JP2006236639A - Manufacturing method of plasma display panel and transfer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a PDP having such high sensitivity that can form a pattern even by a direct imaging method, excellent in workability, further, capable of suitably forming elements constituting the PDP, and excellent in pattern form (for example, dielectric layer, barrier rib, electrode, resistor, phosphor, color filter, black matrix), and to provide a transfer film suitably used for the manufacturing method. <P>SOLUTION: A resist film containing a specified photosensitizer, and a resin layer containing inorganic powder are used for the manufacturing method of the plasma display panel and the transfer film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a plasma display panel and a transfer film suitably used for the production method.

  In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, 3 denotes a partition, and cells are defined by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of reducing the resistance of the transparent electrode 4, 6 is an address electrode fixed to the glass substrate 2, and 7 is Fluorescent material held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is on the surface of the glass substrate 2 so as to cover the address electrode 6. The formed dielectric layers 10 are protective films made of, for example, magnesium oxide. In the color PDP, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  Such a PDP dielectric, partition, electrode, phosphor, color filter, black stripe (matrix), etc. are produced by forming a photosensitive inorganic powder-containing resin layer on a substrate and forming a pattern. A photolithographic method in which a pattern is left on the substrate by irradiating the film corresponding to the above with ultraviolet rays and then developing is suitably used. Among these steps, a method of performing ultraviolet irradiation through a photomask using a high-pressure mercury lamp as a light source (hereinafter referred to as a batch exposure method) was used. However, in recent PDP production lines, a direct imaging exposure method (hereinafter also referred to as “DI method”) in which a laser is used as a light source and a mask is not used has been studied due to an increase in the size of a glass substrate. ing. The DI method is more suitable for exposure of a large glass substrate than the batch exposure method in that an expensive and difficult-to-manage mask is unnecessary, and the panel design can be easily changed.

JP-A-6-67425 JP 2000-305262 A

  However, since the laser used in the DI method has a single wavelength and the exposure energy is very small compared to ultraviolet rays and the like conventionally used, the photosensitive inorganic powder-containing resin layer is exposed by the DI method. Has a problem that the pattern cannot be formed due to insufficient sensitivity. In addition, even if the exposure can be performed, the amount of exposure must be increased, so that there is a problem that it takes time to scan and the manufacturing throughput is low.

The present invention has been made based on the above situation.
A first object of the present invention is a PDP component (for example, a dielectric layer, a partition wall, an electrode, a resistor) having high sensitivity capable of forming a pattern even by the DI method, excellent workability, and excellent pattern shape. It is an object of the present invention to provide a method for producing a PDP capable of suitably forming a body, a phosphor, a color filter and a black matrix.
A second object of the present invention is to provide a transfer film which can form a PDP component having high sensitivity, excellent workability, and excellent pattern shape.
Further objects of the present invention will become apparent from the following description.

  In the first PDP production method of the present invention (hereinafter also referred to as “production method I”), an inorganic powder-containing resin layer is formed on a substrate, and the following formula (1) is formed on the inorganic powder-containing resin layer. ) And at least one selected from a compound represented by the following formula (2) (hereinafter also referred to as “compound (2)”): Forming a film, exposing the resist film to form a latent image of the resist pattern, developing the resist film to reveal the resist pattern, and etching the inorganic powder-containing resin layer to form a resist pattern The panel material which has an inorganic pattern is formed by the method including the process of forming the pattern of the inorganic powder containing resin layer corresponding to, and baking the said pattern.

[In the formula, Q ¹ is a heterocyclic group having 3 to 17 carbon atoms or —CO—Z (wherein Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3′-coumarin group); Q ^{2 to} Q ⁶ are each independently an alkyl group having 1 to 4 carbon atoms. ]

  The second PDP production method of the present invention (hereinafter also referred to as “production method II”) comprises a resist film containing at least one selected from the compound (1) and the compound (2), and an inorganic powder-containing resin layer. Is formed on a support film, the laminated film is transferred onto a substrate, a resist film constituting the laminated film is exposed to form a latent image of a resist pattern, and the resist film is developed. The resist pattern is revealed, the inorganic powder-containing resin layer is etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern, and the method includes a step of firing the pattern, A panel material having a pattern is formed.

