred are n-pentane, neohexane, 2,3-dimethylbutane, n-hexane, cyclopentane, cyclohexane, n-hebutane, and the like.

The alcohols are preferably chain or cyclic saturated or unsaturated alcohols having 1 to 17 carbon atoms, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and 5ec- Butyl alcohol, tert-butyl alcohol, pentyl alcohol, 5ec-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-
1-butanol, impentyl alcohol, tert-
Pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, ■-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol,
2-ethyl-1-butanol, 1-to-1-tanol, 2-
1-tanol, 3-1-tanol, 1-octatool,
2-octatool, 2-ethyl-1-hexanol, 1
~nonanol, 3.5.5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol , 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, atonitinol, 2
, 6-dimethyl-4-heptatool, trimethylnonyl alcohol, tetradecyl alcohol, heptadecyl alcohol and the like. More preferably,
Examples include methanol, ethanol, and 10-bill alcohol.

1 to 9 saturated or unsaturated hydrocarbon groups) are preferred, including acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl butyl ketone, methyl isobutyl ketone,
2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, mesityl oxide, holon, methyl-n-amyl ketone, ethyl butyl ketone, methylhexyl ketone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-bentanedione, di It is selected from acetone alcohol, acetophenone, fenchen, etc. More preferred are acetone, methyl ethyl ketone and the like.

The halogenated hydrocarbons are preferably saturated or unsaturated halogenated hydrocarbons having 1 to 4 carbon atoms, such as dichloromethane, carbon tetrachloride, chloroform, 1.1-dichloroethane, 1.2-dichloroethane, 1, 1.1-) dichloroethane, 1.1.2- trichloroethane, 1.
1.1.2-tetrachloroethane, 1.1.2.2-tetrachloroethane, pentachloroethane, 1.1-dichloroethylene, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, trichlorethylene, tetrachloroethylene, 1 -chloropropane, 2
-chloropropane, 0-dichlorobenzene, 1-bromopropane, 2-bromopropane, etc. More preferably dichloromethane, i, i, t
-trichloroethane, trans-1,2-dichloroethylene, cis-R2-dichloroethylene, trichloroethylene, tetrachloroethylene, 0-dichlorobenzene, 2-bromopropane, etc.

As aromatics, benzene derivatives and naphthalene derivatives are preferred, and benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, sec-butylbenzene, triethylbenzene, diisopropylbenzene, alkylbenzene sulfonic acid, phenol, mesitylene, naphthalene, tetralin, It is selected from butylbenzene, p-cymene, cyclohexylbenzene, pentylbenzene, dibentylbenzene, dodecylbenzene, biphenyl, 0-cresol, m-cresol, p-cresol, xylenol, and the like.

More preferred are alkylbenzenesulfonic acids, phenol, and the like.

As the esters, those represented by the following general formula are preferable, including R+ -CO0-R2, COORa R+-CO0-R2-CO0-R3, (COOR+)
2, ◎-COOR+ COOR2 (herein, R1, R2, R3, R4, R5, R6 are H or a hydrocarbon group having 1 to 19 carbon atoms and having a saturated or unsaturated bond).

Specifically, methyl formate, ethyl formate, propyl formate,
Butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, 5ec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 5ec-hexyl acetate, 2 -Ethyl butyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, 10 butyl pionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, 2 -Hydroxy-2
- Ethyl methylpropionate, butyl stearate, pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl abietate, benzyl abietate, bis adipate - 2-Ethylhexyl, γ-butyrolact, diethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, bis sebacate -2-ethyl, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis-2-ethylhexyl phthalate, dioctyl phthalate, and the like. More preferably methyl acetate,
Ethyl acetate, etc.

The resist that can be peeled off according to the present invention is not limited in any way, and examples include positive or negative photoresists, deep ultraviolet resists, X-ray or electron beam resists, and the like.

Photoresist materials include acrylic type for dry film resist, quinone diazide type based on phenol and cresol novolac resin, and cis-1,4-
There are cyclized rubber type and polycinnamic acid type based on polyisoprene as the main component, deep ultraviolet resists include polymethyl methacrylate, polymethyl isopropenyl ketone, etc., and electron beam and X-ray resists include polymethyl Methacrylate, glycidyl methacrylate-ethyl acrylate copolymer, etc. are known, and the resist stripping agent of the present invention is effective for any of them.

The method for removing the resist is not limited in any way, and ordinary spray methods, dipping methods, etc. can be employed.

[Example] Practical Examples 1 to 13 A resist stripping test was conducted using the resist stripping agents shown in Table 1 below. Dry Film Resis) (Lami
After creating a circuit using a copper-clad laminate laminated with ner (manufactured by Dynachem) through exposure, development, and etching steps, the resist film was removed using a microscope after being immersed in a resist remover for 15 minutes at room temperature. I observed the situation. The results are shown in Table 1.

Table 1 [Effects of the Invention] As is clear from the Examples, the resist stripping agent of the present invention has an excellent resist stripping effect.

Furthermore, it is advantageous in that it has fewer adverse effects on plastics and the like than conventionally used chlorinated solvents.

Agent I2-3. H; 1 outsider

Claims (1)

[Claims] 1. A resist stripping agent containing an unsaturated chlorinated fluorinated hydrocarbon having 3 carbon atoms as an active ingredient. 2. The unsaturated chlorinated fluorinated hydrocarbon is 1-chloro-2-fluoropropene, 2,3-dichloro-3,3-difluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1 , 2-dichloro-3,3,3-trifluoropropene, 1,3-dichloro-1,3,3-trifluoropropene, 1,3-dichloro-2,3,3-trifluoropropene, 3,3 -dichloro-1,1,3-
The resist stripping agent according to claim 1, which is trifluoropropene or 3,3-dichloro-2,3-difluoropropene. 3. Hydrocarbons, alcohols,
The resist stripping agent according to claim 1, containing at least one selected from ketones, halogenated hydrocarbons, aromatics, and esters.