JP2594112B2 - Positive photosensitive resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel positive photosensitive resin composition, and more particularly, to a resin containing an iminosulfonate group, which is used for manufacturing printed wiring boards, integrated circuits, and the like. The present invention relates to a novel photosensitive resin composition useful for a resist for fine processing or a lithographic printing plate.

2. Description of the Related Art A so-called positive photosensitive resin, which becomes soluble by photodecomposition due to actinic radiation such as ultraviolet rays, generally has a higher resolution than a negative photosensitive composition, so it is used for manufacturing printed wiring boards and integrated circuits. Is widely used as an etching protection material. As these positive-type photosensitive resin compositions, those obtained by adding a quinonediazide compound to an alkali-soluble novolak resin are most common.However, since the material is a novolak resin made by a condensation polymerization method, there is a large variation in performance, Although the softening temperature is high despite the relatively low molecular weight, there is a problem that the resist film is brittle or the sensitivity is lower than that of the chloride type negative photoresist because a large amount of a quinonediazide compound is added.
As an attempt to improve these, a compound in which a quinonediazidosulfonyl group is incorporated into a dihydroxy compound (JP-A-58-182632) or a condensate of a bisphenol-type compound and quinonediazide-sulfonyl chloride (JP-A-58-182)
No. 58-203434) in combination with an alkali-soluble novolak resin to improve sensitivity. However, the disadvantages of using novolak resins have not been improved. In place of the alkali-soluble novolak resin, an acrylic resin having a number average molecular weight of 500 to 10,000 is used as a copolymer of a monoolefinic unsaturated compound and an α, β-ethylenically unsaturated carboxylic acid, and this may be combined with a quinonediazide compound. It has been proposed (JP-A-58-43451).
No.), uniform film performance, mechanical properties of resist,
There is a difficulty in controlling alkali developability, and it has not been put to practical use. Furthermore, in these technologies, the quinonediazide compound is dissolved in an organic solvent, but not in an aqueous alkali solution, and utilizes the property that the compound becomes indenecarboxylic acid via ketene by ultraviolet irradiation and becomes soluble in an aqueous alkali solution. However, since photodecomposition of quinonediazide is carried out by ultraviolet light having an absorption wavelength range of about 400 nm, there is a problem that high resolution cannot be expected with light in a short wavelength range.

In addition, as a positive photosensitive resin composition, a technique using a polymer having an ortho-nitrocarbinol ester group (for example, Japanese Patent Publication No. 58-2696, Japanese Patent Application Laid-Open No. 60-17445, etc.) or photodecomposition is used. A second photolysis reaction is used to solubilize the acid (see, for example,
-126236, JP-A-61-141442, etc.) are known. However, in the former, various types such as insufficient photosensitivity and in the latter, poor stability over time, etc. There are drawbacks, none of which have been put to practical use.

Problems to be Solved by the Invention Therefore, flexibility, based on a resin excellent in adhesion, excellent in stability over time, the absorption wavelength range to a shorter wavelength range, for example, 20
Positive photosensitive resin compositions that can be varied over a wide range from 0 nm to 400 nm currently in practical use, can be expected to have high resolution in a short wavelength range, and have excellent resolution have been demanded. It is an object of the present invention to meet the challenge.

Means for Solving the Problems According to the present invention, the object is to provide at least one compound represented by the formula (Wherein R ₁ and R ₂ are the same or different groups and each represents hydrogen,
An alkyl, acyl, phenyl, naphthyl, anthryl or benzyl group, or R ₁ and R ₂ can form an alicyclic ring together) The iminosulfonate group content in the range of 1.5 X 10 ^-4 ~ 2.5 X 10 ^-3 equivalents / g, does not contain a functional group that causes polymerization by the action of sulfonic acid generated by photolysis of the imino sulfonate group, It is achieved by a positive photosensitive resin composition comprising a gas resin selected from the group consisting of a polyester resin, an epoxy resin and an epoxidized polybutadiene resin having a number average molecular weight in the range of 700 to 5,000.

More specifically, the resin has an iminosulfonate group represented by the above formula (I) in at least one side chain or at the terminal of the main chain of a skeleton resin composed of a polyester resin, an epoxy resin, and a non-epoxidized polybutadiene resin. And
It does not contain a functional group that causes ring-opening polymerization with sulfonic acid, for example, a glycidyl group and an epithiopropyl group, and has an iminosulfonate group content in a resin molecule of 1.5 × 10 ^{−4 to} 2.5 × 10 ⁻³ equivalent.
/ g, preferably in the range of 2.5 × 10 ^{-4 to} 1.5 × 10 ^-3 ,
Expression by photolysis Is alkali-soluble when the group is removed.