  Moreover, the transfer film of the present invention comprises a resist film containing at least one selected from the compound (1) and the compound (2), an inorganic powder and a resin containing an inorganic powder and a binder resin on a support film. It has a laminated film with a layer.

Hereinafter, the present invention will be described in detail.
<PDP production method I>
In the production method I of the present invention, [1] an inorganic powder-containing resin layer forming step, [2] a resist film forming step, [3] a resist film exposing step, [4] a resist film developing step, [ 5) An inorganic powder-containing resin layer etching step, and [6] an inorganic powder-containing resin layer pattern firing step form a panel material having an inorganic pattern. Here, the panel material having an inorganic pattern is not particularly limited as long as it is a PDP component, and examples thereof include a partition, an electrode, a dielectric, a resistor, a phosphor, a color filter, and a black matrix.

[1] Formation process of inorganic powder-containing resin layer In the production method of the present invention, the inorganic powder-containing resin layer is formed by various methods such as screen printing, roll coating, spin coating, and cast coating. After applying the powder-containing resin composition, it can be formed by drying the coating film. Among them, a transfer film is used, and the inorganic powder-containing resin layer constituting the transfer film is transferred to the surface of the substrate. It is preferable to form by the method to do.
The transfer film has a support film and an inorganic powder-containing resin layer formed on the support film, and a protective film layer is provided on the surface of the inorganic powder-containing resin layer. May be. The specific configuration of the transfer film will be described later.

An example of the transfer process is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film is overlaid on the surface of the glass substrate so that the surface of the resin layer containing the inorganic powder is in contact with it, and this transfer film is heated. After thermocompression bonding with a roller or the like, the support film is peeled off from the inorganic powder-containing resin layer. As a result, the inorganic powder-containing resin layer is transferred and adhered to the surface of the glass substrate. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C., the roll linear pressure by the heating roller is 1 to 5 kg / cm 2, and the moving speed of the heating roller is 0.1 to 10.0 m / min. Can show. Further, the glass substrate may be preheated, and the preheat temperature can be set to 40 to 100 ° C., for example.
In the production method of the present invention, it is preferable to transfer and form a laminate composed of a plurality of inorganic powder-containing resin layers having different solubility in the etching solution on the substrate. By etching such a laminated body, anisotropy in the depth direction with respect to etching occurs, so that a material layer residual portion having a rectangular shape or a preferable cross-sectional shape close to a rectangle can be formed.
In addition, the lamination | stacking number of an inorganic powder containing resin layer shall be 10 or less normally, Preferably it shall be 2-5. Here, as a method of forming a laminate comprising n layers of inorganic powder-containing resin layers on a substrate, (1) the inorganic powder-containing resin layer (one layer) formed on the support film is transferred n times. (2) The method of (2) above from the viewpoint of simplification of the transfer process, although (2) the method of batch transfer of a laminate comprising an inorganic powder-containing resin layer of n layers may be used. Is preferred.

[2] Resist Film Forming Step In this step, a resist film is formed on the surface of the formed inorganic powder-containing resin layer. The resist constituting the resist film may be either a positive resist or a negative resist, and the specific composition thereof will be described later.
The resist film 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.
Moreover, you may form by transferring the resist film formed on the support film to the surface of an inorganic powder containing resin layer. According to such a forming method, it is possible to improve the process (high efficiency) in the resist film forming process, and to achieve uniform film thickness of the formed inorganic powder pattern.
The thickness of the resist film is usually 0.1 to 40 μm, preferably 0.5 to 20 μm.

[3] Resist Film Exposure Step In this step, a resist pattern latent image is formed on the surface of the resist film formed on the inorganic powder-containing resin layer by a method of scanning with laser light. Exposure in the case of irradiation with a laser usually consideration of productivity or the like, 0.01~50mJ / cm ^2, preferably 0.5~20mJ / cm ^2. In addition, a solid laser, a gas laser, a semiconductor laser, a liquid laser, or the like is used as a laser to be used, and a wavelength of from 350 nm that is an ultraviolet region light to about 600 nm that is a visible light region can be used. Commonly used wavelengths in this region are 405 nm, 442 nm, 488 nm, 532 nm, and the like.
Further, this step may be performed by a conventional method of selectively irradiating (exposing) radiation such as ultraviolet rays through an exposure mask. The ultraviolet irradiation apparatus used in this method is not particularly limited, and examples include an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device, and the like. It is done.

[4] Step of developing resist film In this step, the exposed resist film is developed to reveal a resist pattern (latent image).
Here, as development processing conditions, depending on the type of resist film, etc., the type / composition / concentration of developer, development time, development temperature, development method (for example, dipping method, rocking method, shower method, spray method, Paddle method), developing device and the like can be selected as appropriate.
By this development process, a resist pattern composed of a resist remaining portion and a resist removal portion is formed.
This resist pattern acts as an etching mask in the next process (etching process), and the constituent material of the resist remaining portion (photocured resist) is more resistant to the etching solution than the constituent material of the inorganic powder-containing resin layer. A low dissolution rate is required.

[5] Inorganic powder-containing resin layer etching step In this step, the inorganic powder-containing resin layer is etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern.
That is, in the inorganic powder-containing resin layer, a portion corresponding to the resist removal portion of the resist pattern is dissolved in the etching solution and selectively removed. When the etching process is further continued, the glass substrate surface is exposed at a portion corresponding to the resist removal portion in the inorganic powder-containing resin layer. Thereby, the inorganic powder containing resin layer pattern comprised from a material layer residual part and a material layer removal part is formed.
Here, as the etching treatment conditions, depending on the type of the inorganic powder-containing resin layer, etc., the type / composition / concentration of the etchant, the treatment time, the treatment temperature, the treatment method (for example, immersion method, rocking method, shower method) , Spray method, paddle method), processing apparatus, and the like can be appropriately selected.
In addition, by selecting the type of the resist film and the inorganic powder-containing resin layer so that the same solution as the developing solution used in the developing step can be used as the etching solution, the developing step and the etching step are performed. It becomes possible to carry out continuously, and it is possible to improve the manufacturing efficiency by simplifying the process.
Here, the resist residual portion constituting the resist pattern is gradually dissolved during the etching process, and is completely removed at the stage where the inorganic powder-containing resin layer pattern is formed (at the end of the etching process). Preferably there is.
Note that even if part or all of the remaining resist portion remains after the etching process, the remaining resist portion is removed in the next baking step.

[6] Inorganic powder-containing resin layer pattern firing step In this step, the inorganic powder-containing resin layer pattern is subjected to a firing treatment to form a dielectric, partition, electrode, resistor, phosphor, color filter, black matrix, or the like. Form. As a result, the organic substance in the remaining part of the material layer is burned out to form an inorganic layer such as a glass layer, a metal layer, or a phosphor layer, and a dielectric, partition, electrode, resistor, phosphor on the surface of the glass substrate. A panel material formed with a pattern such as a color filter or a black matrix can be obtained.
Here, the temperature of the baking treatment is required to be a temperature at which the organic substance in the material layer residual portion is burned off and the inorganic powder is fused, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

<PDP production method II>
Examples of the production method II in the present invention include formation methods according to the following steps (1) to (3).
(1) After forming a resist film on a support film, an inorganic powder-containing resin layer is laminated on the resist film. Here, when forming the resist film and the inorganic powder-containing resin layer, a roll coater or the like can be used, thereby forming a laminated film having excellent film thickness uniformity on the support film. Can do.
(2) The laminated film of the resist film and the inorganic powder-containing resin layer formed on the support film is transferred onto the substrate. Here, the transfer conditions may be the same as those in the “transfer process of the inorganic powder-containing resin layer”.
(3) Perform the same operations as the “resist film exposure process”, “resist film development process”, “inorganic powder-containing resin layer etching process” and “inorganic powder-containing resin layer pattern baking process”. .
According to the above method, since the inorganic powder-containing resin layer and the resist film are collectively transferred onto the substrate, it is possible to further improve manufacturing efficiency by simplifying the process.

Below, the material used for each said process, various conditions, etc. are demonstrated.
<Board>
As the substrate material, for example, a plate-like member made of an insulating material such as glass, silicon, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide or the like. For the surface of the plate-like member, chemical treatment with a silane coupling agent or the like, if necessary, plasma treatment; thin film formation treatment by an ion plating method, a sputtering method, a gas phase reaction method, a vacuum deposition method, etc. Such an appropriate pretreatment may be performed.

<Transfer film>
The transfer film used in the production method of the present invention comprises a support film and an inorganic powder-containing resin layer formed on the support film, and a protective film layer is formed on the surface of the inorganic powder-containing resin layer. It may be provided.
In addition, as the transfer film used in the production method of the present invention, the transfer film of the present invention having a laminated film of a resist film described later and an inorganic powder-containing resin layer on a support film is particularly preferably used. Hereinafter, the components of the transfer film of the present invention will be described in detail.

(1) Support film:
The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. When the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic powder-containing resin layer can be stored and supplied in a state of being wound in a roll. Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.
In addition, it is preferable that the mold release process is performed to the surface of the support film. Thereby, peeling operation of a support film can be easily performed in the transfer process mentioned later.

(2) Resin layer containing inorganic powder:
The inorganic powder-containing resin layer constituting the transfer film is a paste-like inorganic powder-containing resin composition containing inorganic powder, a binder resin and a solvent as essential components (for example, a partition wall forming composition, an electrode forming material). A composition, a composition for forming a dielectric, a composition for forming a resistor, a composition for forming a phosphor, a composition for forming a color filter, and a composition for forming a black matrix) on the support film, It can be formed by drying to remove part or all of the solvent.

(3) Inorganic powder-containing resin composition The inorganic powder-containing resin composition used for producing the transfer film contains (a) inorganic powder, (b) a binder resin, and (c) a solvent. A paste-like composition.

(A) Inorganic powder The inorganic powder used in the inorganic powder-containing resin composition of the present invention varies depending on the type of forming material.
For example, examples of the inorganic powder used for the partition wall forming material and the dielectric forming material include glass powder, preferably glass powder having a softening point of 400 to 600 ° C.
Specific examples of suitable glass powder include: 1. Mixture of lead oxide, boron oxide and silicon oxide (PbO-B ₂ O ₃ —SiO ₂ system) _2. a mixture of zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₃ —SiO ₂ system); _3. Mixture of lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system) 4. A mixture of lead oxide, zinc oxide, boron oxide and silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ system); 5. Mixture of bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system), 6. A mixture of zinc oxide, phosphorus oxide, silicon oxide (ZnO—P ₂ O ₅ —SiO ₂ system), 7. A mixture of zinc oxide, boron oxide, potassium oxide (ZnO—B ₂ O ₃ —K ₂ O system), 8. a mixture of phosphorus oxide, boron oxide, aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system); 10. Mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO—P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ system) 10. A mixture of zinc oxide, phosphorus oxide and titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system); A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide (ZnO—B ₂ O ₃ —SiO ₂ system—K ₂ O system), 12. 12. Mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO system), Examples thereof include a mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, and aluminum oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO—Al ₂ O ₃ system).
Examples of the inorganic powder used for the electrode forming material include Ag, Au, Al, Ni, Ag—Pd alloy, Cu, Cr, and Co.

