JP2002241440A - Alkali-soluble polymer and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that is developable with an aqueous alkaline solution, has high sensitivity and high resolution, is tackfree, has good heat resistance, etching resistance and storing stability, and is easy to be removed when used as an etching resist, and to provide an alkaline soluble resin as a constituent thereof. SOLUTION: This photosensitive resin composition comprises an alkaline soluble polymer having a vinyl group and a carboxy group in a side chain that is obtained by reacting a copolymer comprising a segment having a carboxyl group with a compound having one or more ethylenic double bonds and isocyanato groups in a molecule, as well as a compound having an ethylenic double bond, and a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for removing unexposed portions easily with a dilute alkaline solution during photocuring,
The exposed portion relates to an insoluble photosensitive resin composition and an alkali-soluble polymer as a component thereof, and is widely used in the printing industry, the electronics industry, and the like.

[0002]

2. Description of the Related Art With the development of metal processing industry, electronics industry, printing, paint and ink industry, etc., photosensitive resin has been widely used in various fields. The main specific applications are (a) production of copper-clad laminates by partial metal etching, production of precision electronic circuits such as LSI, (b) production of printing resin plates, and (c) screen printing. Such as ink. Therefore, the final purpose of use, conditions,
Modification of the photosensitive resin is naturally required from the viewpoint of simplification of the process on the creator side and environmental considerations. At present, various types of photosensitive resins having different characteristics are commercially available and marketed.

The photosensitive resin has two types, a positive resist in which an exposed portion is removed during a developing process to obtain a positive pattern, and a negative resist in which an unexposed portion is removed and a negative pattern is obtained. is there. In general, a negative type has better sensitivity, adhesion to a substrate, and chemical resistance than a positive type, and a positive type has better resolution and dry etching resistance than a negative type.

The following steps are used when fabricating a circuit by partially etching a metal foil or the like using this negative photosensitive resin, or fabricating a resin plate for printing. A negative mask is placed on the thin film of the applied photosensitive resin composition, the exposed portion is cured by irradiating light through the negative mask, and the non-exposed portion is removed by washing. It is eluted by immersion to produce a circuit. Further, in the plate making for printing, an etching step is unnecessary.

A conventional photosensitive resin composition is obtained by polymerizing a (meth) acrylic polymerizable monomer or the like.
A polymer compound having an unsaturated double bond in the molecular structure,
Some include a photopolymerization initiator and a photocrosslinking agent. As a characteristic of such a photosensitive resin composition, development is often performed using an organic solvent, which is not preferable in terms of environmental protection, and its use is problematic.

On the other hand, various photosensitive resin compositions which can be developed with an aqueous alkali solution without using an organic solvent have been disclosed. In particular, as a liquid photoresist, one using a copolymer of methacrylic acid and an alkyl methacrylate (Japanese Patent Publication No. 54-34327), an unsaturated carboxylic acid and an alkyl methacrylate having an alkyl group having 4 or more carbon atoms. Use of a copolymer having a glass transition point of 80 ° C. or higher with an ester (Japanese Patent Publication No. 58-12577), a copolymer of an unsaturated carboxyl group-containing monomer with a styrene type monomer or a non-acidic vinyl compound (JP-B-55-38961), 15 to 40 parts by weight of an α, β-unsaturated carboxylic acid, 15 to 45 (meth) acrylic acid alkyl esters and 40 to 6 styrene-type monomers.
Using a copolymer consisting of 0% by weight (Japanese Patent Publication No. 54-1979)
No. 25957) is known, but in any case, the requirements were not sufficiently satisfied in terms of developability (patterning characteristics), chemical resistance and heat resistance.

Under these circumstances, a photosensitive resin has been developed which is mainly composed of an acrylic resin having a high acid value and whose properties are relatively easily improved, and which reacts with an aliphatic epoxy group-containing vinyl compound such as glycidyl (meth) acrylate. And
139,191, JP-A-3-172301,
JP-A-3-280059, JP-A-10-7747
And Japanese Patent Application Laid-Open No. 11-327139. Recently, in order to improve properties such as water resistance and adhesion to a substrate, a reaction product obtained by adding an alicyclic epoxy group-containing unsaturated resin to the high acid value vinyl resin by a ring-opening reaction has been proposed. Japanese Unexamined Patent Publication No. Hei.
No. 10726, Japanese Patent Application Laid-Open No. 10-17614, and the like. This resin is described as being characterized in that it has good curability, adhesion and water resistance, and that the surface tackiness after drying the coating film is remarkably lower than that of a conventional resin. Further, it is necessary to remove the etching resist after the completion of the etching. However, since many resists form a permanent film typified by a solder resist, it is not easy to remove the film.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high sensitivity and high resolution which can be developed using an alkaline aqueous solution, and which is tack-free, and has heat resistance, etching resistance and storage stability. An object of the present invention is to provide a photosensitive resin composition which is favorable and can be easily removed when used as an etching resist, and an alkali-soluble resin which is a component thereof.

