JPH01128068A - Releasing agent for resist - Google Patents

Abstract

PURPOSE:To obtain the novel releasing agent for a resist instead of a chlorine type solvent by incorporating trichlorodifluoroethane in the releasing agent as an effective component. CONSTITUTION:Said releasing agent contains the trichlorodifluoroethane as the effective component. The trichlorodifluoroethane is incombustibility and has the excellent releasing power for the resist, and is the excellent solvent having a less adverse influence against the materials of a printed board and a semiconductor. The three kinds of the isomers in said trichlorodifluoroethane are known. Said isomers are used independently or in a mixture thereof. Another various kinds of components may be incorporated in the releasing agent according to a purpose. For example, in order to improve the releasing power against the resist, at least one kind of org. solvents selected among hydrocarbons, alcohols, ketones, chlorinated hydrocarbons, aromatics or esters, etc. is incorporated in the releasing agent. Thus, the releasing effect to the resist is improved, and the adverse influence against the plastics, etc., is lessened in comparison with a chlorine type releasing agent.

Description

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

[Conventional technology] When creating printed circuit boards and semiconductor circuits.

Finally, there is a step of stripping off the resist after etching. Conventionally, chlorinated solvents such as methylene chloride, ketone chloroethylene, and 0-dichlorobenzene have been used in this step.

[Problems to be Solved by the Invention 1] The present invention proposes a new resist '1. in place of chlorinated solvents in order to suppress the use of conventionally used chlorinated solvents, which are undesirable from the standpoint of groundwater contamination. It is L1-like to propose 'l fil deletion.

[Means for Solving Problem E] The present invention has been made to achieve the above-mentioned object 1, and contains trichlorodifluoroethane as an active ingredient.
This paper presents a resist stripping agent that can be used as a resist stripper.

Trichlorodifluoroethane, which is an active ingredient in the resist h+++ stripping of the present invention, is nonflammable, has excellent resist stripping power, and is an excellent solvent that is less likely to form ν in the material of printed circuit boards and 71'-conductors. Trichlorodifluoroethane includes 1,1,2-1-sachloro-2,2-difluoroethane (hereinafter referred to as RI 22), 1.2.2-1-lichloro-1,2-difluoroethane (hereinafter referred to as R122a), and 1.1. Three types of isomers of I-trichloro-2,2-difluoroethane (hereinafter referred to as R122b) are known, but these! 1i can be used alone or as a mixture of two or more of these.

The resist stripping agent of the present invention can contain various other components depending on various purposes. For example, hydrocarbons,
At least one organic solvent selected from alcohols, ketones, chlorinated hydrocarbons, aromatics, Nisdels, etc.
It can contain seeds. The content ratio of these I+ljl solvents in the resist stripping agent is 0 to 50% by weight, preferably 10 to 40% by weight, and more preferably 20 to 3% by weight.
It is 0% by weight. If the mixture of trichlorodifluoroethane 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, isohebane, 3-methylhexane%2.4-dimethylpentane, [1-octane, 2
-Methylhebutane, 3-methylhebutane, 4-methylhebutane.

2.2-dimethylhexane, 2.5-dimethylhexane, 3.3-dimethylhexane, 2-methyl-3-ditylpenkun, 3-methyl-3-ethylbenkun, 2゜3,
3-t-limethylbentane, 2,3.4-1-limethylbentane, z, 2.3-trimethylpentane, isooctane, nonane, 2.2.5-trimethylhexane, decane, dodencane, 1-pentene, 2-Pentene.

1-hexene, 1-octene, 1-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane,
It is selected from bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, tetralin, amylene, amylnaphthalene, and the like. More preferably, r
l-pentane, n-hexane, rl-hebutane, etc.

The alcohols are preferably linear or cyclic saturated or unsaturated alcohols having 1 to 17 carbon atoms, such as methanol, ethanol, rl-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-butyl alcohol, isobutyl alcohol, 'tart-
Butyl alcohol, pentyl alcohol, 5ec-amyl alcohol, 1-ethyl-! -propanol, 2-methyl-1-butanol, isopentyl alcohol, L
erL-pentyl 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-octatool, 2-octanol, 2 -Ethyl-1-hexanol, l-nonanol, 3.5.5-1-rimedyl 1
-hexanol, 1-decanol, I-undecanol, l-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol.

Cyclohexanol, 1-methylcyclohexanol,
selected from 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, avinitinol, 2,6-dimethyl-4-heptatool, trimethylnonyl alcohol, tetradecyl alcohol, heptadecyl alcohol, etc. It is something. More preferably methanol or ethanol.

Examples include isopropyl alcohol.

Ketones include R-CO-R', R-CO,R
-GO-R' - "CO r-CIll -t CD-R", R-GO-R'', R-CD-R' (
Here, R, Il', Il" are preferably any of the following (saturated or unsaturated hydrocarbon groups having 1 to 9 carbon atoms), and are preferably acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone. , 2-hexanone, methyl-〇-butylketone, methylbutylketone, 2-heptanone, 4-heptanone, diisobutylketone, acetonylacetone, mesityl oxide, boron, methyl-〇-amylketone, ethylbutylketone, methylhexylketone, It is selected from cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanedione, diacetone alcohol, acetophenone, fenchone, etc. More preferred are acetone, methyl ethyl ketone, etc.

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. 11-dichloroethane, 1.1.
2-trichloroethane, 1,1.1.2-tetrachloroethane, 1,1,2.2-tetrachloroethane, pentachloroethane, 1.1-dichloroethylene, 1.2-dichloroethylene, trichlor It is selected from ethylene, tetrachlorethylene, etc. More preferred are methylene chloride, 1.1.1-trichloroethane, trichlorethylene, and tetrachloroethylene.

As the aromatic compound, benzene derivatives and naphthalene derivatives are preferred, and benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene,
Secondary butylbenzene, triethylbenzene, diisopropylbenzene, styrene, alkylbenzene sulfonic acid, phenol, mesitylene, naphthalene, tetralin,
It is selected from butylbenzene, p-cymene, cyclohexylbenzene, pentylbenzene, dibentilbenzene, dodecylbenzene, biphenyl, 0-cresol, m-cresol, and xylenol. More preferred are alkylbenzenesulfonic acids, phenol, and the like.

As the Nisdels, R-rich ones represented by the following general formula are preferable: R, -COO-R,, +1. -C-R
,-COO-R,.

■ OR.

COOR 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, methyl propionate, isopentyl propionate, methyl acetate.

Ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isoacetate, ethyl 2-hydroxy-2-methylbrobionate, butyl stearate, pentyl stearate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl abietate, benzyl abietate, bis-2-ethylhexyl adipate, γ-butyrolact, diethyl oxalate, dibutyl oxalate, dibentyl oxalate, diethyl malonate, maleic acid Dimethyl, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sepacate, bis-2-ethylhexyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis-2-phthalate
Some are selected from ethylhexyl, dioctyl phthalate, etc. More preferred are methyl acetate, ethyl acetate and the like.

The resist that can be peeled off according to the present invention is not limited in any way, and may include positive or negative type resists for pre-exposure, resists for deep ultraviolet exposure, and resists for X-rays or electron beams. Materials for resists for light exposure include quinonediazide based on phenol and Talezol novolak resins, cyclized rubber based on cis-1,4-polyisoprene, and polycinnamic acid. UV resists include polymethyl methacrylate, polymethyl isopropenyl ketone, etc., and electron beam and X-ray resists include polymethyl methacrylate 1. Glycidyl methacrylate
Ethyl acrylate cofn combination, methyl methacrylate-
Although methacrylic acid copolymers and the like are known, the resist stripping agent of the present invention is effective for both.

The method for removing the resist is not limited at all, and a conventional spray method, a method of dipping and stirring, shaking, applying ultrasonic waves, etc. can be adopted.

[Examples] Examples 1 to 9 A resist stripping test was conducted using resist stripping agents shown in Table 1 below. Photoresist film (Lam1n
After creating a circuit using a printed circuit board (copper-clad laminate) laminated with cr (manufactured by Dynachem) through exposure, development, and etching steps, it was immersed in a resist remover for 5 minutes at room temperature. After taking it out, the state of peeling of the cured film was observed using a microscope.

The results are shown in Table 1.

Table 1 () shows the mixing ratio [wt%] O: good peeling Δ: small amount remaining It is excellent.

Also, compared to conventional chlorine-based strippers, it is 2S more harmful to plastics used in printed wiring boards. The fact that there are few J's is also an advantage.

Claims (2)

[Claims] (1) A resist stripping agent containing trichlorodifluoroethane as an active ingredient. (2) Claim 1, wherein the resist stripper contains at least one selected from hydrocarbons, alcohols, ketones, chlorinated hydrocarbons, aromatics, or esters. The resist stripping agent described.