JPH06194847A - Developing liquid for negative type photoresist - Google Patents

Abstract

PURPOSE:To provide a developing liquid having performance same as 1,1,1- trichloroethane for developing the photoresist composed essentially of a photosensitive polyhydroxyether resin. CONSTITUTION:The developing liquid is characterized by using a 6-12C aromatic compound or a solvent mixture containing a 6-12C aromatic compound in an amount of >=50weight% as the developing liquid for developing liquid for developing the negative type photoresist composed of the photosensitive polyhydroxyether resin obtained by reaction with a polyhydroxyether resin with glycidyl (meth)acrylate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a negative photoresist for printed wiring boards. More specifically,
The present invention relates to a developer for developing a negative photoresist for a printed wiring board, which contains a photosensitive polyhydroxyether resin obtained by a reaction of a polyhydroxyether resin and glycidyl (meth) acrylate as a main component.

[0002]

2. Description of the Related Art Conventionally, 1,1,1-trichloroethane, which is non-hazardous and nonflammable, has been used as a developing solution for negative photoresists for printed wiring boards.
Also when developing a negative photoresist containing a photosensitive polyhydroxyether resin obtained by the reaction of a polyhydroxyether resin and glycidyl (meth) acrylate as a main component, JP-B-60-39693 and JP-A-3- As disclosed in JP-A-212644 and JP-A-3-287659, 1,1,1-trichloroethane is used as a developing solution.

[0003]

However, in recent years, it has been decided that 1,1,1-trichloroethane will be completely abolished due to the problem of ozone layer depletion, and a substitute for 1,1,1-trichloroethane as a developing solution is strongly required. It's starting to happen. Although 1,1,1-trichloroethane has a problem of ozone layer depletion, in a negative photoresist mainly containing a photosensitive polyhydroxyether resin obtained by the reaction of polyhydroxyether resin and glycidyl (meth) acrylate, It is a developer having characteristics such that the non-exposed area is completely dissolved and the exposed area is not dissolved at all, that is, the so-called dissolution selectivity is good and scum generation is small. An object of the present invention is to provide a 1,1, 1- as a developing solution for developing a negative photoresist containing a photosensitive polyhydroxy ether resin as a main component, which is obtained by reacting a polyhydroxy ether resin with glycidyl (meth) acrylate. It is to provide a developer having equivalent performance as a substitute for trichloroethane.

[0004]

As a result of intensive studies in view of the above problems, the present inventors have found that an unsubstituted or substituted aromatic hydrocarbon having a specific carbon number or a mixed solvent containing the aromatic hydrocarbon is The present invention has been accomplished by finding that a developing solution having good dissolution selectivity and less scum generation and having equivalent performance as a substitute for 1,1,1-trichloroethane can be obtained.

According to the first aspect of the present invention, in developing a negative photoresist containing a photosensitive polyhydroxy ether resin as a main component, which is obtained by reacting a polyhydroxy ether resin with glycidyl (meth) acrylate. , An aromatic compound having 6 to 12 carbon atoms or 6 to 12 carbon atoms
A developer for a negative photoresist, comprising a mixed solvent containing 12 aromatic compounds of 50% by weight or more as a developer.

According to a second aspect of the present invention, the mixed solvent is
50% by weight or more of an aromatic compound having 6 to 12 carbon atoms, and the balance of at least one selected from the group consisting of ethers, aliphatic saturated or unsaturated hydrocarbons, ketones, esters, amides and alcohols. The negative photoresist developing solution according to claim 1, which is a solvent.

That is, the present invention develops a negative photoresist containing a photosensitive polyhydroxyether resin obtained by the reaction of a polyhydroxyether resin and glycidyl (meth) acrylate as a main component, and has 6 carbon atoms.
It is a developing solution for a negative photoresist, wherein a developing solution is a mixed solvent containing 50% by weight or more of alkylbenzene having 12 to 12 carbon atoms or alkylbenzene having 6 to 12 carbon atoms. The photosensitive polyhydroxy ether resin used in the present invention comprises, for example, a polyhydroxy ether resin represented by the general formula (Formula 1) described in JP-B-60-39693 and a glycidyl (meth) acrylate. It is a photosensitive resin obtained by an epoxy ring-opening addition reaction.
Such a photosensitive resin is prepared by dissolving 1 part by weight of polyhydroxy ether in 10 parts by weight of glycidyl (meth) acrylate and using 80 parts by weight of 0.1 parts by weight of potassium hydroxide, triethylamine, triethylbenzylammonium chloride as a catalyst. It can be obtained by reacting at a temperature of 120 ° C. for 4 to 8 hours.