[0009]

According to the present invention, there is provided the following general formula (1) containing a segment having a carboxyl group.
Is an alkali-soluble polymer comprising the modified polymer represented by

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A second aspect of the present invention provides a copolymer containing a segment having a carboxyl group represented by the following general formula (2), wherein one or more ethylenic double bonds and an isocyanate group are contained in one molecule. An alkali-soluble polymer characterized by being a modified polymer having a vinyl group and a carboxyl group in a side chain obtained by reacting a compound having the same.

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A third aspect of the present invention is characterized in that it comprises (A) the alkali-soluble polymer according to the first or second aspect, (B) a compound having an ethylenic double bond, and (C) a photopolymerization initiator. A photosensitive resin composition.

[0012] The invention of claim 4 is that the (A) alkali-soluble polymer 5 is used for the entire photosensitive resin composition.
The photosensitive resin according to claim 23, comprising 0 to 95% by weight, (B) 4 to 40% by weight of a compound having an ethylenic double bond, and (C) 1 to 10% by weight of a photopolymerization initiator. A composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The (A) alkali-soluble polymer used in the present invention is obtained by adding a compound having at least one ethylenic double bond and an isocyanate group in one molecule to a copolymer containing a segment having a carboxyl group. A modified polymer having a vinyl group and a carboxyl group in the side chain obtained by the reaction and represented by the following general formula (1). Examples of the copolymer containing a segment having a carboxyl group include a compound represented by the general formula (2).

[0015]

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[0016]

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Specific examples of the copolymer containing a segment having a carboxyl group include a methacrylic acid-acrylic ester copolymer, a methacrylic acid-methacrylic ester copolymer, and an acrylic acid-acrylic ester copolymer. And a methacrylic acid-acrylic acid ester copolymer. More specifically, examples of the ester site include, but are not limited to, methyl, ethyl, n-butyl, tetrahydrofurfuryl, benzyl, and phenyl esters.

The compound having at least one ethylenic double bond and an isocyanate group in one molecule includes a compound represented by the following general formula (3). For example, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, allyloxyethyl isocyanate and the like can be mentioned, but not limited thereto.

[0019]

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The rate of introduction of an ethylenic double bond into the copolymer containing a segment having a carboxyl group by isocyanate is from 1 to unit (n) of the copolymer containing a segment having a carboxyl group. It is preferably in the range of 50%. If the amount is less than 50%, the effect of introduction is not exhibited, and a resist with high sensitivity and high resolution cannot be obtained. On the other hand, if it is more than this, the alkali solubility of the photosensitive resin composition is undesirably reduced.

The reaction of the above-mentioned copolymer containing a segment having a carboxyl group with an isocyanate group-containing unsaturated compound is described in, for example, Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" Taiseisha, 1981, 44- As described on page 45, the corresponding amide can be produced by decarboxylation by heating without a catalyst. That is, in the present invention, a modified polymer ((A) an alkali-soluble polymer) is obtained by the above reaction.

The molecular weight of the alkali-soluble polymer (A) is 1,000 or more by weight average molecular weight and 100,000
If it is less than this, the strength of the cured film will be significantly reduced, and if it is more than this, the solubility will be reduced, making it difficult to prepare the resist, which is not preferred. Considering sensitivity and resolution, the weight average molecular weight is 5,
More preferably, it is in the range of 000 or more and 20,000 or less. Further, 5 to the entire photosensitive resin composition.
Preferably it is in the range of 9 to 95% by weight.

The acid value (based on JIS K-1557) of the alkali-soluble polymer (A) used in the present invention is 50 to 1
Preferably it is in the range of 50 mg KOH / g. When the acid value is 50 mgKOH / g or less, it becomes difficult to remove the uncured composition during development with a dilute aqueous alkaline solution. on the other hand,
When the acid value is 150 mgKOH / g or more, an image may flow during development with a dilute alkaline aqueous solution, or the moisture resistance of the cured film may be deteriorated.