Incidentally, it has been found that polyester resins, epoxy resins, and epoxidized polybutadiene resins for the above alkali-solubility purpose are usually particularly preferably those having a number-average molecular weight in the range of 700 to 5,000. Alternatively, the molecular weight is fluid due to the ratio with any other functional groups that can be present in these resins, and is essentially an alkali-insoluble polymer itself, which is used when the group of the formula (II) is released. Any of the above resins can be conveniently used as long as it is alkali-soluble at a practical dissolution rate and as long as an epoxy ring or the like which is subjected to ring-opening polymerization with sulfonic acid does not remain.

The resin according to the present invention is represented by the following formula: (Wherein R ₁ and R ₂ are as described above) are alkali-insoluble polymers having a photodegradable iminosulfonate group, and are new in that they do not contain a functional group that causes ring-opening polymerization with sulfonic acid. Resin. We have previously given the formula A vinyl resin having an iminosulfonate group represented by is soluble in a solvent such as tetrahydrofuran to form a film, and irradiated with ultraviolet light. The group was removed and the resulting sulfonic acid was polymerized by the cross-linking reaction of the glycidyl group to become solvent-insoluble, and was found to be useful as a negative photosensitive resin.Journal of Polymer Science Vol. 2
6, 119-124 (1986). In this study, the photodecomposition reaction of the above iminosulfonate group was further advanced. (Wherein R ₁ and R ₂ are as described above, respectively) The light absorption wavelength range of the iminosulfonate group represented by the formula is changed between about 200 and 400 nm by the substituents of R ₁ and R ₂ , It was found that by the removal of the group represented by the formula, the alkali-insoluble polymer can be converted to an alkali-soluble polymer as long as it does not contain a functional group that causes ring-opening polymerization with a sulfonic acid group in the molecule. The present invention was found to be extremely useful as a resin composition, and completed the present invention. still,
The resin of the present invention is clearly distinguished from the vinyl resin as the negative photosensitive material in that the resin does not contain a functional group that causes ring-opening polymerization with sulfonic acid in the molecule.

The resin according to the present invention has, for example, the formula (Wherein R ₁ and R ₂ are the same or different groups and each represents hydrogen,
Represents an alkyl, acyl, phenyl, naphthyl, anthryl or benzyl group, or R ₁ and R ₂ can form an alicyclic ring together) with hydroxylamine Obtain the expression A sulfonic acid halide having an α, β-ethylenically unsaturated bond in an oxime compound represented by the formula: CH ₂ CHCH—Y—SO ₂ X (V) (where X is a halogen, Y is an organic group) is a base, for example Formula obtained by reacting in the presence of pyridine, (Wherein R ₁ , R ₂ , and Y are each as described above) by using a monomer having an iminosulfonate group represented by the following formula: That is, a polyester resin can be obtained by subjecting the above-mentioned monomer having an iminosulfonate group to an addition reaction with an unsaturated polyester resin obtained using a polybasic acid having an unsaturated group, and in the case of epoxy resin and epoxidized polybutadiene resin Can be conveniently prepared by, for example, reacting an acrylic acid or the like with an epoxy group to introduce an α, β-ethylenically unsaturated bond, and then subjecting the monomer having an iminosulfonate group to an addition reaction.

The sulfonic acid halide represented by the formula (V) is a compound having an α, β-ethylenically unsaturated bond and a sulfonic acid that is easily available or easily synthesized, for example, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, Method of reacting phosphorus pentachloride with vinyl sulfonic acid or potassium salt of 2-acrylamido-2-methylpropanesulfonic acid (Journal of Polymer Science 2)
1 , 781 (1985)).

As the oxime represented by the formula (IV), various compounds are known, and for example, the following compounds are advantageously used. 2-propanone oxime, acetoaldoxime, methyl ethyl ketoxime, 3-heptanone oxime, cyclohexanone oxime, 1,2-cyclohexanedione dioxime, biacetyl monooxime, acetophenone oxime, P-chloroacetophenone oxime, P-nitroacetophenone oxime , O-nitroacetophenone oxime, P-methylacetophenone oxime, P-
Phenylacetophenone oxime, benzophenone oxime, methyl α-naphthyl ketoxime, 9-anthrylbenzyl ketoxime, tetralone oxime, fluorenone oxime and the like. Instead of using the above-mentioned monomer having an iminosulfonate group, the resin according to the present invention is:
For example, it can be produced by halogenating a resin having a sulfone group at the side chain or at the terminal of the main chain, followed by reaction with an oxime compound represented by the formula (IV).