[0008]

[Chemical 1]

The developer of the present invention is an unsubstituted or substituted aromatic compound having 6 to 12 carbon atoms or a mixed solvent containing 50% by weight or more of the aromatic compound. Examples of the unsubstituted or substituted aromatic compound having 6 to 12 carbon atoms include benzene, toluene, o-xylene, p-xylene, m-xylene, iso-propylbenzene, n-propylbenzene and 1-methyl-3-ethylbenzene. , 1-methyl-
4-ethylbenzene, 1,3,5-trimethylbenzene, 1-methyl-2-ethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene,
Indane, cumene, iso-butylbenzene, sec-
Butylbenzene, 1,3-diethylbenzene, 1-methyl-3-n-propylbenzene, 1,4-diethylbenzene, 1,3-diethyl-5-ethylbenzene, 1,2
-Diethylbenzene, 1-methyl-2-n-propylbenzene, 1,4-dimethyl-2-ethylbenzene, 1,
3-dimethyl-2-ethylbenzene, 1,2-dimethyl-4-ethylbenzene, 1,2-dimethyl-3-ethylbenzene, 1,2,4,5-tetramethylbenzene,
Examples thereof include 1,2,3,5-tetramethylbenzene, methylindane, tetralin, p-cymene, cyclohexylbenzene, pentylbenzene, mixed xylene, solvent naphtha and the like. Further, these developing solutions may be used alone or in combination of two or more kinds as necessary.

The solvent used in the mixed solvent is at least one solvent selected from the group consisting of ethers, saturated or unsaturated aliphatic hydrocarbons, ketones, esters, amides and alcohols.

Examples of ethers include ethers having 4 to 15 carbon atoms such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol diethyl ether and diphenyl ether.

Examples of the aliphatic saturated or unsaturated hydrocarbon include hexane, heptane, octane, cyclohexane, methylcyclohexane, cyclohexane, dipentene, decalin, petroleum benzine, ligroin, etc. Hydrocarbons may be mentioned.

Examples of ketones include ketones having 4 to 10 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, phorone and cyclohexanone.

Examples of the esters include ethyl acetate, butyl acetate, ethyl propionate, ethyl lactate, ethyl pyruvate, ethyl acetate and the like having 4 carbon atoms.
The esters of 10 to 10 can be mentioned.

Examples of amides include amides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide.

Examples of alcohols include alcohols having 1 to 10 carbon atoms such as ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monoethyl ether and diethylene glycol monomethyl ether.

Regarding the mixing ratio of the aromatic compound used in the mixed solvent, depending on the composition of the photoresist, it may be advantageous that the ratio of the aromatic compound is large, or conversely, it may be advantageous to use the mixed solvent. However, it cannot be decided unconditionally because it is appropriately selected and used. But,
Usually, the mixing ratio of the aromatic compound is 50% by weight or more, preferably 70% by weight or more.

The photoresist which can be used in the present invention basically comprises a photosensitive polyhydroxyether resin, a photopolymerization initiator, a crosslinking agent and a diluting solvent. If desired, reactive diluents, fillers and the like can be added.

As the photopolymerization initiator that can be used in the present invention, known ones can be used, for example, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether,
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone, aromatic ketones such as benzophenone and 4,4′-bisdialkylaminobenzophenone ,
And a combination of two or more of these can be mentioned. Although the addition amount of the photopolymerization initiator is not particularly limited, it can be used in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the photosensitive polyhydroxyether resin.

Examples of the crosslinking agent usable in the present invention include trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and pentaerythritol. Acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipeentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexane The Olde Acrylate, polyethylene glycol diacrylate, epoxy acrylate, urethane acrylate, and the like, and combinations of two or more thereof. The amount of the crosslinking agent added is not particularly limited, but it can be used in an amount of 10 to 30 parts by weight with respect to 100 parts by weight of the photosensitive polyhydroxyether resin.

When using these, for example, first, the above-mentioned photosensitive polyhydroxyether resin, photopolymerization initiator,
A photoresist solution is prepared by dissolving a crosslinking agent and, if necessary, a reactive diluent and a filler in methyl ethyl ketone, ethyl cellosolve acetate or the like. Next, this photoresist solution is applied to a desired thickness on a substrate using a curtain coater, a roll coater, a spin coater, etc.
Bake at a temperature of 0-150 ° C. The photoresist layer thus formed is exposed through a negative mask by using an ultrahigh pressure mercury lamp, a high pressure mercury lamp or the like as a light source.

Next, development is performed using the developing solution of the present invention. The developing method is not particularly limited, and a known method can be used. That is, it may be immersed in the developing solution as it is, may be subjected to ultrasonic treatment, or may be developed by spraying. The development temperature is not particularly limited, and it is generally desirable to use it at room temperature, but the temperature can be raised to about 100 ° C. if necessary. The developed substrate is left as it is or rinsed with methanol, ethanol, isopropanol or the like, and then baked to form a negative pattern.