Further, in the above-mentioned reaction between the carboxyl group and the isocyanate group, the ratio of the copolymer containing the segment having the carboxyl group to the compound having the ethylenic double bond and the isocyanate group is not particularly limited. Is the resin after the reaction ((A) alkali-soluble polymer)
The double bond is usually 1.0 to 3.5 mol per kg (that is, the double bond equivalent is 1,000 to 286 g / mol, unsaturated group).
And preferably 1.5 to 3.5 mol (equivalent to a double bond equivalent of 667 to 333 g / mol unsaturated group). The double bond of the (A) alkali-soluble polymer is 1.
If the amount is less than 0 mol, a sufficient photocured product may not be obtained. On the other hand, when it is more than 3.5 mol, there are problems such as film residue at the stage of removing the resist and sufficient storage stability cannot be obtained.

The compound (B) having an ethylenic double bond used in the present invention may be, for example, a compound such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, ethylene bisacrylamide, etc. Boiling vinyl monomers, and
Mono (meth) acrylic esters such as methanol, ethanol, 1-pronol, 1-butanol, 2-ethylhexanol and ethylene glycol, and further, ethylene glycol, diethylene glycol, polyethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, Examples thereof include di- or poly (meth) acrylates such as pentaerythritol, but are not limited thereto.

The photopolymerization initiator (C) used in the present invention comprises:
Photopolymerization initiators that generate radical species by actinic radiation, specifically, benzoin alkyl ethers such as benzoin isopropyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, 2-hydroxy- 2-methyl-
Α-hydroxy ketones such as 1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- Α-aminoketones such as 1 (4-morpholinophenyl) butanone-1, bisacylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphone oxide, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-
Bisimidazoles such as 1,1′-biimidazole and bis (2,4,5-triphenyl) imidazole;
Thioxanthones such as -diethyl-9H-thioxanthen-9-one, N-arylglycines such as N-phenylglycine, organic azides such as 4,4'-diazidochalcone, 3,3 ', 4,4 Organic peroxides such as' -tetra (tert-butylperoxycarboxyl) benzophenone; Photochem. Sci. T
echnol. , 2,283 (1987). And specific examples thereof include iron arene complexes, trihalogenomethyl-substituted s-triazines, sulfonium salts, diazonium salts, phosphonium salts, selenonium salts, arsonium salts, iodonium salts and the like.

Further, if necessary, sensitizers such as benzophenones such as Michler's ketone and thioxanthones may be added.

The (B) compound having an ethylenic double bond contained in the photosensitive resin composition of the present invention can be in the range of 2 to 50% by weight based on the whole photosensitive resin composition. And preferably 4 to 40% by weight. In addition, when the addition amount is more than this, there arises a problem that the surface tackiness of the photosensitive resin composition is increased and the contact exposure cannot be performed. On the other hand, if it is less than this, the crosslinked density of the cured product cannot be sufficiently obtained, so that cracks and cracks are apt to occur after development, which causes a problem when it is applied to an etching resist. Further, the amount of the photopolymerization initiator (C) can be in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the whole photosensitive resin composition. . Since the amount of addition is limited by the thickness of the photosensitive resin to be formed and the optical density of the thickness, it is preferable to use the additive within a range where the optical density does not exceed 2.
The sum of (A) the alkali-soluble polymer, (B) the compound having an ethylenic double bond, and (C) the photopolymerization initiator is 100% in total.

In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, if necessary, compatible additives such as a polymerization inhibitor, a plasticizer, a stabilizer, a surfactant, a coloring agent, a leveling agent, Coupling agents and the like can be added as long as the object of the present invention is not impaired.

The photosensitive solution obtained by appropriately selecting each component as described above and mixing them at an arbitrary ratio is used in a known manner such as a bar coater, an applicator, a doctor blade, a roll coater, a spin coater, a roll coater, a die coater, and a comma coater. Is applied onto a metal substrate such as zinc, iron, copper, aluminum, or an alloy thereof, or a substrate such as a metal vapor deposition plate, glass, or a plastic film typified by polyester. The substrate may be surface-treated with heat treatment, surface polishing, etching, chemicals or the like to improve the properties.