As described above, the resin according to the present invention has the formula The iminosulfonate group represented by 1.5 × 10 ^{-4 in the} molecule
~ 2.5 × 10 ^-3 eq / g, preferably 2.5 × 10 ^{-4 to} 1.5 × 10 ^-3
Equivalent / g must be included. This is because if the amount of iminosulfonate group is less than this range, the solubility of the resin will be low when treated with an Ali Ali solution after photolysis, and if it is more than the above range, the solubility will be excessive, resulting in a sharp increase in contrast. It is not possible.

The resin of the present invention must not contain a functional group that causes ring-opening polymerization with sulfonic acid, such as a glycidyl group and an epithiopropyl group, as a pendant group. This is because, when such a group is present, the sulfonic acid group generated by photolysis serves as a catalyst, and the functional group does not dissolve in an alkali developing solution due to a ring opening reaction and cannot be used as a positive photosensitive resin. . A sulfonic acid group that does not cause ring-opening polymerization can of course be arbitrarily present in the resin.

The resin of the present invention also When the group is separated, a sulfonic acid is generated and the alkali-soluble substance is obtained. Such solubility is preferably controlled mainly by the molecular weight of the skeletal resin used,
In the case of polyester, epoxy, and epoxidized polybutadiene resin with a number average molecular weight, the purpose can be achieved with about 700 to 5000, and those having a molecular weight range of such as resin flowability, alkali solution solubility after photolysis, etc. It is particularly preferred in that respect.

When using a functional group containing an amino group, after photolysis,
Acid development can be performed.

All of the resins of the present invention are exposed to actinic radiation. Is decomposed into -SO ₃ H And the characteristic that the light absorption maximum wavelength can be freely selected within the range of about 200 to 400 nm depending on the type of the oxime, that is, the absorption maximum when, for example, 2-propanone oxime is selected as the oxime. 190 nm; 192 nm for cyclohexanone oxime; 237 nm for 1,2-cyclohexanedione dioxime; 228 nm for biacetyl monooxime; 242 nm for acetophenone oxime; 252 nm for benzophenone oxime; 254 n for fluorenone oxime
m; 360 nm; tetralone oxime has a different maximum absorption maximum region such as 254 nm, so that the resin can be selected according to the exposure equipment. A positive image can be obtained.

The photosensitive resin composition of the present invention is prepared by dissolving in various solvents. Examples of the solvent include glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. Cellosolve esters; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; and esters such as ethyl acetate and butyl acetate.

The phenomenon liquid of the photosensitive resin composition of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium metasilicate; primary amines such as ethylamine and n-propylamine; diethanolamine and diethanolamine. Secondary amines such as -n-propylamine; tertiary amines such as triethylamine and triethanolamine; aqueous solutions of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; For acid development, an acidic aqueous solution of acetic acid, oxalic acid, citric acid, boric acid, phosphoric acid or the like is used.

All the resin compositions according to the present invention are rich in flexibility,
Therefore, excellent adhesion to the substrate, excellent stability over time because the photosensitive group is incorporated in the resin, absorption wavelength 200 ~ 400
Positive photosensitive resin composition that can be changed freely down to nm and has high resolution in the short wavelength range and excellent resolution. Fine resist in the manufacture of integrated circuits for printed wiring boards, photosensitive material in lithographic printing plates Is extremely useful.

Hereinafter, the present invention will be described with reference to examples. All parts and percentages used in the examples are by weight unless otherwise stated.

Synthesis Example 1 a) Synthesis of tetralone oxime p-styrene sulfonate 250 parts of pyridine in a separable flask having an internal volume of 500 ml,
Add 96 parts of tetralone oxime, cool to 10 ° C or less,
120 parts of styrenesulfonyl chloride are gradually dropped, and 2
The reaction was performed at 0 ° C. or lower for 3 hours. 250% of 5% hydrochloric acid in ice water
After 0 parts of the mixture was dropped and stirred, and 500 parts of chloroform was added for extraction, the solvent was decompressed and removed to obtain a reaction product. From IR and NMR spectra, it was confirmed that the product was tetralone oxime p-styrene sulfonate.