[0023]

The present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. (Synthesis example of photosensitive polyhydroxy ether resin) 20 g of phenoxy resin (PKHH, Union Carbide Co., Ltd.), glycidyl methacrylate (Nissan Yushi Co., Ltd. 200 ml of Bremmer G) was added, and the temperature of the oil bath was raised to 100 ° C. with stirring. When the resin was dissolved, 1.0 g of triethylbenzylammonium chloride was added, and the mixture was reacted at an oil bath temperature of 100 ° C. for 5 hours. After cooling the dark brown solution to 60-70 ° C, 100
The resin was precipitated by pouring into 0 ml of methanol. The resin was filtered and washed with 400 ml of methanol. Further, dissolve in about 50 ml of tetrahydrofuran and
The purification method of precipitation with 1 l of methanol was repeated 4 times. By vacuum-drying at 40 ° C. for 6 to 7 hours, 23 g of a photosensitive resin was obtained. The introduction ratio of glycidyl methacrylate to the hydroxy group of the phenoxy resin is proton NM.
It was 65% from the measurement result of R.

Example 1 100 parts by weight of the photosensitive polyhydroxyether resin obtained in the synthesis example, 3 parts by weight of 2-ethylanthraquinone, and 30 parts by weight of pentaerythritol tetraacrylate were dissolved in 200 parts by weight of ethyl cellosolve acetate to obtain a photo. A resist solution was prepared. This photoresist solution was applied onto a copper-blackened substrate of a glass epoxy substrate using a spin coater. Baking was performed at 80 ° C. for 30 minutes to form a 55 μm resist layer. Then, using a jet printer (Oak Seisakusho Co., Ltd.), exposure was performed at 400 mj / cm ² using a Kodak step tablet as a mask. Then p-
It was immersed in xylene for 3 minutes and developed. The obtained resist pattern did not show fine wrinkles, droops, or tails. Further, swelling of the resist layer due to the developing solution was not observed, and a sharp pattern was obtained. For reference, a rinse with isopropanol was subsequently performed, but no change was observed in the resist pattern. The swelling of the resist layer and the determination of the resist pattern were carried out by observing the developed substrate with a stereoscopic microscope (50 times) and checking for pattern distortion, peeling, swelling, or the like.

Example 2 Solvent naphtha type Solfine ™ (trimethylbenzenes: 45) was used as a developing solution.
%, Methylethylbenzenes: 35%, propylbenzenes: 7%, other: 13%, manufactured by Showa Denko KK), but the same operation as in Example 1 was performed. As a result, the obtained resist pattern was free of fine wrinkles, droops, and tails.

Comparative Example 1 The same operation as in Example 1 was carried out except that 1,1,1-trichloroethane was used as the developing solution. As a result, the obtained resist pattern was free of fine wrinkles, droops, and tails. In addition, no swelling of the resist layer due to the developing solution was observed, and Examples 1 and 2
The result was exactly the same.

(Examples 3 to 8) The same operation as in Example 1 was carried out except that the mixed solvent containing Solfine TM shown in Table 1 was used as the developing solution. The evaluation results are also shown in Table 1.

[0028]

[Table 1]

Comparative Example 2 The same operation as in Example 1 was carried out except that tetrahydrofuran was used as the developing solution. As a result, the resist layer was swollen and the pattern was partially peeled off.

[0030]

The developer of the present invention is used as a developer for developing a negative photoresist containing a photosensitive polyhydroxyether resin obtained as a main component by the reaction of a polyhydroxyether resin and glycidyl (meth) acrylate. , 1,1-trichloroethane has the same performance, good dissolution selectivity, and a sharp pattern can be obtained without causing swelling of the resist layer. In addition, the developer of the present invention has no ozone layer depletion problem and is a global environment-friendly developer, and therefore has high industrial utility value.

Claims (2)

[Claims] 1. A fragrance having 6 to 12 carbon atoms in developing a negative photoresist containing a photosensitive polyhydroxy ether resin as a main component obtained by a reaction of a polyhydroxy ether resin and glycidyl (meth) acrylate. A developer for a negative photoresist, which comprises a mixed solvent containing a group compound or an aromatic compound having 6 to 12 carbon atoms in an amount of 50% by weight or more. 2. A mixed solvent comprising 50% by weight or more of an aromatic compound having 6 to 12 carbon atoms and the balance of ethers, aliphatic saturated or unsaturated hydrocarbons, ketones, esters, amides and alcohols. The negative photoresist developing solution according to claim 1, which is at least one solvent selected from the group consisting of: