JP2003131369A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new negative photosensitive resin composition developable with a dilute alkali solution and having good resolution, excellent etching resistance and such good removability that it is dissolved in an aqueous alkali solution. SOLUTION: The photosensitive resin composition comprises (A) an alkali- soluble copolymer having a terminal ethylenically unsaturated group and a carboxyl group in a side chain, (B) one or more of the photopolymerizable compounds of formula (1) having at least one polymerizable ethylenically unsaturated group in one molecule and (C) a photopolymerization initiator. In the formula (1), R1 is H or methyl; m is 0, 1 or 2; and R2 is alkylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition applicable to photoresists, etching resists, pigment-dispersed resists, printing industry, electronics. It is widely used in industries.

[0002]

2. Description of the Related Art Conventionally, resin components (binders, reactive binders, reactive monomers or mixtures thereof), photoinitiators, sensitizers have been used in the printing industry, paint / ink industry, metalworking industry, electronics industry, etc. A photosensitive resin composed of a crosslinking agent has been widely used. The main applications are photoresists for metal partial etching, photoresists for manufacturing precision electronic circuits such as LSI,
Examples include a photosensitive resin for producing a resin plate for printing, an ink for screen printing, and a colored photoresist for producing a color filter. In recent years, with the demand for higher performance, photosensitive resins with high resolution and high sensitivity for forming finer patterns have been desired, and various types of photosensitive resins with different characteristics are commercially available on the market. Has been done.

There are two types of the above-mentioned photosensitive resins, a positive type resist in which an exposed portion is removed and a positive pattern is obtained during development processing, and a negative type resist in which an unexposed portion is removed and a negative pattern is obtained. is there. Generally, the negative type is superior to the positive type in sensitivity, adhesion to a substrate, and chemical resistance, and the positive type is superior to the negative type in resolution and dry etching resistance.

When a circuit is produced by partially etching a metal foil or the like or a printing resin plate is produced using this negative photosensitive resin, the following steps are used. A negative mask is placed on the thin film of the coated photosensitive resin composition, the exposed portion is cured by light irradiation through the negative mask, and the non-exposed portion is removed by washing, and then the exposed metal portion is exposed to an etching solution. A circuit is produced by elution by immersion. Further, the printing process does not require an etching step.

The 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 its molecular structure,
Some include a photopolymerization initiator and a photocrosslinking agent. Many of the characteristics of such a photosensitive resin composition are those which are developed using an organic solvent, which is not preferable from the viewpoint of environmental protection, and its use has been a problem.

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

Under these circumstances, a photosensitive resin obtained by reacting a vinyl compound having an aliphatic epoxy group such as glycidyl (meth) acrylate mainly with a high acid value acrylic resin whose properties are relatively easily improved is Developed, JP 1
-139619, JP-A-3-172301, JP-A-3-280059, JP-A-10-77.
No. 47, JP-A No. 11-327139, and the like. Further, 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 is particularly Japanese Patent Laid-Open No. 6-138659 and Japanese Patent Laid-Open No.
Nos. 0-10726 and 10-176614 are proposed. It is described that this resin has good curability, adhesion, and water resistance, and that the surface tackiness after drying the coating film is remarkably lower than that of conventional resins. Further, as the etching resist, it is necessary to remove the resist after the etching is completed, but since many resists form a permanent film represented by a solder resist, it is not easy to remove the film.

[0008]

The object of the present invention is that it can be developed using an alkaline aqueous solution, has high sensitivity and high resolution, is tack-free, and has good etching resistance when used as an etching resist. Moreover, it is to provide a photosensitive resin composition capable of easily dissolving and removing the resist.

[0009]

According to the invention of claim 1,
At least one of (A) an alkali-soluble copolymer having a terminal ethylenically unsaturated group and a carboxyl group in its side chain and (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule A photosensitive resin composition, characterized in that at least one kind comprises a photopolymerizable compound (C) photopolymerization initiator represented by the following formula (1).