b) Synthesis of polyester resin having iminosulfonate group Maleic anhydride 7 was placed in a separable flask having an internal volume of 1.
3.5 parts, adipic acid 110 parts, neopentyl glycol 295
1 part, xylene 14 parts and dibutyltin oxide 0.2 part
After the temperature was raised to 40 ° C and maintained for 1 hour, the internal temperature was raised to 200 ° C over 3 hours, and the reaction was continued until the acid value of the carboxylic acid reached 20. After the temperature was lowered to 80 ° C., 160 parts of xylene and 80 parts of ethylene glycol monobutyl ether were added, and 20 parts of styrene separately prepared and 140 parts of tetralone oxime p-styrene sulfonate obtained in the above a), t-butyl peroxy 9 parts of 2-ethylhexanoate and di-t-
A mixed solution of 4.5 parts of butyl peroxide was added dropwise and reacted at 140 ° C. for 3 hours to obtain a modified polyester resin having an imisulfonate group having a molecular weight of about 3200 and a solid content of 70.4%.

Synthesis Example 2 a) Acetophenone oxime 2-acrylamide-2-
Synthesis of Methylpropanesulfonate Synthesis Example 1 in which Synthesis Example 1 a) was replaced with 96 parts of terolalone oxime and 81 parts of acetophenone oxime, and 120 parts of p-styrenesulfonyl chloride with 140 parts of 2-acrylamide-2-methylpropanesulfonyl chloride.
By performing the same operation as in a), acetophenone oxime 2-acrylamido-2-methylpropanesulfonate was obtained.

b) Synthesis of polyester resin having iminosulfonate group Maleic anhydride 7 was placed in a separable flask having an internal volume of 2.
3.5 parts, azelaic acid 141 parts, hydrogenated bisphenol A240
Parts, 1.6 parts of hexanediol, 118 parts of xylene, and 20 parts of xylene, and 0.1 part of dibutyltin oxide. The mixture was heated to 140 ° C and maintained for 1 hour. Then, the internal temperature was raised to 200 ° C over 3 hours, and the acid value of the carboxylic acid was increased. The reaction continued until the number reached 30. After the temperature was lowered to 80 ° C., 200 parts of xylene and 90 parts of ethylene glycol monobutyl ether were added, and 20 parts of styrene prepared separately and 162 parts of acetophenoxime 2-acrylamide 2-methylpropane sulfonate obtained in the above a) were added. 9 parts of -butylperoxy 2-ethylhexanoate and di-t-
A mixture of 4.5 parts of butyl peroxide was added dropwise and reacted at 140 ° C. for 3 hours to obtain a modified polyester resin having an iminosulfonate group having a molecular weight of about 3000 and a solid content of 70.0%.

Synthesis Example 3 b) Synthesis of epoxy resin having iminosulfonate group In a separable flask having an internal volume of 1, 150 parts of ethylene glycol monoethyl ether acetate, epoxy equivalent of 950
285 parts of bisphenol A type epoxy resin
After dissolving at 50 ° C. and lowering the temperature to 100 ° C., 26 parts of methacrylic acid, 3 parts of tetramethylammonium chloride and 0.02 part of hydroquinone were added and reacted for 2 hours. The temperature was lowered to 80 ° C., and a mixture of 67 parts of methyl ethyl ketoxime methallyl sulfonate obtained in Synthesis Example 5a), 150 parts of dioxane and 5 parts of azobisisobutyronitrile was added dropwise over 2 hours. An epoxy resin having a solid content of 55.1% and having iminosulfonate groups was obtained.

Synthesis Example 4 b) Synthesis of epoxy resin having iminosulfonate group In a separable flask having an internal volume of 1, 200 parts of ethylene glycol monoethyl ether acetate, an epoxy equivalent of 1
380 parts of bisphenol A type epoxy resin 900 were added and dissolved at 150 ° C., the temperature was lowered to 100 ° C., and 18 parts of methacrylic acid, 3 parts of tetramethylammonium chloride and 0.02 part of hydroquinone were added and reacted for 2 hours. 80 ℃
Tetralone oxime p-styrene sulfonate 66
, A mixture of 150 parts of dioxane and 5 parts of azobisisobutyronitrile was added dropwise over 2 hours.
An epoxy resin having an iminosulfonate group having a solid content of 56.4% was obtained.