When the photosensitive solution is prepared, it may be diluted with an appropriate solvent if necessary, but in this case, it is necessary to apply the solvent on a substrate and then dry it. As the solvent,
Dichloromethane, chloroform, acetone, 2-butanone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxy acetate, 2-butoxyethyl acetate, 2-methoxyethyl ether,
2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate,
Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4
-Dioxane and the like.

Although the film thickness varies depending on the application field, it is usually 1
It is good to set it in the range of 70 μm. Next, the obtained coated product is dried at room temperature or with a heater to form a photosensitive layer. The heating temperature can be a temperature at which the composition and the substrate do not deteriorate, for example, 120 ° C.

On the photosensitive layer formed by the above method,
After adhering a photomask having a predetermined pattern, for example, by exposing with an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, etc. By developing with a liquid, an image faithful to the mask pattern can be obtained.

Specific examples of the alkali component of the diluted alkaline aqueous solution used in the present invention include hydroxides, carbonates, bicarbonates, and the like of metals such as lithium, sodium, and potassium.
Inorganic bases such as phosphates, primary amines such as pyrophosphate, benzylamine and butylamine, secondary amines such as dimethylamine, dibenzylamine and diethanolamine;
Tertiary amines such as trimethylamine, triethylamine and triethanolamine; cyclic amines such as morpholine, piperazine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide and trimethyl Ammonium hydroxides such as phenylammonium hydroxide and choline; sulfonium hydroxides such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide and dimethylbenzylsulfonium hydroxide; and mixtures of these alkali components and buffers. Can these one
Species or a mixture of two or more can be used.

The amount of the alkali component used in the dilute aqueous alkali solution for development is not particularly limited as long as it is a level that allows a dilute alkali. For example, a 0.5 to 5% by weight aqueous solution of sodium carbonate is usually used as a diluted alkaline aqueous solution. As described above, the developed resist pattern film may be further heated at a temperature of 100 to 250 ° C. for 10 minutes to
Post bake for about 3 hours is performed. Thereby, the polymerization and curing of the cured film can be further advanced, and the heat resistance, the etching resistance, the adhesion and the like can be improved.

The photosensitive resin composition of the present invention is used for a photoresist, an etching resist, a solder resist, a dry film resist, a printing plate, and the like. The resist pattern formed on the substrate is treated with an etchant to transfer and form a desired pattern on the substrate. The etchant is not particularly limited, but is usually ferric chloride,
An aqueous solution of cupric chloride or the like is used. After the completion of the etching treatment, the cured film is removed using a concentrated alkaline aqueous solution, but dissolution is more preferable than peeling from the viewpoint of sticking to a substrate and adhesion of foreign matter.

Hereinafter, embodiments of the present invention will be described with reference to specific examples, but the present invention is not limited to the examples described below. Further, since the photosensitive resin composition of the present invention is extremely sensitive to light, in order to prevent exposure by unnecessary light such as natural light, all operations are performed in yellow,
Or, it goes without saying that it is performed under red light.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A detailed embodiment will be described below.

<Synthesis Example 1: A-1> A mixture of 30 parts by weight of styrene, 35 parts by weight of butyl acrylate, 35 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was heated to 110 ° C. in a nitrogen gas atmosphere. Was added dropwise over 3 hours to 50 parts by weight of n-butanol and 40 parts by weight of methyl isobutyl ketone in the reaction vessel held in the above. One hour after the addition, a mixture of 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of methyl isobutyl ketone was added dropwise for 1 hour, and the mixture was allowed to stand for another 5 hours to obtain a high acid value acrylic resin (acid number 260 ) A solution was obtained. Next, 90 parts by weight of methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko KK) and 0.14 parts by weight of hydroquinone monomethyl ether were added to the solution, and the modified copolymer was reacted at 80 ° C. for 5 hours while blowing air. A solution was obtained. After allowing the modified copolymer solution to cool to room temperature, it was added dropwise little by little to 1500 parts by weight of diethyl ether and reprecipitated, followed by filtration and drying to obtain a modified copolymer ((A) an alkali-soluble polymer). Was. (Acid value about 20, number of unsaturated bonds 1.98 / 1000, number average molecular weight about 15,000)

<Synthesis Example 2: A-2> A mixture of 40 parts by weight of n-butyl methacrylate, 35 parts by weight of butyl acrylate, 25 parts by weight of acrylic acid, and 1 part by weight of azobisisobutyronitrile was mixed under a nitrogen gas atmosphere. The modified copolymer ((A) alkali-soluble polymer, acid value) was prepared in the same manner as in Synthesis Example 1 except that it was dropped into 90 parts by weight of n-butanol in a reaction vessel maintained at 110 ° C. over 3 hours. About 10, the number of unsaturated bonds is 2.07 / 1000, and the number average molecular weight is about 30,000).

