JPH11307907A - Manufacture of electrode and transfer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable formation of a high precision pattern, and improve workability practically as compared with the conventional method by using a transfer film, when an electrode constituting an electrode wiring and a salient electrode of a printed wiring board, a multilayer circuit board, a multi-chip module, an LCD, an LSI, etc., is formed. SOLUTION: This manufacturing method of an electrode contains a process in which a conductive paste layer 21 formed on a support film is transferred on a board 11, a resist film is formed on the conductive paste layer, a latent image of a resist pattern is formed by exposuring the resist film to a light, a resist pattern is made apparent by developing the resist film, a pattern of the conductive paste layer corresponding the resist pattern is formed by etching the conductive paste layer, and the pattern is baked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes it possible to form a high-definition pattern in the formation of electrode wiring and projecting electrodes for printed circuit boards, multilayer circuit boards, multi-chip modules, LCDs and LSIs, etc. In addition, the present invention relates to a method for manufacturing an electrode which can substantially improve workability by using a transfer film as compared with a conventional method.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for miniaturization, high definition, and high density of electrode wiring and projection electrodes of printed circuit boards, multilayer circuit boards, multi-chip modules, LCDs, LSIs, and the like.

Conventionally, such electrode manufacturing methods include (1) an etching method in which a metal thin film is formed by sputtering or vapor deposition, a resist is applied, exposed, developed, and then a pattern of the metal thin film is formed with an etchant. (2) a screen printing method in which a non-photosensitive conductive paste composition is screen-printed on a substrate to obtain a pattern, which is baked;
(3) forming a film of a photosensitive conductive paste composition on a substrate, irradiating the film with ultraviolet rays through a photomask, and developing the film to leave a pattern on the substrate;
A photolithography method for firing this is known.

[0004] However, the above-mentioned etching method has problems such as the necessity of vacuum equipment and low throughput in the process. In the screen printing method, there is a limit to the formation of a pattern of 100 μm or less due to high definition, and there is a problem that ordinary printing cannot cope with the resolution. In the photolithography method, 5 to 20
When a pattern having a thickness of μm was formed, the sensitivity in the depth direction of the conductive paste layer was insufficient, and a material having a wide development margin was not obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrode material which can form a high-definition pattern by a simple method which cannot be achieved by the above-mentioned etching method, screen printing method and photolithography method. It is in. That is, the present inventors separated the resist film and the conductive paste layer, which are photosensitive components, further formed a laminated film of the resist film and the conductive paste layer on the support film, formed on the support film Transferring the laminated film onto the substrate, exposing the resist film constituting the laminated film to form a latent image of the resist pattern, developing the resist film to make the resist pattern visible, The layer is etched to form a pattern of the conductive paste layer corresponding to the resist pattern, and the electrode is formed by a method including a step of baking the pattern.
According to such a manufacturing method, it is possible to form an electrode having a high-definition pattern and excellent surface uniformity, and to form a composite film (film) in which a film-forming material layer is formed on a support film. Hereinafter, also referred to as a “transfer film”) is advantageous in that it can be wound and stored in a roll shape.

A first object of the present invention is to provide a method for manufacturing an electrode having a novel method for forming an electrode. A second object of the present invention is to provide a method for manufacturing an electrode capable of forming a pattern with high dimensional accuracy.
A third object of the present invention is to provide a method of manufacturing an electrode which is capable of substantially improving workability as compared with a conventional manufacturing method and which has excellent manufacturing efficiency.

[0007]

The method of manufacturing an electrode according to the present invention is characterized in that an electrode is formed using a conductive paste layer formed on a support film. In particular,
Transfer the conductive paste layer formed on the support film onto the substrate, form a resist film on the conductive paste layer,
The resist film is exposed to light to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the conductive paste layer is etched to form a conductive paste corresponding to the resist pattern. An electrode is formed by a method including a step of forming a layer pattern and baking the pattern.

The preferred embodiments of the manufacturing method of the present invention are as follows. (A) The etching solution is an alkaline solution. (B) The developing solution used for the developing process and the etching solution used for the etching process are the same solution.

Further, according to the manufacturing method of the present invention, a laminated film of a resist film and a conductive paste layer is formed on a supporting film, and the laminated film formed on the supporting film is transferred onto a substrate. Forming a latent image of the resist pattern by exposing the resist film constituting the resist pattern, developing the resist film to reveal the resist pattern, etching the conductive paste layer to form a conductive pattern corresponding to the resist pattern; An electrode is formed by a method including a step of forming a pattern of a paste layer and baking the pattern.

[0010]

In the production method of the present invention, the conductive paste layer comprises a conductive paste composition in which conductive particles are dispersed.
Rather than being formed directly on a rigid substrate, it is formed by coating on a flexible support film. For this reason, as a method for applying the paste-like composition, an application method using a roll coater or the like can be employed, whereby the conductive paste layer having a large film thickness and excellent uniformity in film thickness can be used. For example, 1 to 20
μm ± 1 μm) on the support film. Then, the conductive paste layer thus formed can be reliably formed on the substrate by a simple operation of transferring the conductive paste layer to the surface of the substrate. Therefore, according to the manufacturing method of the present invention, it is possible to improve the process (higher efficiency) in the process of forming the conductive paste layer and to improve the quality (higher definition) of the formed pattern. .