Synthesis Example 5 b) Synthesis of epoxy resin having iminosulfonate group In a separable flask having an internal volume of 1, 180 parts of ethylene glycol monoethyl ether acetate, epoxy equivalent of 9
50 bisphenol A type epoxy resin (285 parts) was added and dissolved at 150 ° C., the temperature was lowered to 100 ° C., and acrylic acid (22 parts), tetramethylammonium chloride (3 parts) and methoquinone (0.02 part) were added and reacted for 2 hours. The temperature was lowered to 80 ° C., and a mixture of 97 parts of acetophenoxime 2-acrylamido-2-methylpropanesulfonate obtained in Synthesis Example 2a), 140 parts of dioxane and 5 parts of azobisisobutyronitrile was added dropwise over 2 hours. After that, an epoxy resin having a molecular weight of about 2000 and a solid content of 55.2% and having imisulfonate groups was obtained.

Synthesis Example 6 b) Synthesis of polybutadiene resin having iminosulfonate group To a separable flask having an internal volume of 1, 435 parts of Idemitsu polybutadiene R-45EPT (epoxidized polybutadiene manufactured by Idemitsu Petrochemical Co., Ltd.) and 150 parts of ethylene glycol monomethyl ether acetate were added. The mixture was dissolved at 100 ° C., and 22 parts of acrylic acid, 3 parts of teramethylammonium chloride, and 0.02 part of hydroquinone were added and reacted for 2 hours. The temperature was lowered to 80 ° C and the chlorenone oxime p-styrene sulfonate 120
, 150 parts of dioxane and 5 parts of azobisisobutyronitrile were added dropwise over 2 hours, and then a molecular weight of about 40 parts was obtained.
A polybutadiene resin having an iminosulfonate group having a solid content of 65.2% was obtained. Synthesis Example 7 b) Synthesis of a polybutadiene resin having an iminosulfonate group Idemitsu polybutadiene R-45EPT (manufactured by Idemitsu Petrochemical Co., Ltd.) , 290 parts of epoxidized polybutadiene) and 150 parts of ethylene glycol monoethyl ether acetate were added and dissolved at 100 ° C, and 17 parts of methacrylic acid, 2 parts of tetramethylammonium chloride, and 0.02 parts of hydroquinone were added and reacted for 2 hours. The temperature was lowered to 80 ° C. and benzophenone oxime p-styrene sulfonate 73 was used.
, A mixture of 150 parts of dioxane and 4 parts of azobisisobutyronitrile was added dropwise over 2 hours, and then a molecular weight of about 36 was obtained.
A polybutadiene resin having an iminosulfonate group having a solid content of 55.4% was obtained.

Example 1 40 parts of the modified polyester resin having an iminosulfonate group obtained in Synthesis Example 1b) was dissolved in a mixed solvent of 40 parts of ethylene glycol monoethyl ether and 40 parts of methyl ethyl ketone, and the solution was filtered through a Millipore filter having a pore size of 0.2 μm. A photosensitive solution was prepared. The photosensitive solution thus prepared was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to form a film having a thickness of 1.3 μm.
Was obtained.

A line-and-space pattern was adhered to the photosensitive layer, irradiated with a low-pressure mercury lamp having a light intensity of about 10 mW / cm ² at 254 nm for 60 seconds, and developed with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds. However, by observation with an electron microscope, it was resolved to a line and space of 0.8 μm, and no peeling or cracking of the resist was observed. When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 2 40 parts of the modified polyester resin having an iminosulfonate group obtained in Synthesis Example 2b) was dissolved in a mixed solvent of 40 parts of ethylene glycol monoethyl ether and 40 parts of methyl ethyl ketone, and the solution was filtered through a Millipore filter having a pore size of 0.2 μm. A photosensitive solution was prepared. The photosensitive solution thus prepared was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to form a film having a thickness of 1.3 μm.
Was obtained.

Adhere a line and space pattern to this photosensitive layer
The low-pressure mercury lamp light intensity at 254nm is about 10 mW / cm ² 6
Irradiation for 0 second and development with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds revealed that the film was developed to a line and space of 0.9 μm by observation with an electron microscope, and that no peeling or cracking of the lens was observed. When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 3 40 parts of the epoxy resin having an iminosulfonate group obtained in Synthesis Example 3b) was dissolved in a mixed solvent of 24 parts of ethylene glycol monoethyl ether and 24 parts of methyl ethyl ketone,
A photosensitive solution was prepared by filtration through a millipore filter having a pore size of 0.2 μm. The photosensitive solution thus prepared was applied to a silicon oxide film wafer using a spinner, and then heated to 80 ° C.
And dried in an oven for 10 minutes to obtain a coating film having a thickness of 1.2 μm.

