JP2000343031A - Resin applying method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To uniformly apply a resin layer on a pattern formed on a long-length substrate with irregularity of an upper resin layer being eliminated. SOLUTION: In this applying method, when patterns lined up on a substrate are divided into components parallel to the longitudinal direction of the substrate and components vertical to the longitudinal direction thereof, pattern arrangement is made so that the parallel components are longer than the vertical components. In this way, parallel to the parallel components of the patterns, the resin layers can be continuously applied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin coating method used in the field of electronic materials and the like.
The present invention relates to a continuous coating method for uniformly and uniformly applying an upper resin layer on a pattern formed on a long substrate.

[0002]

2. Description of the Related Art Conventionally, a method of applying a resin on a long substrate, a die coater, a reverse coater, a comma coater,
Reverse coaters and the like have been used, but in a pattern in which the underlying patterns formed on a long substrate are randomly arranged or aligned, the length of one pattern is defined as a component parallel to the longitudinal direction of the substrate. When the upper resin layer is applied continuously while moving the substrate in the longitudinal direction, the pattern blocks the flow of liquid when the vertical component is arranged so that the vertical component when divided into the component perpendicular to the longitudinal direction is longer. Also, there is a problem that the coating liquid does not flow around the base pattern, or the applied resin rises only in the pattern portion, and the entire substrate is not uniformly applied. Furthermore, when performing the pattern processing of the upper resin layer, the pattern processing may cause unevenness or a problem after the pattern processing due to the above-described causes.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object of the present invention is to form an upper resin layer on a pattern formed on a long substrate. An object of the present invention is to provide a continuous coating method for performing uniform coating without unevenness.

[0004]

According to the present invention, when a pattern aligned on a substrate is divided into a component parallel to the longitudinal direction of the substrate and a component perpendicular to the longitudinal direction, a parallel component is obtained. Is arranged in a pattern such that is longer than a vertical component, and a resin layer is continuously applied in parallel to a parallel component of the pattern.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The substrate used in the present invention is not particularly limited, but is preferably a resin film or a metal foil wound on a reel or a composite thereof, and further, a polyimide film or a copper foil wound on a reel. It is preferably a composite of a stainless steel foil or a polyimide film and a copper foil or a stainless steel foil.

The method of forming an aligned pattern on a substrate is not particularly limited. In the case of a polyimide-copper foil composite, a resist is applied to the copper foil side, and is exposed and developed on the aligned pattern. After forming the resist pattern,
Etch the copper foil. After the etching, the resist is removed to obtain a copper wiring pattern on the polyimide film.

[0008] After the photosensitive polyimide precursor resin is applied to the substrate, it is dried. Thereafter, the polyimide pattern is obtained by exposing, developing, and heat-treating the aligned pattern. Further, if necessary, a metal wiring can be formed on the polyimide pattern using a resist agent.

According to the present invention, when a pattern aligned on a substrate is divided into a component parallel to the longitudinal direction of the substrate and a component perpendicular to the longitudinal direction, the parallel component is longer than the vertical component. It is characterized by arranging a pattern and continuously applying a resin layer in parallel with the parallel component of the pattern, preferably the length of the parallel component of the pattern is at least twice the length of the vertical component, More preferably, it is three times or more.

[0010] Patterns are randomly arranged,
When the length of one pattern is divided into a component parallel to the longitudinal direction of the substrate and a component perpendicular to the longitudinal direction, if the ratio of the parallel component / vertical component is smaller than twice, the upper resin layer When applying the substrate while moving the substrate in the longitudinal direction, the pattern blocks the flow of the liquid, the coating liquid does not wrap around the pattern, or the applied resin rises only at the part of the pattern, There is a problem that the whole is not uniformly applied. Furthermore, when patterning the upper resin layer, there is a problem that the upper resin layer cannot be uniformly etched due to uneven thickness.

The upper resin layer is not particularly limited, such as polybenzoxazole or a precursor thereof, polyimide or a precursor resin thereof, but is preferably a polyimide precursor resin or a polyimide resin in terms of heat resistance. If necessary, it is preferably a photosensitive polyimide precursor resin.

The photosensitive polyimide precursor resin used in the present invention is obtained by adding a photosensitizer, an initiator and a sensitizer to a polymer having a structural unit represented by the general formula (1) as a main component, if necessary. Things can be mentioned.

[0013]

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In the general formula (1), R¹Is at least two
A trivalent or tetravalent organic group having the above carbon atoms
You. R¹As a preferred specific example, pyromellitic acid residue
Group, biphenyltetracarboxylic acid residue, terphenylte
Toracarboxylic acid residue, naphthalenetetracarboxylic acid residue
Group, diphenyl ether tetracarboxylic acid residue, diphe
Nyl sulfone tetracarboxylic acid residue, benzophenone
Tracarboxylic acid residue, 2,2'-bis (3,4-dical
Boxyphenyl) hexafluoropropane residue
But not limited thereto. R^TwoIs at least
It represents a divalent organic group having two or more carbon atoms. R^Two
Preferred specific examples of the phenylenediamine residue, di
Aminodiphenyl ether residue, 2,2'-bis (tri
Fluoromethyl) -4,4'-benzidine residue, 1,4
-Bis (4-aminophenoxy) benzene residue, 1,3
-Bis (4-aminophenoxy) benzene residue, 4,
4'-bis (4-aminophenoxy) biphenyl residue,
Diaminodiphenyl sulfone residue, diaminodiphenyl
Sulfide residues, diaminobenzanilide residues, etc.
But not limited thereto. R^ThreeIs a hydroxyl group,
-OR^Four, -NHR^Four, -O^-N ⁺R^FourR^FiveR⁶R⁷Chosen from
Represents a group. Where R^FourIs at least one ethylenic
A group having an unsaturated bond, R^Five, R⁶, R⁷Is hydrogen
Represents an atom or an organic group having 1 to 10 carbon atoms, and is the same
But they may be different. Z¹Is hydroxyl or ethyl
An organic group having an unsaturated bond, Z^TwoIs hydrogen or ethyl
It represents an organic group having a lenic unsaturated bond. n is 3 to 10
000, and m is 1 or 2.

[0015] These polymers can be obtained by the following method. R ³ is -OR ⁴ (R ⁴ is as defined above)
Is obtained by reacting an acid dianhydride with an alcohol having one kind of ethylenically unsaturated bond, and then reacting with a diamine using a dehydrating condensing agent such as dicyclohexylcarbodiimide. be able to. R ³ is —ON ⁺ R ⁴ R ⁵ R ⁶ R ⁷ (R ⁴ ,
R ⁵ , R ⁶ , and R ⁷ are the same as those described above). As a method for polymerizing the compound, a polyamic acid obtained by reacting an acid dianhydride with a diamine has one kind of ethylenically unsaturated bond. It can be obtained by mixing an amine and ionically bonding to the carboxyl group of the amic acid. As a method for polymerizing a compound in which R ³ is —NHR ⁴ (R ⁴ is the same as described above), a polyamic acid obtained by reacting an acid dianhydride with a diamine is added to a polyamic acid in the presence of a base catalyst. It can be obtained by reacting with an isocyanate having a kind of ethylenically unsaturated bond. As a method for polymerizing a compound in which R ³ is a hydroxyl group and Z ¹ is an organic group having an ethylenically unsaturated bond, an acid dianhydride is reacted with a mixture of a diamine and an aminobenzene having an unsaturated bond as a substituent. Can be obtained. As a method for polymerizing a compound in which R ³ is a hydroxyl group and Z ² is an organic group having an ethylenically unsaturated bond, trimellitic acid having an unsaturated bond as a substituent and an acid dianhydride are added to a diamine. It can be obtained by reacting.

The polymer in the present invention may be composed of only the structural unit represented by the general formula (1),
It may be a copolymer or a blend with another structural unit. At this time, the structural unit represented by the general formula (1) is
Preferably, it is contained at 0% or more. The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

Examples of the photosensitive agent used in the present invention include, but are not limited to, compounds represented by formula (2) and 4- (2'-nitrophenyl) -4-hydropyridines.

[0018]

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R ⁸ , R ⁹ and R ¹⁰ are organic groups having 1 to 30 carbon atoms, at least one of which contains an ethylenically unsaturated double bond.

Preferred specific examples of the general formula (2) include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, Examples include, but are not limited to, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylmethacrylamide, diethylaminoethylacrylamide, vinylpyridine and the like.
As a specific example of the 4- (2'-nitrophenyl) -4-hydropyridine derivative, 2,6-dimethyl-
3,5-dicyano-4- (2'-nitrophenyl)-
1,4-dihydropyridine, 2,6-dimethyl-3,5
-Diacetyl-4- (2'-nitrophenyl-1,4-
Dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-
Dihydropyridine and the like can be mentioned.

The photoinitiator used in the present invention includes N
Aromatic amines such as -phenyldiethanolamine, N-phenylglycine and Michler's ketone; cyclic oxime compounds represented by 3-phenyl-5-isoxazolone; and 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime. Chain oxime ester compounds, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzyl ketone, and fluorene, and thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, but are not limited thereto. .

Examples of sensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, coumarin compounds such as 3,3'-carbonylbis (diethylaminocoumarin), benzanthrone and phenanthrenequinone. Aromatic ketones such as those generally used for photocurable resins and those used as charge transfer agents for electrophotography are preferably used.

The photoinitiator and the sensitizer are used in an amount of 0.0
1 to 30% by weight, more preferably 0.1 to 20% by weight
It is preferred to add. Care must be taken when the ratio is out of this range, since the photosensitivity is lowered and the mechanical properties of the polymer are lowered. These photoinitiators and sensitizers alone,
Alternatively, two or more kinds can be used in combination.

In order to enhance the photosensitivity of the composition of the present invention, a photoreactive monomer can be appropriately used. As photoreactive monomers, 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate,
Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylenebismethacrylamide, methylenebisacrylamide, and the like, but are not limited thereto. .

The photoreactive monomer is used in an amount of 1 to 3 based on the polymer.
It is preferable to add in the range of 0% by weight. If the ratio is outside this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered. These photoreactive monomers can be used alone or in combination of two or more.

The method of continuously applying the photosensitive polyimide precursor on the long substrate in the longitudinal direction in the traveling direction is not particularly limited, but roll coating such as a reverse coater, a comma coater, and a slit die coater is possible. Immediately after being applied, drying is performed to obtain a long composite on which a photosensitive polyimide precursor composition film is formed. Drying is preferably performed in the range of 50 to 180 ° C, more preferably in the range of 60 to 150 ° C, using an oven, a hot plate, an infrared ray, a heat roll, or the like. The drying time is preferably from one minute to several hours. The film thickness can be adjusted by changing the application means, the solid content concentration and the viscosity of the composition, and is usually applied so as to be in the range of 0.1 to 150 μm.

Next, exposure is performed using a mask having a desired pattern. The exposure amount is 50 to 2000 mJ /
A range of cm ² is preferred.

Next, a relief pattern is obtained by dissolving and removing the unexposed portion with a developing solution. An appropriate developer can be selected according to the structure of the polymer, but an aqueous alkali solution such as ammonia, tetramethylammonium hydroxide, diethylaminoethanol, diethanolamine, or an additive such as alcohol is added to the aqueous alkali solution. And the like can be preferably used. Also, N-methyl-2-pyrrolidone, N
-Acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or the like alone or methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate , Ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propylene carbonate, 2-heptanone, ethyl acetate, etc. It can be preferably used.

The development can be carried out by dipping the coating film in a developer, applying ultrasonic waves while dipping, or applying a liquid flow to the coating film surface while dipping.

Next, it is preferable to wash the relief pattern formed by development with a rinsing liquid. As the rinsing liquid, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyribate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, and ethyl-3, which have good miscibility with the developing solution, are used.
-Ethoxypropionate, propylene carbonate, 2-heptanone, ethyl acetate or water is preferably used.

The relief pattern polymer obtained by the above treatment is a heat-resistant polyimide-based polymer precursor, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment temperature is preferably from 250 ° C. to 450 ° C. 25
When the temperature is 0 ° C. or lower, the performance such as chemical resistance is insufficient, and there is an obstacle to the formation of a thin film on the upper portion of the polyimide. The heat treatment is usually performed in an inert gas atmosphere such as a nitrogen gas atmosphere or in a vacuum while increasing the temperature stepwise or continuously.

[0032]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 A photosensitive polyimide UR-3140 manufactured by Toray Co., Ltd. was coated using a reverse coater and oven-integrated apparatus at a coating speed of 0.25.
m / min, oven conditions 90 ° C. × 20 minutes, thickness 25 μm,
It was applied on a long stainless steel foil having a width of 10 cm and dried. 1cm × 0.3 using a contact aligner made by Canon
10cm × 10c with patterns of size cm aligned
The mask is set so that the long side of the pattern is parallel to the longitudinal direction of the substrate using a mask of 300 m.
Exposure of J / cm ² was performed. Do this work continuously,
The photosensitive polyimide coating on the long substrate was all exposed.

The transport speed of this sample was adjusted using a developer DV-822 manufactured by Toray Co., Ltd. controlled at 25 ° C. so that the time during which the sample was charged into the developing tank in the continuous developing apparatus was 5 minutes. The sonic immersion development was performed. Subsequent to the developing tank, ultrasonic immersion rinsing was performed in an isopropyl alcohol rinsing tank. Thereafter, drying was performed by nitrogen blowing. This long sample is wound around a 5 mm spacer,
Heat treatment was performed in nitrogen for 30 minutes at + 350 ° C. × 1 hour to obtain a polyimide pattern having a thickness of 6 μm.

On the entire surface of the substrate on which the polyimide pattern is formed, use a sputtering device to form a film having a thickness of 60 nm or 700 nm.
Of chromium and copper were continuously formed in this order. A positive resist was applied on the formed Cr / Cu sputtered film using a reverse coater and an oven-integrated apparatus and dried. 40 mm at all wavelengths using a mask in which a 0.6 cm × 0.1 cm resist opening is formed on the polyimide pattern formed on the long stainless steel foil using a contact aligner made by Canon.
An exposure of 0 mJ / cm ² was performed. Using a resist developer, the resist was continuously patterned. Then, 5 μm of copper sulfate plating was performed on the Cu surface where the resist was developed.
After forming a Cu plating layer of m, nickel and gold were each plated to a thickness of 50 nm. The resist was continuously etched with 2.5% NaOH. By etching the unsputtered portions of the Cu sputter film and the Cr sputter film, 0.6 cm × 0.1 c
m metal pattern was obtained.

While moving the long stainless steel foil having the metal pattern formed on the polyimide pattern in the longitudinal direction, the photosensitive polyimide UR-3100 made by Toray Co., Ltd.
Coating and drying were performed at 25 m / min and oven conditions of 90 ° C. × 20 minutes. At this time, the polyimide precursor coating was applied uniformly in the plane without any foreign matter.

Example 2 The polyimide precursor film of UR-3100 of Example 1 was formed using a contact aligner made by Canon and a mask having a size of 0.8 cm × 0.2 cm covering the metal pattern. , 150 mJ / cm ² . This operation was continuously performed to expose the entire photosensitive polyimide film on the long substrate.

The transport speed of this sample was adjusted using a Toray developer DV-822 controlled at 25 ° C. so that the time during which the sample was charged into the developing tank in the continuous developing apparatus was 3 minutes, and The sonic immersion development was performed. Subsequent to the developing tank, ultrasonic immersion rinsing was performed in an isopropyl alcohol rinsing tank. Thereafter, drying was performed by nitrogen blowing. This long sample is wound up with a 5 mm spacer, and 140 ° C x 3
Heat treatment was performed in nitrogen for 0 minute + 350 ° C. × 1 hour to obtain a cover polyimide pattern. The pattern consisting of polyimide / metal wiring / polyimide on stainless steel was all good.

Example 3 1 cm on a long Kapton film having a width of 10 cm and a thickness of 25 μm
A copper plating layer having a thickness of 0 μm was formed. On the copper plating layer side, a positive resist was applied and dried using a reverse coater and an oven-integrated device. Using a contact aligner manufactured by Canon Inc. and a mask having a resist pattern of 1 cm × 0.4 cm formed on a copper plating layer, 40 nm at all wavelengths.
An exposure of 0 mJ / cm ² was performed. Using a resist developer, the resist was continuously patterned. Then, after etching the copper-plated portion where the resist does not remain, the resist was continuously etched with 2.5% NaOH, so that 1 cm ×
A 0.4 cm copper pattern was obtained.

While moving the long polyimide film on which the copper pattern was formed in the long direction, the photosensitive polyimide UR-3100 manufactured by Toray Co., Ltd. was applied using a reverse coater and an oven integrated device at an application speed of 0.25 m / min. Coating and drying were performed at oven conditions of 90 ° C. for 20 minutes. At this time, the polyimide precursor coating was applied uniformly in the plane without any foreign matter.

Comparative Example 1 An experiment was performed in the same manner as in Example 1 except that a mask was set so that the long side of the pattern was perpendicular to the longitudinal direction of the long substrate. As a result, after applying and drying the cover layer,
The portion where the underlayer pattern was present protruded, and the portion without the underlayer was flat and large unevenness occurred in the plane. Also, when looking only at the portion where the underlayer is present, the front and back portions of the underlayer pattern are thicker at the front and thinner at the rear, resulting in unevenness in the direction of travel of the substrate when the cover layer is applied. did.

[0042]

According to the present invention, when an upper resin layer is coated on a base pattern formed on a long substrate by using a continuous coating apparatus, the upper resin layer is uniformly applied without being affected by the unevenness of the base pattern. Can be.

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Claims (9)

[Claims] When a pattern aligned on a substrate is divided into a component parallel to the longitudinal direction of the substrate and a component perpendicular to the longitudinal direction, the pattern is arranged such that the parallel component is longer than the vertical component. And applying a resin layer continuously to the parallel component of the pattern. 2. The resin coating method according to claim 1, wherein the length of the parallel component of the pattern is at least twice the length of the vertical component. 3. The method according to claim 1, wherein the substrate is a resin film, a metal foil, or a composite thereof. 4. The method according to claim 3, wherein the resin film is a polyimide film. 5. The method according to claim 3, wherein the metal foil is a copper foil or a stainless steel foil. 6. The resin coating method according to claim 3, wherein the composite is a composite of a polyimide film and a copper foil or a composite of a polyimide film and a stainless steel foil. 7. The method according to claim 1, wherein the material of the pattern formed on the substrate is at least one of a heat-resistant resin and a metal foil. 8. A resin layer to be applied, wherein a polyimide precursor resin is applied and converted to polyimide by heat treatment, or a polyimide resin is applied.
A method for applying the resin described in the above. 9. The method according to claim 8, wherein the resin layer to be applied is a photosensitive polyimide precursor.