<Synthesis Example 3: A-3> A mixed solution containing 20 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate, 40 parts by weight of benzyl methacrylate, and 0.03 part by weight of azobisdimethylvaleronitrile was mixed in a nitrogen gas atmosphere. And 85 parts by weight of dipropylene glycol monomethyl ether in a reaction vessel maintained at 95 ° C.
The modified copolymer ((A)) was operated in the same manner as in Synthesis Example 1 except that it was added dropwise to 0.02 parts by weight of rt-butylperoxy-2-ethylhexanoate over 4 hours and then left for 5 hours.
1. alkali-soluble polymer, acid value about 10, number of unsaturated bonds
07/1000, number average molecular weight about 38,000).

Example 1 The modified copolymer of Synthesis Example 1 (A
1) in 60 parts by weight of dipentaerythritol hexaacrylate (Aronix M-400, Toagosei Co., Ltd.)
40 parts by weight) and 5 parts by weight of 2,4-diethyl-9H-thioxanthen-9-one (manufactured by Aldrich Co.)
It was dissolved in 120 parts by weight of (2-ethoxyethoxy) ethyl acetate to obtain a photosensitive solution. Blue plate glass (1.1 mm thick, 5 inch square) which was degreased, washed with water and dried
Was coated with a doctor blade to a thickness of 10 μm, and dried at 80 ° C. for 10 minutes to form a photosensitive layer.

Immediately after exposing the photosensitive layer side at 500 mJ / cm ² using a super high pressure mercury lamp (HMW-532, manufactured by Oak Manufacturing Co., Ltd.) through a mask film,
% Sodium carbonate aqueous solution, Koda
k PhotographicStep Tablet
No. 2 (hereinafter referred to as gray scale) sensitivity is 7
And the resolution was 40 μm. This sensitivity is 24 hours after exposure.
The case where development was carried out after standing for a long time did not change.

Example 2 Dipentaerythritol hexaacrylate was converted to trimethylolpropane triacrylate (Aronix M-309, manufactured by Toagosei Co., Ltd.)
The same operation as in Example 1 was conducted, except that 30 parts and 10 parts of ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300, manufactured by Toagosei Co., Ltd.) were used. The gray scale sensitivity was 6, and the resolution was 35 μm. This sensitivity did not change when developed after standing for 24 hours after exposure.

Example 3 The modified copolymer of Synthesis Example 1 (A
The same operation as in Example 1 was carried out except that -1) was replaced with the modified copolymer (A-2) in Synthesis Example 2, the gray scale sensitivity was 6 and the resolution was 40 μm. This sensitivity did not change when developed after standing for 24 hours after exposure.

<Example 4> The modified copolymer of Synthesis Example 1 (A
The same operation as in Example 1 was performed except that -1) was replaced with the modified copolymer (A-3) of Synthesis Example 3, the gray scale sensitivity was 7 and the resolution was 30 μm. This sensitivity did not change when developed after standing for 24 hours after exposure.

Example 5 The modified copolymer of Synthesis Example 1 (A
-1) The same operation as in Example 2 was performed, except that the modified copolymer (A-2) in Synthesis Example 2 was used. The gray scale sensitivity was 7 and the resolution was 40 μm. This sensitivity did not change when developed after standing for 24 hours after exposure.

<Example 6> The modified copolymer of Synthesis Example 1 (A
The same operation as in Example 2 was carried out except that -1) was replaced with the modified copolymer (A-3) in Synthesis Example 3, the gray scale sensitivity was 7 and the resolution was 35 μm. This sensitivity did not change when developed after standing for 24 hours after exposure.

Example 7 The procedure of Example 7 was repeated except that 2,4-diethyl-9H-thioxanthen-9-one (manufactured by Aldrich) was replaced with 1-hydroxycyclohexylphenyl ketone (Irgacure 184, Ciba Specialty Chemicals). When operated in the same manner as in Example 1, the gray scale sensitivity was 5 and the resolution was 40 μm.
This sensitivity did not change when developed after standing for 24 hours after exposure.