[0010]

[Chemical 2]

In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents a value of 0 or 1 or 2, and R ₂ represents an alkylene group. The invention according to claim 2 is such that (A) the alkali-soluble polymer is 50 to 95% by weight, (B) the photopolymerizable compound is 4 to 40% by weight, and (C) the photopolymerization with respect to the entire photosensitive resin composition. The photosensitive resin composition according to claim 1, further comprising 1 to 10% by weight of an initiator. The invention of claim 3 is characterized in that the photopolymerizable compound (B) contains the photopolymerizable compound represented by the general formula (1) in an amount of 1 to 20% by weight based on the whole photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 2, wherein

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The (A) alkali-soluble polymer used in the present invention is obtained by reacting a copolymer containing a segment having a carboxyl group with an epoxy compound having one or more ethylenic double bonds in one molecule, It is a modified polymer having a vinyl group and a carboxyl group in the side chain. The copolymer containing the segment having a carboxyl group,
Specifically, a methacrylic acid-acrylic acid ester copolymer, a methacrylic acid-methacrylic acid ester copolymer, an acrylic acid-acrylic acid ester copolymer, a methacrylic acid-acrylic acid ester copolymer and the like can be mentioned. More specifically, as the ester moiety, methyl, ethyl, n
-Butyl, tetrahydrofurfuryl, benzyl, phenyl ester and the like can be mentioned, but not limited thereto.

The weight average molecular weight of the (A) alkali-soluble polymer is about 1,000 or more, about 100,0.
It is preferably 00 or less, and when it is smaller than this, the strength of the cured film is remarkably lowered, and when it is larger than this, the solubility is lowered and the preparation of the resist becomes difficult, which is not preferable. Considering sensitivity and resolution, the weight average molecular weight is more preferably in the range of 5,000 or more and 20,000 or less. Further, it is preferably in the range of 59 to 95% by weight with respect to the entire photosensitive resin composition.

The acid value (according to JIS K-1557) of the alkali-soluble polymer (A) used in the present invention is 50 to 2
It is preferably in the range of 00 mgKOH / g. When the acid value is 50 mgKOH / g or less, it becomes difficult to remove the uncured composition during development with a dilute alkaline aqueous solution. on the other hand,
When the acid value is 200 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 deteriorate.

The formula (1) which is essential as the photopolymerizable compound (B) having an ethylenically unsaturated group used in the present invention.
The compound represented by is obtained by esterifying an aromatic tetracarboxylic dianhydride and an alcohol compound having an ethylenic double bond. This component is an esterification of an aromatic tetracarboxylic dianhydride and an alcohol compound having an ethylenically unsaturated group under the condition that the carboxylic acid group derived from the aromatic tetracarboxylic dianhydride remains in the product. It is a compound obtained by reacting. As the esterification reaction product, 2 mol of an alcohol compound having an ethylenic double bond reacts with 1 mol of an aromatic tetracarboxylic dianhydride to have an ester bond in the molecule, and the remaining carboxylic acid. A compound having an acid group, that is, a product having two half-esters in the molecule is preferable. Examples of the aromatic tetracarboxylic dianhydride used include pyromellitic dianhydride.

As the alcohol compound having an ethylenic double bond, 2-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polycaprolactone-modified methacrylate, polycaprolactone-modified acrylate and the like can be mentioned. In addition, in use, one kind or a mixture of two or more kinds may be used.

The resulting esterification reaction product is a product having two half-esters in the molecule or a mixture containing the ester and tri- and tetra-esters, an alcohol used in excess, and the like. The obtained esterification reaction product may be used as it is as the component (B) or may be used in the molecule.
Isolate the product with one half ester (B)
You may use it as an ingredient.

In addition to these, generally commercially available monomers capable of radical polymerization can be mixed and used. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, methacrylamide,
High-boiling-point vinyl monomers such as diacetone acrylamide and ethylene bis acrylamide, as well as methanol,
Ethanol, 1-pronol, 1-butanol, 2-ethylhexanol, mono (meth) acrylic esters such as ethylene glycol, ethylene glycol,
Examples thereof include, but are not limited to, di- or poly (meth) acrylic acid esters such as diethylene glycol, polyethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol.

The (C) photopolymerization initiator used in the present invention is
It is a photopolymerization initiator that generates radical species by actinic radiation, and specifically includes benzoin alkyl ethers such as benzoin isopropyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-. 2-methyl-
Α-Hydroxyketones 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-trimethylpentylphosphonoxide; 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-
Bisimidazoles such as 1,1′-biimidazole and bis (2,4,5-triphenyl) imidazole, 2,4
-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 Starting with organic peroxides such as'-tetra (tert-butylperoxycarboxyl) benzophenone, J. Photochem. Sci. T
echnol. , 2,283 (1987). Examples of the compounds described in 1., iron iron complex, trihalogenomethyl-substituted s-triazine, sulfonium salt, diazonium salt, phosphonium salt, selenonium salt, arsonium salt, iodonium salt and the like. Furthermore, if necessary, benzophenones such as Michler's ketone,
A sensitizer such as thioxanthones may be added.

The photopolymerizable compound (B) having an ethylenic double bond contained in the photosensitive resin composition of the present invention is
It can be in the range of 2 to 50% by weight, preferably 4 to 40% by weight, based on the entire photosensitive resin composition. If the addition amount is more than this, the surface tackiness of the photosensitive resin composition increases, and problems such as inability to perform contact exposure of the mask occur. On the other hand, if it is less than the above range, a sufficient crosslink density of the cured product cannot be obtained, so that cracks and splits are likely to occur after development, and problems occur when it is applied to an etching resist. More preferably, the amount of the monomer represented by the formula (1) is preferably 1 to 20 parts by weight. Below this, the alkali solubility of the resist film after etching, which is the object of the present invention, remarkably decreases and the dissolution residue and insoluble matter are reduced. It often occurs. Further, if it is more than this, there are many cases where problems such as outflow of patterns and floating occur in the developing process. More preferably, it has 10 to 25
By mixing and using parts by weight of the polyfunctional photopolymerizable monomer, a fine pattern having good alkali developability and etching resistance can be obtained. further,
The amount of the (C) photopolymerization initiator can be in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the entire photosensitive resin composition. The addition amount is limited by the film thickness of the photosensitive resin to be formed and the optical density of the film thickness, so it is desirable to use it in the range where the optical density does not exceed 2. The total of the respective weight% of the (A) alkali-soluble polymer, (B) photopolymerizable compound having an ethylenic double bond, and (C) photopolymerization initiator is 100%.

In addition to the above components, the photosensitive resin composition of the present invention may optionally contain compatible additives such as a polymerization inhibitor, a plasticizer, a stabilizer, a surfactant, a colorant, a leveling agent, A coupling agent and the like can be added within a range that does not impair the object of the present invention.

As described above, the photosensitive solution obtained by appropriately selecting the respective components and mixing them at an arbitrary ratio is publicly known as a bar coater, applicator, doctor blade, roll coater, spin coater, roll coater, die coater, comma coater and the like. It is applied to a metal substrate such as zinc, iron, copper, aluminum, or an alloy thereof, or a metal vapor-deposited plate, glass, a substrate such as a plastic film typified by polyester, by using the coating means. The substrate may be surface-treated by heat treatment, surface polishing, etching, chemicals or the like to improve its characteristics.

When the photosensitive solution is prepared, it may be diluted with a suitable solvent if necessary, but in that case, it is necessary to dry after coating on the substrate. As the solvent,
Dichloromethane, chloroform, acetone, 2-butanone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxyacetate, 2-butoxyethylacetate, 2-methoxyethylether,
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 can be mentioned.

The film thickness varies depending on the application field, but usually 1
It is preferable that the thickness is in the range of 70 μm. Then, the obtained coated material is dried at room temperature or with a heater to form a photosensitive layer. The drying temperature may be a temperature at which the composition and the substrate are not deteriorated, for example, 120 ° C.

On the photosensitive layer formed by the above method,
A photomask having a predetermined pattern is brought into close contact, and exposed to, for example, 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., and the light-irradiated portion is polymerized or cross-linked, followed by dilute alkali development. By developing with a liquid, an image faithful to the mask pattern can be obtained.

Specific examples of the alkaline component of the dilute aqueous alkaline solution used in the present invention include hydroxides, carbonates and bicarbonates 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, trimethyl Examples include phenylammonium hydroxide, ammonium hydroxides such as choline, trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, sulfonium hydroxides such as dimethylbenzylsulfonium hydroxide, and mixtures of these alkaline components and buffer solutions. Yes these one
One kind or a mixture of two or more kinds can be used.

The amount of the alkali component used in the dilute alkaline aqueous solution for development is not particularly limited as long as it is a dilute alkali. For example, a 0.5 to 5 wt% sodium carbonate aqueous solution is usually used as the dilute alkaline aqueous solution. As described above, the resist pattern film subjected to the development treatment may be further subjected to a temperature of 100 to 250 ° C. for 1 minute to 3 minutes, if necessary.
Post bake for about an hour. This makes it possible to further accelerate the polymerization and curing of the cured film and improve heat resistance, etching resistance, adhesion and the like.

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

The embodiments of the present invention will be described below 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 to unnecessary light such as natural light, all work is performed in yellow,
It goes without saying that it is done under a red light.

[0030]

EXAMPLES Detailed examples will be shown below.

<Synthesis Example 1: A-1> 10.9 g of pyromellitic dianhydride was placed in a flask having an internal volume of 100 ml.
-Hydroxyethyl acrylate 11.6 g, paratoluenesulfonic acid monohydrate 0.3 g, 4-methoxyphenol 11 mg, and N, N-dimethylformamide
40 ml was charged. In a nitrogen atmosphere, the reaction was carried out at 65 ° C. for 6.5 hours with stirring. The reaction mixture was poured into 800 ml of water, and the product was extracted with 200 ml of chloroform. After washing twice with water, the mixture was concentrated with an evaporator. Furthermore, it was dried at 45 ° C. under a reduced pressure of about 1 mmHg for 7.5 hours to obtain 27.8 g of the target product as a colorless liquid. <Synthesis example 2: A-2>

In a flask having an internal volume of 100 ml, 10.9 g of pyromellitic dianhydride and lactone-modified methacrylate (Plaxel FM1D manufactured by Daicel Chemical Co., Ltd.) 2
5.0 g, 0.3 g of paratoluenesulfonic acid monohydrate,
13 mg of 4-methoxyphenol and 40 ml of N, N-dimethylformamide were charged. Under a nitrogen atmosphere,
The mixture was reacted at 65 ° C. for 6.5 hours with stirring. After cooling to room temperature, 200 ml of methylene chloride was added and washed with water twice. The methylene chloride layer was dried over anhydrous sodium sulfate and then concentrated by an evaporator. Furthermore, about 1 mmHg
It was dried under reduced pressure at 50 ° C. for 7.5 hours to obtain 32.9 g of a liquid target product.

<Synthesis Example 3: A-3> In a flask having an inner volume of 100 ml, 10.9 g of pyromellitic dianhydride and pentaerythritol triacrylate (Aronix M
-305 Toa Gosei Co., Ltd.) 14.9 g, 2-hydroxyethyl acrylate 5.8 g, triethylamine 0.1.
g, 4-methoxyphenol 17 mg, and N, N-
13.5 g of dimethylformamide was charged. Under a nitrogen atmosphere, the reaction was carried out at 65 ° C. for 8 hours with stirring. After cooling to room temperature, it was subjected to evaluation without any particular purification.

<Synthesis Example 4: A-4> In a flask having an internal volume of 100 ml, 10.9 g of pyromellitic dianhydride, 36.6 g of lactone-modified methacrylate (Placcel FM2D, manufactured by Daicel Chemical Industries, Ltd.), and triethylamine 0.1.
g, 4-methoxyphenol 17 mg, and N, N-
20.3 g of dimethylformamide was charged. Under nitrogen atmosphere, the reaction was carried out at 65 ° C. for 7 hours with stirring. After cooling to room temperature, it was subjected to evaluation without particular purification.

