JP2002317005A - Photo-polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photo-polymerizable resin composition having a high sensitivity especially to ultraviolet light or visible light, capable of being cured with a picture-drawing laser and also excellent in preservation stability after a membrane formation on a base substrate and after the picture-drawing. SOLUTION: This photo-polymerizable resin composition consists of (A) a polymerizable component containing at least one addition-polymerizable compound having an ethylenically unsaturated bond, (B) a photo-polymerization initiator, (C) a chain transfer agent, (D) a thermal polymerization inhibitor, and (E) tetrazole or its derivative, or triazole or its derivative, and preferably contains 0.5-10 mass % photo-polymerization initiator (B), 0.2-5 mass % chain transfer agent (C), 0.01-0.1 mass % thermal polymerization inhibitor (D) and 0.01-0.5 mass % tetrazole or its derivative, or triazole or its derivative (E).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable resin composition, and in particular, has high photosensitivity to ultraviolet light and visible light, and can be cured by an ultraviolet laser or a visible laser.
And a photopolymerizable resin composition having extremely excellent stability.

[0002]

2. Description of the Related Art Conventionally, in an exposure pattern forming technique of drawing by scanning with a laser beam, a photopolymerizable resin composition with high sensitivity has been desired in order to shorten the drawing time due to productivity problems. For this reason, the sensitivity has been increased by using a chain transfer agent in addition to the photopolymerization initiator and the sensitizer (Japanese Patent Application Laid-Open No.
No. 1-72915). However, when these are formed on the substrate by coating or lamination,
If the cross-linking reaction proceeds with the standing, or if the drawing is left after the drawing, the cross-linking reaction similarly proceeds from the vicinity of the exposed portion to the unexposed portion. For this reason, the copper surface of the base material is oxidized to cause copper burning, undeveloped portions are left undeveloped, resolution of the resist is reduced, and the yield of pattern formation is reduced.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems, and in particular, can be cured by laser drawing with high sensitivity to ultraviolet light or visible light, and can be used after forming a film on a substrate. It is another object of the present invention to provide a photopolymerizable resin composition having excellent storage stability after drawing.

[0004]

The object of the present invention is to provide a polymerizable component (A) having at least one addition-polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator (B), and a chain transfer agent (C). ), A thermal polymerization inhibitor (D), and a photopolymerizable resin composition comprising tetrazole or a derivative thereof, or triazole or a derivative thereof (E).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The polymerizable component (A) having at least one kind of addition-polymerizable compound having an ethylenically unsaturated bond used in the present invention may be composed of only an addition-polymerizable compound having an ethylenically unsaturated bond. And these compounds and a binder resin such as a polymer. The addition-polymerizable compound having an ethylenically unsaturated bond may be any monomer, oligomer, or prepolymer having an ethylenically unsaturated bond that causes addition polymerization by the action of a photopolymerization initiator. In order to obtain high reactivity, those having an acryloyl group or a methacryloyl group are preferred.

Examples of these monomers having an acryloyl group or a methacryloyl group include polyether acrylate or polyether methacrylate, polyester acrylate or polyester methacrylate, polyol acrylate or polyol methacrylate, epoxy acrylate or epoxy methacrylate, urethane acrylate or Examples include monomers and oligomers such as urethane methacrylates. These monomers and oligomers are used alone or in combination of two or more.

The binder resin used in combination with these monomers and oligomers is intended to impart various functions such as developability and adhesion to a substrate.
It is appropriately selected according to the purpose. For example, copolymers of acrylic acid esters, methacrylic acid esters, styrene, acrylonitrile, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylamide, methacrylamide and the like can be used. One of these copolymers may be used, or two or more of them may be mixed and used at an appropriate ratio. For example, in the case of an alkali-type resist that is developed and peeled off using an aqueous alkali solution, 3 to
Acrylic resin containing an α, β-unsaturated carboxyl group monomer containing 15 carbon atoms as a copolymerizable component is preferable,
Most preferred are acrylic acid and methacrylic acid.