Adhere a line and space pattern to this photosensitive layer
1 low-pressure mercury lamp light intensity at 254nm is about 10 mW / cm ²
Irradiation for 00 seconds and development with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, the image was resolved to 0.6 μm line ad space by observation with an electron microscope, and no peeling or cracking of the resist was observed. . When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 4 40 parts of the epoxy resin having an iminosulfonate group obtained in Synthesis Example 4b) was dissolved in a mixed solvent of 24 parts of ethylene glycol monoethyl ether and 24 parts of methyl ethyl ketone, and the solution was filtered through a Millipore filter having a pore diameter of 0.2 μm and exposed to light. A liquid was prepared. The thus prepared photosensitive solution was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to obtain a coating film having a thickness of 1.2 μm.

Adhere a line and space pattern to this photosensitive layer
The low-pressure mercury lamp light intensity at 254nm is about 10 mW / cm ² 6
Irradiation for 0 second, and development with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, the image was resolved to 0.8 μm line and space by observation with an electron microscope, and no peeling or cracking of the resist was observed. . When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 5 40 parts of the epoxy resin having an iminosulfonate group obtained in Synthesis Example 5b) was dissolved in a mixed solvent of 24 parts of ethylene glycol monoethyl ether and 24 parts of methyl ethyl ketone, and the solution was filtered through a 0.2 μm pore diameter Millipore filter and exposed. A liquid was prepared. The photosensitive solution thus prepared was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to obtain a film having a thickness of 1.3 μm.

Adhere a line and space pattern to this photosensitive layer
The low-pressure mercury lamp light intensity at 254nm is about 10 mW / cm ² 6
Irradiation for 0 second, and development with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, the image was resolved to 0.8 μm line and space by observation with an electron microscope, and no peeling or cracking of the resist was observed. . When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 6 40 parts of the polybutadiene resin having an iminosulfonate group obtained in Synthesis Example 6b) were dissolved in a mixed solvent of 32 parts of ethylene glycol monoethyl ether and 32 parts of methyl ethyl ketone, and the solution was filtered through a Millipore filter having a pore size of 0.2 μm and exposed to light. A liquid was prepared. The photosensitive solution thus prepared was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to obtain a film having a thickness of 1.3 μm.

A line-and-space pattern is adhered to this photosensitive layer, and a high-pressure mercury lamp with a 365 nm light intensity of about 5 mW / cm ² is used.
Irradiation for 40 seconds and development with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds resulted in resolution to 0.8 μm line and space by observation with an electron microscope, and no peeling or cracking of the resist was observed. . When the photosensitive solution was evaluated for three months, the same results as above were obtained.

Example 7 40 parts of the polybutadiene resin having an iminosulfonate group obtained in Synthesis Example 7b) was dissolved in a mixed solvent of 24 parts of ethylene glycol monoethyl ether and 24 parts of methyl ethyl ketone, and the solution was filtered through a Millipore filter having a pore size of 0.2 μm and exposed to light. A liquid was prepared. The photosensitive solution thus prepared was applied on a silicon oxide film wafer using a spinner, and then dried in an oven at 80 ° C. for 10 minutes to obtain a film having a thickness of 1.3 μm.

A line-and-space pattern was adhered to the photosensitive layer, irradiated with a high-pressure mercury lamp having a light intensity at 254 nm of about 10 mW / cm ² for 60 seconds, and developed with a 2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds. However, by observation with an electron microscope, it was resolved to a line and space of 0.9 μm, and no peeling or cracking of the resist was observed. When the photosensitive solution was evaluated after lapse of three months, the same results as above were obtained.

Continuation of the front page (72) Inventor Katsumi Ishikawa 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (56) References JP-A-61-251652 (JP, A) JP-A-1-124848 (JP) , A)

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein at least one
Two expressions (Wherein R ₁ and R ₂ are the same or different groups and each represents hydrogen,
An alkyl, acyl, phenyl, naphthyl, anthryl or benzyl group, or R ₁ and R ₂ can form an alicyclic ring together) The iminosulfonate group content in the range of 1.5 X 10 ^-4 ~ 2.5 X 10 ^-3 equivalents / g, does not contain a functional group that causes polymerization by the action of sulfonic acid generated by photolysis of the imino sulfonate group, A positive photosensitive resin composition comprising a gas resin selected from the group consisting of a polyester resin, an epoxy resin, and an epoxidized polybutadiene resin having a number average molecular weight in the range of 700 to 5,000.