<Synthesis Example 5: A-5> In a flask having an internal volume of 100 ml, 10.9 g of pyromellitic dianhydride, 34.3 g of lactone-modified acrylate (Placcel FA2D manufactured by Daicel Chemical Co., Ltd.), 0.1 g of triethylamine,
17 mg of 4-methoxyphenol and 19.4 g of N, N-dimethylformamide were charged. Under a nitrogen atmosphere, the reaction was carried out at 65 ° C. for 8 hours with stirring. After cooling to room temperature, it was subjected to evaluation without particular purification.

<Comparative Synthesis Example 1: A-6> Internal volume 100 m
In a 1-liter flask, 11.6 g of 2-hydroxyethyl acrylate, 10.1 g of triethylamine, 11 mg of 4-methoxyphenol, and 3 parts of tetrahydrofuran.
0 ml was charged. 10.2 g of phthalic acid dichloride was added over 30 minutes at room temperature under nitrogen atmosphere and stirring.
The temperature was raised to 55 ° C., and the reaction was further performed for 2.5 hours. After cooling to room temperature, 200 ml of diethyl ether was added and washed with water twice. The ether layer was dried over anhydrous sodium sulfate and then concentrated by an evaporator. The obtained liquid substance was separated and purified with a silica gel column using ethyl acetate as an outflow liquid to obtain 14.6 g of a pale yellow liquid.

<Example 1> As a component (A), a modified copolymer resin (ACA-200M, manufactured by Daicel Chemical Industries, Ltd.) 7
0 parts by weight (solid content conversion value), as the component (B), dipentaerythritol hexaacrylate (Aronix M-
400, Toa Gosei Co., Ltd. 21 parts by weight, 9 parts by weight of the compound (A-1) of Synthesis Example 1 (C) 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopro 2 parts by weight of pan-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals) and 1 part by weight of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) were dissolved in propylene glycol monomethyl ether. Then, a photosensitive resin composition was obtained.

Example 2 As component (B), dipentaerythritol hexaacrylate (Aronix M-4
00, manufactured by Toagosei Co., Ltd.) 15.9 parts by weight, Synthesis Example 2
A photosensitive resin composition was obtained in the same manner as in Example 1 except that 14.1 parts by weight of the compound (A-2) in Example 1 was used.

<Example 3> As the component (B), dipentaerythritol hexaacrylate (Aronix M-4
00, manufactured by Toagosei Co., Ltd.) 17.4 parts by weight, Synthesis Example 3
A photosensitive resin composition was obtained in the same manner as in Example 1 except that 12.6 parts by weight of the compound (A-3) in Example 1 was used.

Example 4 As the component (B), dipentaerythritol hexaacrylate (Aronix M-4
00, manufactured by Toagosei Co., Ltd.), and 17 parts by weight of the compound (A-4) of Synthesis Example 4 were used to obtain a photosensitive resin composition in the same manner as in Example 1.

Example 5 As component (B), dipentaerythritol hexaacrylate (Aronix M-4
00, manufactured by Toagosei Co., Ltd.) and 16 parts by weight of the compound (A-5) of Synthesis Example 5 to obtain a photosensitive resin composition in the same manner as in Example 1.

<Comparative Example> Comparative Synthesis Example 1 as the component (B)
30 parts by weight of the compound (A-6), as the component (C) 2,
A photosensitive resin composition was obtained in the same manner as in Example 1 except that 3 parts by weight of 4-diethylthioxanthone (“Kayakyu DETX-S” manufactured by Nippon Kayaku Co., Ltd.) was added.

Each of the photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Example was placed under a yellow light on a degreased iron plate having a thickness of 1 mm and a side of 10 cm, and a film thickness after drying. Is about 1
After spin coating so as to have a thickness of 0 μm, it was dried at 90 ° C. for 15 minutes. Next, on the dry coating plate, Kodak Pho
tographic Step Tablet No.
2 (hereinafter referred to as gray scale) and a negative mask pattern while being vacuum-adhered to each other, an ultra-high pressure mercury lamp (HMW-5).
32, manufactured by Oak Manufacturing Co., Ltd.) and exposed to 0.2% with a 1 wt% sodium carbonate aqueous solution at 30 ° C.
After developing with a spray pressure of MPa for 90 seconds, post-baking treatment was performed in an oven at 200 ° C. for 4 minutes to form a resist pattern.

The obtained sample was evaluated for tackiness after drying, sensitivity, resolution, adhesion, etching resistance, and alkali film peeling property, and the results shown in Table 1 were obtained. By using the monomer of the present invention as compared with Comparative Example using a monomer having no carboxyl group, a composition having good etching resistance and high alkali solubility could be obtained.

Each photosensitive resin composition obtained in Examples 1 to 5 and Comparative Example and each evaluation method of the cured product were carried out as follows.

1) Tackiness An iron plate coated with a photosensitive resin is cut into a size of 3 × 3 cm, and the resin surfaces are overlapped with each other.
It was heated in an oven at 60 ° C. for 30 minutes while applying a weight of g, and the presence or absence of adhesion between the resins was confirmed. ◯: The plate could be separated without observing adhesion or a trace of contact. Δ: No adhesion was observed, but contact marks were recognized on the resin surface. X: Adhesion was recognized.

2) Sensitivity The number of steps of the step tablet after development was visually judged.

3) Resolution A negative type resolution chart was printed to obtain the minimum pattern size of resolution.

4) Etching resistance The post-baked test piece was etched with a ferric chloride aqueous solution at 70 ° C. for 4 minutes at a spray pressure of 0.5 MPa, washed with water, and the state of the etched pattern was visually evaluated by a microscope. I went. ◯: The coating film was not cracked or dissolved, and no permeation of the aqueous ferric chloride solution was observed at the substrate / coating interface.
Δ: The coating film was not cracked or dissolved, but a slight infiltration of the aqueous ferric chloride solution was observed at the substrate / coating interface.
X: Cracking or dissolution occurred in the coating film, and penetration of the aqueous ferric chloride solution was observed at the substrate / coating interface.

5) Alkali stripping property The sample after etching was immersed in a 30% NaOH aqueous solution at 80 ° C. for 1.5 minutes and then immersed in pure water for 1 minute to confirm the solubility. ◯: The resist film was completely dissolved. Δ: Although the resist film was peeled from the substrate, it was not completely dissolved. X: The resist film was neither peeled off from the substrate nor dissolved.

[0051]

[Table 1]

[0052]

As described above, according to the present invention, it is possible to develop by using an alkaline aqueous solution, has high sensitivity and high resolution, is capable of contact exposure of a mask pattern without tackiness, and further is an etching resist. When used as, a photosensitive resin composition is provided which has good etching resistance and does not cause residual alkali dissolution of the resist-cured film observed in Comparative Examples.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA02 AA09 AA14 AB13                       AB16 AC01 AD01 BC13 BC44                       BC64 BC83 BC85 CA00 CB42                       CC11 FA17                 2H048 BA45 BA48                 4J027 AA01 AJ01 AJ05 CB04 CB10                       CC05 CD10

Claims (3)

[Claims] 1. An alkali-soluble copolymer having a terminal ethylenically unsaturated group and a carboxyl group in the side chain (A), (B)
Among the photopolymerizable compounds having at least one polymerizable ethylenically unsaturated group in the molecule, at least one kind is composed of a photopolymerizable compound (C) photopolymerization initiator represented by the following formula (1). A photosensitive resin composition comprising: [Chemical 1] In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents a numerical value of 0 or 1 or 2, and R ₂ represents an alkylene group. 2. The alkali-soluble polymer (A) in an amount of 50 to 95% by weight, based on the entire photosensitive resin composition,
The photosensitive resin composition according to claim 1, which comprises (B) 4 to 40% by weight of a photopolymerizable compound and (C) 1 to 10% by weight of a photopolymerization initiator. 3. The photopolymerizable compound (B) is composed of a composition containing the photopolymerizable compound represented by the general formula (1) in an amount of 1 to 20% by weight based on the whole photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 2, characterized in that.