The photopolymerization initiator (B) constituting the composition of the present invention includes, for example, known benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, anthraquinones, thioxanthones, benzoin alkyl ethers, Benzyl ketals, triazines, biimidazoles, acyl phosphine oxides, acridines, titanocenes, etc., which can be used alone or in combination of two or more of those suitable for the light source wavelength used. In addition, if necessary, a sensitizer can be used in combination. The content of the photopolymerization initiator in the composition is 0.5 to 0.5 in terms of sensitivity, resist pattern shape, resolution, and the like.
It is desirable to be in the range of 10% by mass.

[0009] The chain transfer agent (C) constituting the composition of the present invention is a component for improving the sensitivity, and is known, for example, N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercapto acid, and the like. Thiazole and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, N-phenylglycine is particularly preferred for improving sensitivity. The content of the chain transfer agent in the composition,
It is desirable to be in the range of 0.2 to 5% by mass.

The thermal polymerization inhibitor (D) constituting the composition of the present invention may be any of known ones such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, tetramethylpiperidine-N-oxyls, pyrogallol,
Catechol, P-benzoquinone, cuperon, N-nitrosophenyl-β-naphthylamine, N-nitrosophenylhydroxylamine aluminum salt and the like. The content of the thermal polymerization inhibitor in the composition is 0.01 to
It is preferably in the range of 0.1% by mass.

Further, the tetrazole or its derivative or the triazole or its derivative (E) constituting the composition of the present invention is the main object of the present invention, which is storage stability after forming a film on a substrate and after drawing. Is used as a stabilizer for improving the viscosity. Specific examples of these include well-known 1H-1,2,3,4-tetrazole, 5 amino-1H-tetrazole, 5methyl-1-tetrazole, 1,2,4 triazole, 5 chlorobenzotriazole, and the like. . The content of the stabilizer (E) in the composition is 0.01 to 0.5% by mass.
Range.

The photopolymerizable resin composition of the present invention comprises a polymerizable component (A) having at least one addition polymerizable compound having an ethylenically unsaturated bond as described above, a photopolymerization initiator (B), a chain The transfer agent (C), the thermal polymerization inhibitor (D), and the stabilizer tetrazole or its derivative, or triazole or its derivative (E) are essential components,
Various additives such as a coloring agent and a plasticizer can be included as needed.

The photopolymerizable resin composition of the present invention having the above-described composition is used in the form of a film on a metal surface such as copper, iron, stainless steel or the like, a glass surface, a ceramic surface or the like. As a method of use, a liquid resist is applied to the surface of a base material, dried and coated with a protective film, or used as a dry film photoresist which is laminated on a base material. The thickness of the photoresist layer varies depending on the application, but is about 5 to 100 μm in thickness after drying.

As a protective film when a liquid resist is used, a polyester film is preferable. The dry film photoresist is prepared by applying a photopolymerizable resin composition dissolved by a suitable organic solvent onto a polyester support film, drying the film, and then laminating a polyolefin protective film.

Next, the resist is exposed using a laser direct drawing machine. The resist sensitivity usually used in a laser direct drawing machine needs to be 10 mJ / cm ² or less from the viewpoint of productivity. After drawing, the unexposed portion is washed and removed using an appropriate developing solution to obtain a resist pattern in a hardened portion. The developer must be safe and stable.
However, what is particularly important is to select a solvent having a large operability of development, that is, a solvent having a large difference in solubility between a cured portion and an uncured portion of the photoresist and a moderately high dissolution rate in the uncured portion. In a general alkali developing type, a dilute aqueous solution of sodium carbonate or the like is preferably used.

[0016]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples.

(Examples 1 to 5, Comparative Examples 1 to 4) Photopolymerizable composition solutions having the compositions of Examples 1 to 5 and Comparative Examples 1 to 4 shown in Table 1 were prepared. The obtained composition was applied on a 20 μm-thick polyester film by a coater. Next, after leaving it to stand for 30 minutes, it was dried in a dryer at 60 ° C. for 30 minutes to obtain a photopolymerizable braid layer having a thickness of 40 μm. Thereafter, the laminate was subjected to heat lamination on a copper-clad laminate with the polyester surface facing upward to obtain a test plate. Lamination conditions were a roll temperature of 100 ° C. and a speed of 1.5 m / min.