Example 8 Jusco Clean N at 60 ° C.
o. 5 An immersion solution for 2 minutes in an aqueous solution (manufactured by Japan Surface Treatment Co., Ltd.), washing and drying treatment on a 42 alloy (42 nickel-iron alloy) plate, using the same photosensitive solution as in Example 1 using a spin coater to form a resist film It was applied to a thickness of about 10 μm. Then, it was dried at 80 ° C. for 10 minutes. An ultra high pressure mercury lamp (H
MW-532, manufactured by Oak Manufacturing Co., Ltd.)
Immediately after exposure at 0 mJ / cm ² , development was performed with a 1% aqueous sodium carbonate solution. After post-baking at 200 ° C. for 10 minutes, the substrate was treated with an aqueous ferric chloride solution (specific gravity: 1.506).
When spray-etching was performed at 50 ° C. for 5 minutes using, a good etching pattern was obtained. further,
When the resist film was immersed in a 20% aqueous sodium hydroxide solution at 60 ° C. for 4 minutes, the resist film was dissolved.

<Comparative Example 1> A reaction mixture containing 30 parts by weight of styrene, 35 parts by weight of butyl acrylate, 35 parts by weight of acrylic acid, and 3 parts by weight of azobisisobutyronitrile was kept at 110 ° C. in a nitrogen gas atmosphere. The mixture was added dropwise to 50 parts by weight of n-butanol and 40 parts by weight of methyl isobutyl ketone in a container over 3 hours. One hour after the addition, a mixture of 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of methyl isobutyl ketone was added dropwise over 1 hour. ) A solution was obtained. The resulting resin solution was reprecipitated in diethyl ether, filtered and dried, and then the copolymer (B-
1) was obtained. The modified copolymer (A-1) is converted to the copolymer (B
The same operation as in Example 1 was performed, except that the gray scale sensitivity was 4, and the resolution was 50.
μm, but the film thickness after development was 4 μm. Further, cracks occurred in the obtained cured film.

<Comparative Example 2> When the same operation as in Example 8 was performed using a photosensitive liquid using the same copolymer (B-1) as in Comparative Example 1, the etching liquid was removed from the periphery of the pattern during etching. Infiltration occurred, the resist film was partially peeled, and etching according to the pattern could not be performed.

[0053]

As described above, according to the present invention, the gray scale sensitivity is as high as 6 to 8 as compared with 4 in the comparative example under the same light amount, and as high as 40 μm or more with respect to the resolution of 50 μm in the comparative example. It is possible to provide a photosensitive resin composition which has high resolution and has good storage stability without causing cracks in a cured film observed in Comparative Examples, and an alkali-soluble polymer as a component thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 220/58 C08F 220/58 290/12 290/12 G03F 7/038 501 G03F 7/038 501 H01L 21 / 027 H01L 21/30 502R F-term (reference) 2H025 AA01 AA02 AA09 AA10 AB15 AC01 BC32 BC42 BC53 BC85 CA01 CA18 CA26 CA28 CA34 CA39 CA48 FA03 FA17 FA29 FA48 4J011 QA02 QA12 QA18 QA19 QA22 QA23 SA31SABSA SA SA87 UA01 WA01 4J027 AA02 AJ06 BA07 BA19 BA24 CB10 CC05 CD10 4J100 AB02P AJ02Q AL03P AM23R CA04 CA05 CA31 HA62 HC51

Claims (4)

[Claims] 1. An alkali-soluble polymer comprising a modified polymer represented by the following general formula (1) containing a segment having a carboxyl group. Embedded image 2. A copolymer containing a segment having a carboxyl group represented by the following general formula (2):
An alkali-soluble polymer which is a modified polymer having a vinyl group and a carboxyl group in a side chain obtained by reacting a compound having an isocyanate group with at least two ethylenic double bonds. Embedded image 3. A photosensitive resin comprising: (A) the alkali-soluble polymer according to claim 1 or 2; (B) a compound having an ethylenic double bond; and (C) a photopolymerization initiator. Composition. 4. An alkali-soluble polymer (A) in an amount of 50 to 95% by weight based on the whole photosensitive resin composition.
The photosensitive resin composition according to claim 3, comprising (B) 4 to 40% by weight of a compound having an ethylenic double bond and (C) 1 to 10% by weight of a photopolymerization initiator.