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method of the present invention will be described below in detail. In the production method of the present invention, [1]
Conductive paste layer transfer step, [2] resist film forming step, [3] resist film exposing step, [4] resist film developing step, [5] conductive paste layer etching step, [6] conductive An electrode is formed by a firing step of the conductive paste layer pattern.

<Transfer Step of Conductive Paste Layer> The manufacturing method of the present invention is characterized in that a transfer film is used and the conductive paste layer constituting the transfer film is transferred to the surface of the substrate. is there. Here, the transfer film includes a support film and a conductive paste layer formed on the support film, and a protective film layer may be provided on a surface of the conductive paste layer. The specific configuration of the transfer film will be described later.

An example of the transfer step is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film 20 is superimposed on the surface of the substrate 11 so that the surface of the conductive paste layer 21 is in contact with the surface of the substrate 11. After thermocompression bonding with a heating roller or the like, the support film 22 is peeled off from the conductive paste layer 21. Thereby, as shown in FIG. 1C, the conductive paste layer 21 is transferred to the surface of the substrate 11 and is brought into close contact therewith. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C.
The roll pressure by the heating roller can be 1 to 5 kg / cm ² , and the moving speed of the heating roller can be 0.1 to 10.0 m / min. The substrate may be preheated, and the preheating temperature may be, for example, 40 to 120 ° C.
When transferring the conductive paste layer, a lower antireflection layer may be provided between the substrate and the transfer film. The antireflection layer is obtained by applying a paste containing, for example, carbon black and drying the paste. In addition, as will be described later, the transfer of the antireflection layer and the conductive paste layer may be performed collectively by using a transfer film having a laminated film including the conductive paste layer and the antireflection layer.

<Step of Forming Resist Film> In this step, a resist film 31 is formed on the surface of the transferred conductive paste layer 21 as shown in FIG. The resist constituting the resist film 31 may be either a positive resist or a negative resist, and the specific composition thereof will be described later. Also, the resist film 3
In the first forming step, an antireflection layer containing an ultraviolet absorber such as a dye may be provided on the transferred conductive paste layer, and a resist film may be formed on the antireflection film. The resist film 31 can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method, and then drying the coating film. Alternatively, the resist composition may be formed by transferring the resist composition formed on the support film to the surface of the conductive paste layer 21. According to such a formation method, it is possible to improve the process (increase the efficiency) in the process of forming the resist film, and to achieve uniformity of the thickness of the conductive pattern to be formed. Resist film 3
The film thickness of 1 is usually 0.1 to 40 μm, preferably 0.5 to 20 μm.

<Exposure step of resist film> In this step, as shown in FIG.
Radiation such as ultraviolet rays is selectively irradiated (exposure) to the surface of the resist film 31 formed thereon via an exposure mask M.
Thus, a latent image of the resist pattern is formed. In the figure, MA and MB are a light transmitting part and a light shielding part in the exposure mask M, respectively. Here, the radiation irradiating apparatus is not particularly limited, such as an ultraviolet irradiating apparatus used in the photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device.

<Developing Step of Resist Film> In this step, a resist pattern (latent image) is made visible by developing the exposed resist film. Here, the development processing conditions include the type, composition, and concentration of the developer, the development time, the development temperature, and the development method (for example, the immersion method, the oscillating method, the shower method,
(Spray method, paddle method), a developing device, and the like can be appropriately selected. As a result of this development step, as shown in FIG.
A resist pattern 35 (a pattern corresponding to the exposure mask M) composed of B and B is formed. The resist pattern 35 functions as an etching mask in the next step (etching step). The constituent material of the resist remaining portion 35A has a lower dissolution rate in the etchant than the constituent material of the conductive paste layer 21. is necessary.

<Step of Etching Conductive Paste Layer> In this step, the conductive paste layer is etched to form a pattern of the conductive paste layer corresponding to the resist pattern. That is, as shown in FIG.
The portion corresponding to the resist removing portion 35B of No. 5 is dissolved in the etching solution and selectively removed. Here, FIG.
(G) shows the state during the etching process. Then, when the etching process is further continued, as shown in FIG. 2H, the substrate surface is exposed at a portion of the conductive paste layer 21 corresponding to the resist removed portion. Here, as the etching processing conditions, the type, composition, concentration, processing time, processing temperature, processing method (for example, immersion method, rocking method, shower method, (Spray method, paddle method), a processing apparatus, and the like can be appropriately selected. In addition, as an etching solution,
The resist film 31 and the conductive paste layer 21 are used so that the same solution as the developing solution used in the developing process can be used.
By selecting the type, the developing step and the etching step can be performed continuously, and the manufacturing efficiency can be improved by simplifying the steps. Here, the resist remaining portion 3 constituting the resist pattern 35
5A is preferably dissolved gradually during the etching process and completely removed at the stage when the conductive paste layer pattern is formed (at the end of the etching process). Even if a part or the whole of the remaining resist portion 35A remains after the etching process, the remaining resist portion 35A is removed in the next baking step.

<Step of firing conductive paste layer> In this step, the conductive paste layer pattern is fired to form electrodes. As a result, the organic material in the remaining portion of the material layer is burned off, the metal layer is formed, and the electrode material 50 having the conductive pattern 40 formed on the surface on the substrate as shown in FIG. Obtainable. Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the remaining portion of the material layer is burned off, and is usually 400 to
2000 ° C. The firing time is usually 10 to 1
00 minutes.

<Another Method for Forming Conductive Pattern> The method for forming a conductive pattern according to the present invention is shown in FIG.
And it is not limited to the method as shown in FIG. Here, as another method for forming the conductive pattern, there can be mentioned a forming method by the following steps (1) to (3). (1) After forming a resist film on the support film, a conductive paste layer is formed on the resist film. Here, when forming a resist film and a conductive paste layer,
A roll coater or the like can be used.
A laminated film having excellent thickness uniformity can be formed on the support film. (2) The laminated film including the resist film and the conductive paste layer formed on the support film is transferred onto the substrate. Here, the transfer conditions may be the same as the conditions in the above-mentioned “transfer step of conductive paste layer”. (3) The same operations as those in the above-mentioned "resist film exposure step", "resist film development step", "conductive paste layer etching step" and "conductive paste layer firing step" are performed. According to the above-described method, the conductive paste layer and the resist film are collectively transferred onto the substrate, so that the manufacturing efficiency can be further improved by simplifying the process.

The following are materials used in each of the above steps,
Various conditions will be described. <Substrate> The substrate material is, for example, a plate-like member made of an insulating material such as ceramic, glass, silicon, polycarbonate, polyester, aromatic amide, polyamide imide, and polyimide. The surface of the plate-like member is subjected to a chemical treatment with a silane coupling agent or the like; a plasma treatment; an ion plating method, as necessary.
An appropriate pretreatment such as a thin film formation treatment by a sputtering method, a gas phase reaction method, a vacuum evaporation method, or the like may be performed.

<Transfer Film> The transfer film used in the production method of the present invention comprises a support film and a conductive paste layer formed on the support film, and a protective film is provided on the surface of the conductive paste layer. A layer may be provided.

(1) Support Film: The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and having flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the conductive paste layer and the antireflection film-forming paste layer are stored in a roll and stored and supplied. can do. Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.

(2) Conductive Paste Layer: The conductive paste layer constituting the transfer film is a paste-like conductive paste composition containing conductive particles, a binder resin and a solvent as essential components on the support film. And drying the coating film to remove part or all of the solvent.

(3) Conductive Paste Composition The conductive paste composition used for producing a transfer film contains (a) conductivity, (b) a binder resin, and (c) a solvent. It is a paste-like composition.

(A) Conductive Particles The conductive particles used in the electrode forming material include Ag,
Au, Cr, Ni, Al, Ag-Pd alloy, Cu and the like can be mentioned.

(B) Binder Resin As the binder resin used in the conductive paste composition of the present invention, various resins can be used. The binder resin contains 30 to 100% by weight of an alkali-soluble resin. It is particularly preferable to use a binder that performs the following. Here, “alkali-soluble” refers to a property of being dissolved by an alkaline etching solution described later and having such a solubility as to perform an intended etching process. Specific examples of such alkali-soluble resins include, for example, (meth) acrylic resins, hydroxystyrene resins, novolak resins, polyester resins, and the like. Among such alkali-soluble resins, particularly preferred are the following copolymers of monomer (a) and monomer (b), or monomer (a), monomer (b) and monomer (c).
And an acrylic resin such as a copolymer thereof.

Monomers (a): acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Carboxyl group-containing monomers such as citraconic acid, mesaconic acid, and cinnamic acid; hydroxyl group-containing such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate Monomers; o-hydroxystyrene, m-
Alkali-soluble functional group-containing monomers represented by phenolic hydroxyl group-containing monomers such as hydroxystyrene and p-hydroxystyrene. Monomer (b): methyl (meth) acrylate, (meth)
(Meth) acrylates other than the monomer (a) such as ethyl acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;
Aromatic vinyl monomers such as styrene and α-methylstyrene; and monomers copolymerizable with monomers (a) represented by conjugated dienes such as butadiene and isoprene. Monomer (c): A polymerizable polymer such as a (meth) acryloyl group is attached to one end of a polymer chain such as polystyrene, poly (methyl) methacrylate, ethyl poly (meth) acrylate, and benzyl poly (meth) acrylate. Macromonomers represented by macromonomers having a saturated group:

The content of the binder resin in the conductive paste composition is usually 1 to 1000 parts by weight, preferably 1 to 1000 parts by weight, per 100 parts by weight of the conductive particles.
00 parts by weight.

(C) Solvent The solvent constituting the conductive paste composition is contained in order to impart appropriate fluidity or plasticity and good film-forming property to the conductive paste composition. The solvent constituting the conductive paste composition is not particularly limited, and examples thereof include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, and lactones. , Sulfoxides, sulfones, hydrocarbons, halogenated hydrocarbons and the like. Specific examples of such a solvent include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates, and alkoxyacetic acid. Esters, propionates, hydroxypropionates, alkoxypropionates, lactates, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates,
Alkoxyacetates, cyclic ketones, acyclic ketones, acetoacetates, pyruvates,
N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineol, N-methyl-2-pyrrolidone and the like can be mentioned. These can be used alone or in combination of two or more. The content ratio of the solvent in the conductive paste composition can be appropriately selected within a range where good film-forming properties (fluidity or plasticity) can be obtained.

In the conductive paste composition, as optional components, a plasticizer, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber,
Various additives such as a filler and a low-melting glass may be contained.

As a method of applying the conductive paste composition on the support film, a method capable of efficiently forming a large (for example, 1 μm or more) coating film having excellent uniformity of the film thickness is required. Specifically, preferred examples include a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a wire coater, and a slit die. The surface of the support film to which the conductive paste composition is applied is preferably subjected to a release treatment. Thereby, in the transfer step described later, the operation of peeling the support film can be easily performed.

The conditions for drying the coating film are, for example, 50 to
The drying temperature is set at 150 ° C. for about 0.5 to 30 minutes, and the residual ratio of the solvent after drying (content in the antireflection film forming paste layer) is usually within 2% by weight.

The thickness of the conductive paste layer formed on the support film as described above varies depending on the content of the conductive particles, the type and size of the member, and is, for example, 1 to 40 μm. . In addition, as a protective film layer that may be provided on the surface of the conductive paste layer,
Examples include a polyethylene film and a polyvinyl alcohol-based film.

<Resist Film (Resist Composition)> In the manufacturing method of the present invention, a resist film is formed on a conductive paste layer, and the resist film is subjected to an exposure treatment and a development treatment to thereby form the conductive paste. A resist pattern is formed on the layer. The resist composition used for forming the resist film includes (1) an alkali-developing radiation-sensitive resist composition, (2) an organic solvent-developing radiation-sensitive resist composition, and (3) an aqueous development-type radiation-sensitive resist. And the like. Hereinafter, these resist compositions will be described.

(1) Alkali Development Type Radiation-Sensitive Resist Composition The alkali development type radiation-sensitive resist composition contains an alkali-soluble resin and a radiation-sensitive component as essential components. Examples of the alkali-soluble resin constituting the alkali-developable radiation-sensitive resist composition include the alkali-soluble resins exemplified as those constituting the binder component of the conductive paste composition. Examples of the radiation-sensitive component constituting the alkali-developable radiation-sensitive resist composition include, for example, (a) a combination of a polyfunctional monomer and a photopolymerization initiator, and (b) a melamine resin and an acid by irradiation with a radiation. Examples thereof include a combination with a photoacid generator, (c) a compound in which an alkali-insoluble compound becomes alkali-soluble by irradiation, and among the above-mentioned combination (a), a polyfunctional (meth) acrylate and The combination of the negative type with the photopolymerization initiator and the positive type (c) are particularly preferable.

Specific examples of the polyfunctional (meth) acrylate constituting the negative-type radiation-sensitive component include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; and poly (meth) acrylates such as polyethylene glycol and polypropylene glycol. Di (meth) acrylates of alkylene glycol; di (meth) acrylates of hydroxyl-terminated polymers such as hydroxypolybutadiene, hydroxypolyisoprene, hydroxypolycaprolactone at both ends; glycerin, 1,2,4- Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as butanetriol, trimethylolalkane, tetramethylolalkane, dipentaerythritol; polyalkylene of trihydric or higher polyhydric alcohol Poly (meth) acrylates of recall adducts; 1,4-cyclohexanediol, 1,
Poly (meth) acrylates of cyclic polyols such as 4-benzenediols; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, Oligo (meth) acrylates such as spirane resin (meth) acrylate and the like can be mentioned.
More than one species can be used in combination.

Further, specific examples of the photopolymerization initiator constituting the negative type radiation-sensitive component include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
1-hydroxycyclohexylphenyl ketone, 2,2
-Dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1
Azo compounds such as azoisobutyronitrile and 4-azidobenzaldehyde or azide compounds; organic sulfur compounds such as mercaptan disulfide; benzoyl peroxide, di-tret
Organic peroxides such as -butyl peroxide, tret-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 1,3-
Bis (trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,3 Trihalomethanes such as 5-triazine; 2,2′-bis (2-chlorophenyl) 4,5
Examples thereof include imidazole dimers such as 4 ′, 5′-tetraphenyl 1,2′-biimidazole, and these can be used alone or in combination of two or more.

On the other hand, positive-type radiation-sensitive compounds include 1,2-benzoquinonediazide-4-sulfonic acid ester of polyhydroxy compound, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide. -5-sulfonic acid ester and 1,2
-Naphthoquinonediazide-6-sulfonic acid ester and the like, in particular, 1,2-naphthoquinonediazide-4
-Sulfonate, 1,2-naphthoquinonediazide-5-sulfonate are preferred. The radiation-sensitive compound can be obtained, for example, by reacting a polyhydroxy compound with quinonediazide sulfonyl chloride in the presence of a basic catalyst. Usually, the ratio (average esterification ratio) of quinonediazidesulfonic acid ester to all hydroxyl groups of the polyhydroxy compound is 20% or more and 100% or less, and preferably 40% or more and 95% or less. If the average esterification rate is too low, it is difficult to form a pattern, and if it is too high, sensitivity may be reduced. Here, the polyhydroxy compound used is not particularly limited, but specific examples include the following compounds.

[0039]

Embedded image

(Where X is₁~ X_FifteenAre the same as each other
One or different, a hydrogen atom, C₁~ C_FourAn alkyl group of
C₁~ C_FourAn alkoxy group of C₆~ C_TenAryl group
Or a hydroxyl group. Where X₁~ X_FiveAnd X₆~ X
_TenAt least one in each combination of water
It is an acid group. Also, Y₁Is a hydrogen atom or C₁ ~ C_Four
Is an alkyl group. )

[0041]

Embedded image

Wherein X _{16 to} X ₃₀ are the same as X _{1 to} X ₁₅ , provided that X _{16 to} X ₂₀ , X _{21 to} X ₂₅ and X
At least one in each of the combinations of the ₂₆ to X ₃₀
One is a hydroxyl group. Y _{2 to} Y ₄ are the same or different from each other, and are a hydrogen atom or a C _{1 to} C ₄ alkyl group. )

[0043]

Embedded image

(Wherein, X _{31 to} X ₄₄ are the same as X _{1 to} X ₁₅ , provided that at least one of X _{31 to} X ₃₅₎
One is a hydroxyl group. Y _{5 to} Y ₈ are the same or different, and each is a hydrogen atom or a C _{1 to} C ₄ alkyl group. )

[0045]

Embedded image

(Wherein, X _{45 to} X ₅₈ are the same or different from each other, and represent a hydrogen atom, a halogen atom, C ₁ -C ₄
Alkyl group, C ₁ -C ₄ alkoxy group, C ₅ -C ₇
Is a cycloalkyl group or a hydroxyl group. However, X ₄₅
At least one in each combination of to X ₄₈ and X ₄₉ to X ₅₃ is a hydroxyl group. Also, Y ₉ and Y
₁₀ is a hydrogen atom, C ₁
-C alkyl radical or a C ₅ -C ₇ cycloalkyl group _4. )

[0047]

Embedded image

Wherein X _{59 to} X ₈₀ are the same as X _{45 to} X ₅₈ described above, provided that X _{59 to} X ₆₃ , X _{64 to} X ₆₇ , and X ₇₂ to X ₇₂ .
At least one in each combination of X ₇₅ and X ₇₆ to X ₈₀ is a hydroxyl group. Y _{11 to} Y ₁₈ are
Hydrogen atoms or C ₁ to
It is a C ₄ alkyl group. )

[0049]

Embedded image

(Where X is₈₁~ X₉₀Are the same as each other
Or differently, a hydrogen atom, C₁~ C_Four An alkoxy group of
C₆~ C_TenIs an aryl group or a hydroxyl group. However,
X₈₁ ~ X₉₀At least one of which is hydroxyl
Group. )

The content ratio of the radiation-sensitive component in the alkali-developable radiation-sensitive resist composition is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of the alkali-soluble resin. . Further, the alkali-developable radiation-sensitive resist composition contains an organic solvent as appropriate in order to impart good film-forming properties. Examples of such an organic solvent include the solvents exemplified as the constituents of the conductive paste composition.

(2) Radiation-sensitive resist composition of the organic solvent development type:
It comprises at least one selected from natural rubber, synthetic rubber, and a cyclized rubber obtained by cyclizing them, and an azide compound as essential components. Specific examples of the azide compound constituting the organic solvent development type radiation-sensitive resist composition include 4,4′-diazidobenzophenone,
4'-diazidodiphenylmethane, 4,4'-diazidostilbene, 4,4'-diazidochalcone, 4,4'-
Examples thereof include diazidobenzalacetone, 2,6-di (4′-azidobenzal) cyclohexanone, and 2,6-di (4′-azidobenzal) -4-methylcyclohexanone. These may be used alone or in combination of two or more. Can be used in combination. The organic solvent-developable radiation-sensitive resist composition generally contains an organic solvent in order to impart good film-forming properties. Examples of such an organic solvent include those exemplified as the constituents of the paste composition for forming an antireflection film.

(3) Aqueous development-type radiation-sensitive resist composition: The aqueous development-type radiation-sensitive resist composition is, for example, a water-soluble resin such as polyvinyl alcohol and at least one selected from a diazonium compound and a dichromate compound. And a seed as an essential component.

The resist composition used in the production method of the present invention may contain, as optional components, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a filler. And various additives such as phosphors, pigments and dyes.

<Exposure Mask> The exposure pattern of the exposure mask M used in the exposure process of the resist film varies depending on the material, but is generally 10 to 500 μm.
It is a stripe of width.

<Developer> The developer used in the resist film developing step can be appropriately selected according to the type of the resist film (resist composition). In particular,
An alkali developer can be used for a resist film made of an alkali-developable radiation-sensitive resist composition, and an organic solvent developer can be used for a resist film made of an organic solvent-type radiation-sensitive resist composition. An aqueous developer can be used for the resist film made of the development-type radiation-sensitive resist composition.

The effective components of the alkali developer include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate,
Ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate , Inorganic alkaline compounds such as ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Organic alkaline compounds such as ethanolamine can be exemplified. The alkali developer used in the resist film developing step can be adjusted by dissolving one or more of the above alkaline compounds in water or the like. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. After the development processing with an alkali developing solution, a washing treatment is usually performed.

Specific examples of the organic solvent developer include organic solvents such as toluene, xylene and butyl acetate, and these can be used alone or in combination of two or more. After the development with the organic solvent developer, rinsing with a poor solvent is performed as necessary. Specific examples of the aqueous developer include water,
Alcohol and the like can be mentioned.

<Etching solution> The etching solution used in the step of etching the conductive paste layer is preferably an alkaline solution. Thereby, the alkali-soluble resin contained in the conductive paste layer can be easily dissolved and removed. Since the conductive particles contained in the conductive paste layer are uniformly dispersed in the alkali-soluble resin, by dissolving the alkali-soluble resin as a binder in an alkaline solution and washing, the conductive particles are simultaneously dispersed. Removed. Here, examples of the alkaline solution used as the etching solution include a solution having the same composition as the developing solution. When the etching solution is the same solution as the alkali developing solution used in the developing step, the developing step and the etching step can be performed continuously, and the manufacturing efficiency is reduced by simplifying the steps. Improvement can be achieved. After the etching with the alkaline solution is performed, usually,
A washing process is performed.

Further, an organic solvent that can dissolve the binder of the conductive paste layer can be used as the etching solution. Examples of such an organic solvent include the solvents exemplified as the constituents of the conductive paste composition. After the etching with the organic solvent is performed, a rinsing with a poor solvent is performed as necessary.

[0061]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively. The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (trade name: HLC-8, manufactured by Tosoh Corporation).
02A) is the average molecular weight in terms of polystyrene measured by the method described in Example 02A).

Synthesis Example 1 A monomer composition comprising 200 parts of N-methyl-2-pyrrolidone, 80 parts of n-butyl methacrylate, 20 parts of methacrylic acid and 1 part of azobisisobutyronitrile was placed in an autoclave equipped with a stirrer. ,
Under a nitrogen atmosphere, the mixture was stirred at room temperature until it became uniform, then polymerized at 80 ° C. for 3 hours, and further subjected to a polymerization reaction at 100 ° C. for 1 hour, and then cooled to room temperature to obtain a polymer solution. Here, the polymerization rate is 98%, and the copolymer precipitated from this polymer solution [hereinafter, referred to as “polymer (A)”
That. ] Has a weight average molecular weight (Mw) of 100,00
It was 0.

Synthesis Example 2 A monomer composition comprising 200 parts of ethyl 3-ethoxypropionate, 85 parts of n-butyl methacrylate, 15 parts of methacrylic acid, and 1 part of azobisisobutyronitrile was charged into an autoclave. A polymer solution was obtained in the same manner as in Synthesis Example 1 except for the above. here,
The polymerization rate was 98%, and the copolymer precipitated from this polymer solution [hereinafter referred to as “polymer (B)”. ] Was 50,000.

Synthesis Example 3 (Synthesis of PAC-1) 4.28 g (0.01 mol) of a compound represented by the following formula (A)
l) was dissolved in 30 g of tetrahydrofuran, and 2.8 g (0.028 mol) of triethylamine was added. While cooling the solution to 0-5 ° C, the 1,2-
Naphthoquinonediazide-5-sulfonyl chloride 7.1
1 g (0.025 mol) was added. After 5 hours, the precipitated triethylamine hydrochloride was filtered and then reprecipitated in 2,000 ml of 0.2% hydrochloric acid aqueous solution diluted with deionized water.
After filtration, washing with water was repeated three times, and then vacuum dried at 40 ° C., to obtain 9.2 g of a condensed compound. This compound was treated with PAC-1 (PAC; Photo Acid Com).
pound).

[0065]

Embedded image

[Production Example 1] Silver powder 75 was used as conductive particles.
0 parts and the polymer (A) 15 as an alkali-soluble resin.
0 parts, 20 parts of polypropylene glycol (molecular weight: 400, manufactured by Wako Pure Chemical Industries, Ltd.) as a plasticizer, and N as a solvent
-Methyl-2-pyrrolidone by kneading with 400 parts of a conductive paste composition for electrode formation [hereinafter, referred to as
It is referred to as “conductive paste composition (1)”. ] Was adjusted. Next, the obtained conductive paste composition (1) was
Polyethylene terephthalate (PE
T) A coating film was formed on a supporting film (200 mm in width, 30 m in length, 38 μm in thickness) using a roll coater. The formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, thereby removing a 20 μm-thick conductive paste layer for electrode formation [hereinafter referred to as “conductive paste layer (1)”. ] Formed on a support film [hereinafter referred to as “transfer film (1)”. ] Was produced.

[Preparation Example 2] 50 parts of polymer (B) as an alkali-soluble resin, 40 parts of pentaerythritol tetraacrylate as a polyfunctional monomer (radiation-sensitive component), and as a photopolymerization initiator (radiation-sensitive component) 2-
5 parts of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 3
-150 parts of ethyl ethoxypropionate were kneaded to prepare a paste-type negative-type alkali-developable radiation-sensitive resist composition (1).

Next, the obtained resist composition was applied to a supporting film (width 200 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET) film.
m) was applied by a roll coater to form a coating film.
The solvent is completely removed by drying the formed coating film at 110 ° C. for 5 minutes, thereby forming a resist film having a thickness of 5 μm [hereinafter referred to as “resist film (1)”. ] Formed on a support film [hereinafter referred to as “transfer film (2)”. ] Was produced.

[Production Example 3] 50 parts of polymer (B) as an alkali-soluble resin, 10 parts of PAC-1 as a photosensitive agent (radiation-sensitive component), and 150 parts of ethyl 3-ethoxypropionate as a solvent were mixed. By kneading, a paste-type positive-tone alkali-developable radiation-sensitive resist composition (2) was prepared.

Next, the obtained resist composition was applied to a support film (width 200 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET) film.
m) was applied by a roll coater to form a coating film.
The solvent is completely removed by drying the formed coating film at 100 ° C. for 5 minutes, thereby forming a 5 μm thick resist film [hereinafter referred to as “resist film (2)”. ] Formed on a support film [hereinafter referred to as “transfer film (3)”. ] Was produced.

<Example 1> [Step of transferring conductive paste layer] A conductive paste layer (1) for forming electrodes was formed on the surface of a 10 cm square alumina substrate.
The transfer film (1) was overlapped so that the surface of the transfer film was brought into contact, and the transfer film (1) was thermocompression-bonded with a heating roller. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 120 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. After the completion of the thermocompression bonding, the support film was peeled off from the conductive paste layer (1). As a result, the conductive paste layer (1) was transferred to the surface of the alumina substrate and brought into close contact therewith. When the film thickness of this conductive paste layer was measured, it was 20 μm.
m ± 1 μm.

[Step of Forming Resist Film] A transfer film (2) is superimposed on the surface of the conductive paste layer (1) so that the surface of the resist film (1) is in contact with the surface of the conductive paste layer (1). The heating roller was thermocompressed under the same crimping conditions as above. After the completion of the thermocompression bonding, the support film was peeled off from the resist film (1). As a result, the resist film (1) was transferred to the surface of the conductive paste layer (1) and brought into close contact therewith. The thickness of the resist film (1) transferred to the surface of the conductive paste layer (1) was measured and found to be in the range of 5 μm ± 1 μm.

[Resist Film Exposure Step] With respect to the resist film (1) formed on the laminate of the conductive paste layers,
Through an exposure mask (a stripe pattern having a width of 40 μm), an i-line (ultraviolet light having a wavelength of 365 nm) was irradiated from an ultrahigh-pressure mercury lamp. Here, the irradiation amount is 400 mJ / cm
^{And 2} .

[Resist Film Developing Step] The exposed resist film (1) is subjected to a developing treatment by a shower method using a 0.1% by weight aqueous solution of potassium hydroxide (25 ° C.) for 30 seconds. I went over it. Next, a water washing treatment with ultrapure water was performed, whereby the uncured resist not irradiated with the ultraviolet rays was removed, and a resist pattern was formed.

[Electrification Step of Conductive Paste Layer] Continuing with the above steps, an etching treatment by a shower method using a 0.1% by weight aqueous solution of potassium hydroxide (25 ° C.) as an etching solution is performed over 3 minutes. Was. Next, a washing treatment and a drying treatment with ultrapure water were performed. ,
A conductive paste layer pattern composed of a material layer remaining portion and a material layer removed portion was formed.

[Baking Step of Conductive Paste Layer] The alumina substrate on which the pattern of the conductive paste layer was formed was subjected to a baking treatment in a baking furnace at a temperature of 800 ° C. for 20 minutes. As a result, an electrode material in which the electrode wiring was formed on the alumina substrate was obtained. When the cross-sectional shape of the electrode in the obtained electrode material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 40 μm ± 2 μm and the height was 8 μm ± 1 μm.
m, and the dimensional accuracy was extremely high.