After standing for 4 hours after lamination, a laser beam condensed to a beam diameter of 30 μm by an optical system using a light of 488 nm wavelength of an argon laser having a power of 2.5 W as a light source is placed on a test plate at a light amount of 510 mJ / cm ^2. By scanning, line, space patterns of 60, 80, and 100 μm were drawn. The overlap of the laser beams at this time is 5
μm. Next, after leaving for 4 hours after exposure, the polyester film was peeled off, and the uncured portion was dissolved and removed using a 1% by mass aqueous sodium carbonate solution to obtain a drawing pattern. The developing spray pressure at this time is 1.5 kg / cm.
^2. Development was performed for 40 seconds at a developer temperature of 30 ° C. Table 1 shows the state of the pattern after development.

[0019]

[Table 1]

(Note) Polymerizable component A-1: Binder resin 65 parts Methyl methacrylate / n-butyl methacrylate / methacrylic acid copolymer (52.5 / 2 5 / 22.5), number average molecular weight 90,000 trimethylolpropane triacrylate 20 parts Polypropylene glycol diacrylate 15 parts Polymerizable component A-2: Binder resin 65 parts Methyl methacrylate / methyl acrylate / styrene / methacrylic acid copolymer (50 / 22.5 / 5 / 22.5) Number average molecular weight 90,000 trimethylol Propane triacrylate 20 parts Polypropylene glycol diacrylate 15 parts Photopolymerization initiator B-1: titanocene / coumarin 6 10/1 Photopolymerization initiator B-2: 2,2'bis (o-chlorophenyl) 4,5,4 ' , 5'-Tetraphenyl 1,2'-biimidazole / ethylmichler's ketone 30/1 chain transfer agent C- : N phenylglycine Thermal polymerization inhibitor D-1: Methoxyhydroquinone Thermal polymerization inhibitor D-2: N, N-diethylhydroxylamine Stabilizer E-1: 1H-1,2,3,4-tetrazole Stabilizer E- 2: 5-amino-1H-tetrazole stabilizer E-3: 5-methyl-1H-tetrazole stabilizer E-4: 1,2,4 triazole Solvent: methyl ethyl ketone / methanol (9/1)

Examples 6 to 10 and Comparative Examples 5 to 8 Photopolymerizable composition solutions having the respective compositions of Examples 6 to 10 and Comparative Examples 5 to 8 shown in Table 1 were prepared. The obtained composition was applied on a 20 μm-thick polyester film by a coater. Next, after leaving it to stand for 30 minutes, it was dried in a dryer at 60 ° C. for 30 minutes to obtain a photopolymerizable braid layer having a thickness of 40 μm. Thereafter, the laminate was subjected to heat lamination on a copper-clad laminate with the polyester surface facing upward to obtain a test plate. Lamination conditions were a roll temperature of 100 ° C. and a speed of 1.5 m / min.

After the lamination was allowed to stand for 4 hours, a laser beam condensed to a beam diameter of 30 μm by an optical system was scanned on a test plate at a light intensity of 10 mJ / cm ² using a light of 351 nm wavelength of 7 W argon laser as a light source. hand,
Line-and-space patterns of 60, 80, and 100 μm were drawn. The laser beam overlap at this time is 5 μm
And Next, after leaving for 4 hours after exposure, the polyester film was peeled off, and the uncured portion was dissolved and removed using a 1% by mass aqueous sodium carbonate solution to obtain a drawing pattern. The developing spray pressure at this time was 1.5 kg / cm ² ,
Developing was performed for 40 seconds at a developing solution temperature of 30 ° C. Table 1 shows the state of the pattern after development.

[0023]

The photopolymerizable resin composition of the present invention can be cured by laser drawing with high sensitivity, particularly to ultraviolet light and visible light, and has storage stability after adhesion to a substrate and after drawing. It is useful as an extremely excellent resist material.

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[Procedure amendment]

[Submission date] May 11, 2001 (2001.5.1
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

After the lamination was allowed to stand for 4 hours, a laser beam condensed to a beam diameter of 30 μm by an optical system using a light of wavelength 488 nm of an argon laser of 2.5 W as a light source was irradiated with a light amount of 5 mJ / cm ^2. Scan on the test plate with equivalent,
Line-and-space patterns of 60, 80, and 100 μm were drawn. The laser beam overlap at this time is 5 μm
And Next, after standing for 4 hours after exposure, the polyester film was peeled off, and the uncured portion was dissolved and removed using a 1% by mass aqueous solution of sodium carbonate to obtain a drawing pattern. The developing spray pressure at this time was 1.5 kg / cm ² ,
Developing was performed for 40 seconds at a developing solution temperature of 30 ° C. Table 1 shows the state of the pattern after development.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019]

[Table 1]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

(Note) Polymerizable component A-1: 65 parts of binder resin [methyl methacrylate / n-butyl methacrylate / methacrylic acid copolymer ( 52.5 / 25 / 22.5), number average molecular weight 90,000] trimethylol Propane triacrylate 20 parts Polypropylene glycol diacrylate 15 parts Polymerizable component A-2: Binder resin 65 parts [methyl methacrylate / methyl acrylate / styrene / methacrylic acid copolymer (50 / 22.5 / 5 / 22.5) number average molecular weight 90,000] trimethylolpropane triacrylate 20 parts polypropylene glycol diacrylate 15 parts Photopolymerization initiator B-1: titanocene / coumarin 6 10/1 Photopolymerization initiator B-2: 2,2'bis (o-chlorophenyl) 4 , 5,4 ', 5'-Tetraphenyl 1,2'-biimidazole / ethylmichler's ketone 30/1 Chain transfer agent C 1: N-phenylglycine Thermal polymerization inhibitor D-1: Methoxyhydroquinone Thermal polymerization inhibitor D-2: N, N-diethylhydroxylamine Stabilizer E-1: 1H-1,2,3,4-tetrazole Stabilizer E -2: 5-amino -1H- tetrazole stabilizer E-3: 5-methyl -1H- tetrazole stabilizer E-4: l, 2,4-tri A tetrazole solvent: methyl ethyl ketone / methanol (9/1)

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Mita 19-2 Kiyohara Industrial Park, Utsunomiya City, Tochigi Pref. FA17 4J002 BC021 BG011 BG041 BG071 BG101 BG121 ED086 EE036 EE056 EE058 EF017 EJ018 EN117 ES008 EU009 EU056 EU078 EU116 EU169 EU186 EV067 EV327 EV328 EW146 FD039 FD206 FD207 FD208 GJ01 GP03 NA03 4 PC08 PC11 QA02 QA03 QA04 QA05 QA06 QA07 QA09 QA37 SA22 SA25 SA34 SA51 SA63 SA64 SA78 SA86 UA02 VA01 WA01

Claims (3)

[Claims] 1. A polymerizable component (A) having at least one addition-polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator (B), a chain transfer agent (C), and a thermal polymerization inhibitor (D). ) And a tetrazole or a derivative thereof, or a triazole or a derivative thereof (E). 2. The composition has a photopolymerization initiator (B) content of 0.5 to 10% by mass, a chain transfer agent (C) content of 0.2 to 5% by mass, and a thermal polymerization inhibitor. When the content of (D) is 0.
The content of tetrazole or a derivative thereof or triazole or a derivative thereof (E) is 0.1 to 0.1% by mass.
The photopolymerizable resin composition according to claim 1, wherein the content is from 0.01 to 0.5% by mass. 3. The method of claim 1, wherein the tetrazole or a derivative thereof is 1H-1,
3. The method according to claim 1, wherein the compound is 2,3,4-tetrazole, 5 amino-1H-tetrazole, or 5methyl-1-tetrazole, and the triazole or a derivative thereof is 1,2,4 triazole or 5 chlorobenzotriazole. Photopolymerizable resin composition.