JP3329777B2 - Photopolymerizable composition for microfabrication - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition for fine processing , and more particularly, to a fine pattern having excellent adhesion to a substrate, high burn-out, and a good shape. The present invention relates to a photopolymerizable composition for fine processing capable of forming a film.

[0002]

2. Description of the Related Art Conventionally, photopolymerizable compositions have been widely used, such as resists for plate making, resists for fine processing, varnishes for photosensitive paints, and adhesives for glass. Such a photopolymerizable composition is generally a composition containing a polymer binder, a photopolymerizable monomer and a photopolymerization initiator. Among them, the photopolymerizable monomer is preferably acrylic acid or methacrylic acid. Acid, 2-
Photopolymerizable compositions which are acrylic compounds such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate are preferably used as resists for fine processing such as production of electronic parts.

In the fine processing using the photopolymerizable composition containing the acrylic photopolymerizable monomer, a pattern made of the photopolymerizable composition is formed on a substrate, and the pattern is used as a mask to form the substrate. The so-called lithographic processing for processing is common, but in recent years, as this fine processing technology has progressed further and finer processing has been required, the characteristics required for the photopolymerizable composition have also been improved. In addition to sensitivity and resolution, it has been required to have good adhesion to a substrate and good burn-out by firing for removing a residual pattern that has become unnecessary after processing the substrate.
A conventional polymer binder, a photopolymerizable composition containing an acrylic compound and a photopolymerization initiator is excellent in sensitivity, resolution, etc., but the adhesion to the substrate, the burn-out property is not sufficient, It has been desired to provide a photopolymerizable composition excellent in these properties.

[0004]

SUMMARY OF THE INVENTION As a photopolymerizable composition satisfying the above demand, the present inventors have previously made at least one photopolymerizable monomer selected from a polymer binder, a specific salicylic acid ester and a phthalic acid diester. Monomer, and a polymerizable composition containing a photopolymerization initiator was proposed, but further research was continued in search of a photopolymerizable composition having better adhesion to a substrate. The present inventors have found that the use of a specific acrylic compound as a monomer makes it possible to obtain a photopolymerizable composition that is more excellent in adhesion to a substrate and in burn-out, thereby completing the present invention. That is,

An object of the present invention is to provide a photopolymerizable composition for fine processing , which is excellent in sensitivity and resolution, and excellent in adhesion to a substrate and burnout.

[0006]

The present invention to achieve the above object is to provide a photopolymerizable composition containing (A) a polymer binder, (B) a photopolymerizable monomer and (C) a photopolymerization initiator. In the above , the component (A) contains at least a cellulose derivative.
Wherein, and component (B) one general formula of 6

[0007]

Embedded image [In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a hydroxyl group or an alkyl group having 1 to 9 carbon atoms which may have a generally formalized 7

[0008]

Embedded image (In the formula, R ³ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a hydroxyl group, and p and q each represent an integer in which the sum of p and q is 14 or less.) R ¹ represents a hydrogen atom, and m and n represent m and n
Is an integer of 14 or less. The present invention relates to a photopolymerizable composition for fine processing, which is at least one selected from acrylic compounds represented by the formula (1).

Hereinafter, the present invention will be described in detail. The photopolymerizable composition of the present invention is a photopolymerizable composition containing the component (A), the component (B) and the component (C), as described above. Hydroxypropyl se
Lurose, ethyl hydroxyethyl cellulose, hydro
Xypropyl methylcellulose phthalate, hydroxy
Cell selected from propyl methylcellulose acetate
Loose derivatives can be mentioned. The cellulose invitation
Conductors may be used alone or in combination of two or more.
No. In addition, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, monomethyl fumarate, fumaric acid Monoethyl, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid,
Hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate,
2-hydroxypropyl methacrylate, hydroquinone monoacrylate, hydroquinone monomethacrylate,
Hydroquinone diacrylate, hydroquinone di 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
N-butyl acrylate, N-butyl methacrylate,
Isobutyl acrylate, isobutyl methacrylate, 2
-Ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, ethylene glycol dimethacrylate,
Triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate, glycidyl methacrylate , Glish Methacrylate ethylene glycol diacrylate, fumarate ester of (meth) acrylate of these exemplified compounds in place of fumarate, maleate ester in place of maleate, crotonic acid ester in place of crotonate, itaconic acid ester in place of itaconate, urethane methacrylate, The polymer or copolymer of styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. is formed by (A).
Per minute. The polymer or copolymer
May be used alone or in combination of two or more.

The content of the component (A) is as follows:
Of the total of 100 parts by weight of the components (B) and (C), 10
It can be contained in the range of up to 80 parts by weight.

Further, (B) component, one general formula of 8

[0012]

Embedded image [In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a hydroxyl group or an alkyl group having 1 to 9 carbon atoms which may have a generally formalized 9

[0013]

Embedded image (In the formula, R ³ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a hydroxyl group, and p and q each represent an integer in which the sum of p and q is 14 or less.) R ¹ represents a hydrogen atom, and m and n represent m and n
Is an integer of 14 or less. ), At least one selected from acrylic compounds represented by formula (B). By containing the component (B), the adhesion of the pattern formed of the photopolymerizable composition to the substrate is improved, and It is also excellent in precision and can perform precision processing well. In particular, general formula 8
When an acrylic compound in which m and n are 0 is used, the adhesion is further improved. Specific examples of the acrylic compound represented by the general formalized 8, there may be mentioned a compound of of 10 to 13, more preferably of 10 and of 11
Acrylic compounds are preferred.

[0014]

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[0015]

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[0016]

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[0017]

Embedded image

The content of the component (B) is as follows:
Of the total of 100 parts by weight of the components (B) and (C), 10
It can be contained in the range of up to 80 parts by weight. When the component (B) is less than the above range, improvement of the photopolymerizable composition cannot be expected, and when it exceeds the above range, the burn-out property is unfavorably deteriorated.

The photopolymerizable composition of the present invention may contain, in addition to the above-mentioned component (B), a known photopolymerizable monomer for improving the properties of the coating film within a range not to impair the object of the present invention.
Examples of the photopolymerizable monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and trimethylolethane triacrylate. , Trimethylolethane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipenta Lithritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate, glycerol methacrylate, cardo epoxy diacrylate, and fumarate of (meth) acrylate of these exemplified compounds Fumaric acid ester instead of itaconate, itaconic acid ester instead of itaconate, and maleate ester instead of maleate.

The content of the photopolymerizable monomer capable of forming a coating film is in the range of 0 to 60 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). Can be contained.

Further, the component (C) includes 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine and 2,4-bis-trichloromethyl-6- ( 2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-
6- (2-bromo-4-methoxy) styrylphenyl-
s-triazine, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-2 -(Pyr-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis (2,3,4,5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis [2 5-difluoro-3- (pyr-1-yl) phenyl] titanium,
1-hydroxycyclohexylphenyl ketone, 2,2
-Dimethoxy-1,2-diphenylethan-1-one,
2-methyl-1- [4- (methylthio) phenyl] -2
Morpholinopropan-1-one, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
-Butan-1-one, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4
-(2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,4-
Diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Acid butyl, 4-dimethylaminobenzoic acid
2-ethylhexyl, 4-dimethylaminobenzoic acid-2
-Isoamyl, 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethylacetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate , Bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, p-dimethylamino Acetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone,
Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-
Dichloro-4-phenoxyacetophenone, pentyl-
Examples thereof include 4-dimethylaminobenzoate and 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer. The component (C) can be used alone or in combination of two or more.

The content of the above (C) is as follows:
In a total of 100 parts by weight of the components (B) and (C), 0.
It can be contained in the range of 1 to 50 parts by weight.

The photopolymerizable composition of the present invention is used by dispersing the above components (A), (B) and (C) in water or dissolving it in an organic solvent. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate DOO, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2
-Ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, and the like. The organic solvents can be used alone or in combination of two or more.

The photopolymerizable composition of the present invention is applied by applying it to a substrate in a liquid state or by screen printing on the substrate, depending on the application. When precision processing such as is required, it is preferable to use a photosensitive film formed by applying and drying the photopolymerizable composition on a flexible film. The photosensitive film is, for example, a flexible film composed of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, or polyvinyl chloride having a thickness of 15 to 125 μm, and a photopolymerizable composition dissolved in a solvent or dispersed in water. Applicator, bar coater,
It can be formed by applying a dried film having a thickness of 10 to 100 μm using a wire bar coater, a roll coater, a curtain flow coater, or the like, and drying. If necessary, a release film may be stuck to stably protect the photosensitive layer when not in use. As the release film, a polyethylene terephthalate film, a polypropylene film, a polyethylene film or the like having a thickness of about 15 to 125 μm coated or baked with silicone is preferable.

Next, the method of using the photopolymerizable composition of the present invention will be described. A coating solution obtained by dissolving the photopolymerizable composition of the present invention in an organic solvent is applied on a glass substrate.
Dry to form a photopolymerizable layer, irradiate it with actinic rays such as ultraviolet rays, excimer lasers, X-rays, and electron beams through a mask for image exposure, and then develop using a general-purpose alkali developer or water. A treatment is performed to dissolve and remove the non-irradiated portions to form a pattern on the glass substrate. Examples of the alkaline component of the alkaline developer used for the development include hydroxides of alkali metals such as lithium, sodium, and potassium, carbonates, bicarbonates, phosphates, pyrophosphates, benzylamine, and butylamine. Secondary amines such as primary amine, dimethylamine, dibenzylamine and diethanolamine; tertiary amines such as trimethylamine, triethylamine and triethanolamine; cyclic amines such as morpholine, piperazine and pyridine; ethylenediamine and hexamethylenediamine Ammonium hydroxides such as polyamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethylphenylbenzylammonium hydroxide Trimethylsulfonium hydroxides, trimethylsulfonium hydroxide, diethyl methyl sulfonium hydroxide, sulfonium hydroxide such as dimethyl benzyl sulfonium hydroxide, choline, and the like silicate-containing buffers.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described, but the present invention is not limited thereto.

[0027]

EXAMPLES Example 1 Each component of the following 1-6. 1. Hydroxypropyl cellulose 10 parts by weight Acrylic compound represented by Chemical formula 14

[0028]

Embedded image 10 parts by weight Irgacure-907 (manufactured by Ciba Specialty Chemicals) 0.5 parts by weight 0.5 parts by weight of diethylthioxanthone A blue phosphor for PDP (BaMgAl ₁₀ O ₁₇ : Eu) 49 parts by weight 6.3 40 parts by weight of 3-methyl-3-methoxybutanol was mixed well to prepare a photopolymerizable composition solution.

Next, the photopolymerizable composition solution prepared above was applied on a soda glass substrate so that the film thickness after drying became 30 μm, and then passed through a test pattern mask with an ultra-high pressure mercury lamp at 50 mJ / cm 2. Ultraviolet light exposure was performed with an irradiation amount of cm ² . Then, use water at a liquid temperature of 30 ° C for 3k.
Spray development was performed for 30 seconds at an injection pressure of g / cm ² to form a pattern. When the adhesiveness of the obtained pattern was evaluated, the remaining minimum line width was 50 μm.

Further, in order to evaluate the burn-out property of the pattern, the pattern was heated at a heating rate of 10 ° C./min.
When a baking treatment for 30 minutes was performed, no pattern was left on the substrate, and it was confirmed that the pattern was completely removed from the substrate.

Example 2 In Example 1, instead of Chemical Formula 14 , Chemical Formula 15

[0032]

Embedded image Example 1 except that the acrylic compound represented by
A photopolymerizable composition solution was prepared in the same manner as described above.

Next, the photopolymerizable composition solution prepared above was applied onto a soda glass substrate so that the film thickness after drying became 30 μm, and then passed through a test pattern mask with an ultrahigh pressure mercury lamp at 100 mJ / m2. Ultraviolet light exposure was performed with an irradiation amount of cm ² . Then, using water at a liquid temperature of 30 ° C., 3
Spray development was performed for 30 seconds at an injection pressure of kg / cm ² to form a pattern. When the adhesiveness of the obtained pattern was evaluated, the remaining minimum line width was 50 μm.

When the same baking treatment as in Example 1 was performed to evaluate the burn-out property of the pattern, it was confirmed that there was no pattern remaining on the substrate and the pattern was completely removed from the substrate. Was.

Example 3 In Example 1, instead of Chemical Formula 14 , Chemical Formula 16

[0036]

Embedded image Example 1 except that the acrylic compound represented by
A photopolymerizable composition solution was prepared in the same manner as described above.