<Example 2> An electrode wiring was formed on an alumina substrate in the same manner as in Example 1 except that the transfer film (2) was changed to the transfer film (3). When the cross-sectional shape of the electrode in the obtained electrode material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 40 μm ± 2 μm.
m, the height was 8 μm ± 1 μm, and the dimensional accuracy was extremely high.

<Example 3> [Preparation of transfer film] A transfer film (4) in which a laminated film of a conductive paste layer and a resist film is formed on a support film by the following operations (a) to (b) ) Was prepared. (A) A positive type alkali-developable radiation-sensitive resist composition (1) used in Example 1 was coated with a PET film as a supporting film (width 200 mm, length 30 m, thickness 3).
8 μm) using a roll coater.
Dry at 0 ° C. for 5 minutes to completely remove the solvent, and a thickness of 5 μm
[Hereinafter referred to as “resist film (1 ′)”. ] Was formed on a support film. (B) The conductive paste composition used in Example 1 (1)
Is coated on the resist film (1 ′) using a roll coater, and the coating film is dried at 100 ° C. for 5 minutes to completely remove the solvent, and a 20 μm-thick conductive paste layer [hereinafter referred to as “conductive paste” Layer (1 ') ". ] To the resist film (1 ')
Formed on top.

[Step of Transferring Laminated Film] A transfer film was superposed on the same alumina substrate as used in Example 1 so that the surface of the conductive paste layer (1 ′) was in contact with the alumina substrate. Was thermocompression-bonded to a heating roller. Here, as the pressure bonding condition, the surface temperature of the heating roller is set to 12
At 0 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. After the completion of the thermocompression bonding, the support film was peeled off from the laminated film [the surface of the resist film (1 ')]. As a result, the laminated film was transferred to and adhered to the surface of the alumina substrate. When the film thickness of this laminated film [the laminated film of the conductive paste layer and the resist film] was measured, it was in the range of 25 μm ± 2 μm.

[Exposure Step / Development Step of Resist Film] The resist film (1 ′) formed on the laminate of the conductive paste layers was exposed to light (irradiation with ultraviolet rays) under the same conditions as in Example 1. Then, a resist pattern was formed on the laminate of the conductive paste layers by performing a developing treatment with a potassium hydroxide aqueous solution and a washing treatment.

[Electric Conductive Paste Layer Etching Step] The conductive paste is etched, washed with water, and dried with an aqueous solution of potassium hydroxide under the same conditions as in Example 1 to form a conductive paste. A layer pattern was formed.

[Baking Step of Conductive Paste Layer] The alumina substrate on which the pattern of the conductive paste layer was formed was subjected to a baking treatment in a baking furnace at a temperature of 800 ° C. for 20 minutes. As a result, an electrode material in which the electrode wiring was formed on the alumina substrate was obtained. When the cross-sectional shape of the electrode in the obtained electrode material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 40 μm ± 2 μm and the height was 8 μm ± 1 μm.
m, and the dimensional accuracy was extremely high.

[0083]

According to the method for manufacturing an electrode of the present invention, the number of steps is substantially reduced as compared with the conventional method, and therefore, an electrode having improved workability can be manufactured. Further, according to the method for manufacturing an electrode of the present invention, a high-definition pattern can be formed as compared with the conventional method.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing a method of manufacturing an electrode according to an embodiment of the present invention in the order of steps.

FIG. 2 is an explanatory cross-sectional view sequentially showing a step that follows the step of FIG. 1 in the manufacturing method according to the embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 11 Substrate 20 Transfer film 21 Conductive paste layer 22 Support film 25 Conductive paste layer pattern 25A Material layer remaining part 25B Material layer removal part 31 Resist film M Exposure mask MA Light transmission part (exposure mask) MB Shield part (exposure) Mask) 35 resist pattern 35A resist remaining portion 35B resist removing portion 40 conductive pattern 50 electrode material

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation

Claims (3)

[Claims] 1. A method according to claim 1, wherein the conductive paste layer formed on the support film is transferred onto a substrate, a resist film is formed on the conductive paste layer transferred onto the substrate, and the resist film is exposed to light. Forming a latent image of the resist pattern, developing the resist film to reveal the resist pattern, etching the conductive paste layer to form a pattern of the conductive paste layer corresponding to the resist pattern, A method for producing an electrode, comprising: forming an electrode by firing. 2. A resist film, a laminated film having a conductive paste layer is formed on a support film, the laminated film is transferred onto a substrate, and the resist film constituting the laminated film is exposed to light to form a resist pattern. A latent image is formed, the resist film is developed to develop a resist pattern, the conductive paste layer is etched to form a pattern of the conductive paste layer corresponding to the resist pattern, and the pattern is baked. A method for manufacturing an electrode, comprising: 3. A transfer film, wherein a laminated film having a resist film and a conductive paste layer is formed on a support film.