Next, the photopolymerizable composition solution prepared above was applied onto a soda glass substrate so that the film thickness after drying became 30 μm, and then passed through a test pattern mask using an ultra-high pressure mercury lamp at 100 mJ / cm 2. Ultraviolet light exposure was performed with an irradiation amount of cm ² . Then, using water at a liquid temperature of 30 ° C., 3
Spray development was performed for 30 seconds at an injection pressure of kg / cm ² to form a pattern. When the adhesion of the obtained pattern was evaluated, the remaining minimum line width was 80 μm.

When the same baking treatment as in Example 1 was performed to evaluate the burn-out property of the pattern, it was confirmed that there was no pattern remaining on the substrate and the pattern was completely removed from the substrate. Was.

Example 4 In Example 1, instead of Chemical Formula 14 , Chemical Formula 17

[0040]

Embedded image Example 1 except that the acrylic compound represented by
A photopolymerizable composition solution was prepared in the same manner as described above.

Next, the photopolymerizable composition solution prepared above was applied onto a soda glass substrate so that the film thickness after drying became 30 μm, and then passed through a test pattern mask with an ultrahigh pressure mercury lamp at 50 mJ / m2. Ultraviolet light exposure was performed with an irradiation amount of cm ² . Then, use water at a liquid temperature of 30 ° C for 3k.
Spray development was performed for 30 seconds at an injection pressure of g / cm ² to form a pattern. When the adhesiveness of the obtained pattern was evaluated, the remaining minimum line width was 60 μm.

When the same baking treatment as in Example 1 was performed to evaluate the burn-out property of the pattern, it was confirmed that there was no pattern remaining on the substrate and the pattern was completely removed from the substrate. Was.

Comparative Example 1 A photopolymerizable composition solution prepared in the same manner as in Example 1 except that pentaerythritol triacrylate was used instead of the photopolymerizable monomer used in Example 1 was used. In order to evaluate the adhesion and burn-out of the pattern, evaluation was performed using the same method as in Example 1. The remaining minimum line width was 200 μm, and a baked residue remained on the substrate. It was confirmed that the property and the burn-out property were poor.

[0044]

The photo-polymer composition for fine processing of the present invention comprises:
In addition to good sensitivity and resolution, it has excellent adhesion to the substrate and burn-out, and can form fine and good patterns with a minimum line width of 100 μm or less, facilitating precision processing of electronic components and the like.

────────────────────────────────────────────────── ─── Continuation of the front page Examiner Yoshiko Maeda (56) References JP-A-6-166721 (JP, A) JP-A-2-8851 (JP, A) JP-A-9-26667 (JP, A) JP-A-5-188592 (JP, A) JP-A-2-8849 (JP, A) JP-A-56-152803 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F7 / 027 G03F 7/032 C08F 2/46 C08F 299/02 C08L 33/14

Claims (5)

(57) [Claims] 1. A photopolymerizable composition containing (A) a polymer binder, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, wherein the component (A) is at least cellulose-inducible.
A polymer binder containing a conductor, wherein the component (B) has the general formula 1 [Wherein, R ¹ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a hydroxyl group, a general formula 2 (In the formula, R ³ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 9 carbon atoms which may have a hydroxyl group, and p and q each represent an integer in which the sum of p and q is 14 or less.) R ² represents a hydrogen atom, and m and n represent an integer in which the sum of m and n is 14 or less. ] The photopolymerizable composition for microfabrication is at least one selected from acrylic compounds represented by the following formula: 2. Component (A) is hydroxypropyl cellulose.
2. The microfabrication device according to claim 1, wherein
Photopolymerizable composition. 3. The photopolymerizable composition for fine processing according to claim 1, wherein the component (B) is an acrylic compound in which m and n in Formula 1 are each 0. 4. The component (B) is represented by the general formula 3 (In the formula, R ¹ may have a hydrogen atom, a hydroxyl group, or a hydroxyl group.
Shows a substituent represented by a good alkyl group having 1 to 9 carbon atoms.
R ² represents a hydrogen atom, and m and n are the total of m and n.
The total indicates an integer of 14 or less. ) Acrylic compound
The photopolymerization for fine processing according to claim 1, wherein
Composition. Wherein component (B) of 4 ## STR4 ## Or 5 The photopolymerizable composition for fine processing according to claim 3 , wherein the composition is an acrylic compound.