Examples of the inorganic powder used for the resistor forming material include RuO ₂ .
The inorganic powder used for the phosphor forming material is Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , ( Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : Red phosphor such as Mn; Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : green phosphor such as Tb; Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ And (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , (Zn, Cd) S: Ag, and the like.
Inorganic powders used for the color filter forming material are red pigments such as Fe ₂ O ₃ , Pb ₃ O ₄ , CdS, CdSe, PbCrO ₄ , PbSO ₄ , Fe (NO ₃ ) ₃ ; Cr ₂ O ₃ , Green pigments such as TiO ₂ -CoO-NiO-ZnO, CoO-CrO-TiO ₂ -Al ₂ O ₃ , Co ₃ (PO ₄ ) ₂ , CoO-ZnO; 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) ・In addition to blue pigments such as Na ₂ S ₄ and CoO-Al ₂ O ₃ , PbCrO ₄ -PbSO ₄ , PbCrO ₄ , PbCrO ₄ -PbO, CdS, TiO ₂ -NiO-Sb ₂ Mention may be made of yellow pigments such as O ₃ ; orange pigments such as Pb (Cr—Mo—S) O ₄ ; purple pigments such as Co ₃ (PO ₄ ) ₂ .
Examples of the inorganic powder used for the black matrix forming material include Mn, Fe, Cr, Ni, Co and oxides and composite oxides thereof.
In addition to the inorganic powder described above, glass powder used for the partition wall forming material and dielectric forming material may be used in combination as the electrode, resistor, phosphor, color filter, and black matrix forming material. In this case, the content ratio of the glass powder is preferably 70% by mass or less based on the total amount of the inorganic powder.

(B) Binder Resin As the binder resin used in the inorganic powder-containing resin composition of the present invention, various resins can be used, but the alkali-soluble resin is contained in a proportion of 30 to 100% by mass. It is particularly preferable to use a binder resin.
Here, “alkali-soluble” refers to the property of being dissolved in an alkaline etching solution described later and having solubility to such an extent that the intended etching process is performed.
Specific examples of such alkali-soluble resins include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins. Of these, (meth) acrylic resins are particularly preferably used.
As said (meth) acrylic-type resin, the copolymer of the monomer which has the following alkali-soluble functional group, and another copolymerizable monomer can be mentioned.

As a monomer having an alkali-soluble functional group, for example,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono Carboxyl group-containing monomers such as (meth) acrylate;
Hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, and (meth) acrylic acid 3-hydroxypropyl; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene And hydroxyl group-containing monomers.

Examples of other copolymerizable monomers include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopenta (meth) acrylate (Meth) acrylic acid esters such as nil;
Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene;
Conjugated dienes such as butadiene and isoprene;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile;
A macro having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as polystyrene, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate benzyl, etc. And macromonomers such as monomers.
These can be used alone or in combination of two or more.

Particularly preferred compositions for the binder resin used in the composition of the present invention include methacrylic acid / 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer, and methacrylic acid / succinic acid mono (2-methacryloyloxy). Ethyl) / 2-hydroxypropyl methacrylate / n-butyl methacrylate copolymer.
The content ratio of the binder resin in the inorganic powder-containing resin composition is usually 1 to 200 parts by weight, preferably 5 to 150 parts by weight, particularly preferably 100 parts by weight of the inorganic powder. The amount is 10 to 120 parts by mass.

(C) Solvent The solvent constituting the inorganic powder-containing resin composition is contained in order to impart appropriate fluidity or plasticity and good film-forming properties to the inorganic powder-containing resin composition.
The solvent constituting the inorganic powder-containing resin composition is not particularly limited. For example, ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, Examples include lactones, sulfoxides, sulfones, hydrocarbons, and halogenated hydrocarbons.
Specific examples of such solvents include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetate esters, hydroxyacetic acid esters, alkoxyacetic acid. Esters, propionic acid esters, hydroxypropionic acid esters, alkoxypropionic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetic acid esters, cyclic ketones, Acyclic ketones, acetoacetic esters, pyruvates, N, N-dialkylformamides, N, N- Examples include alkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineol, N-methyl-2-pyrrolidone, etc., either alone or in combination of two or more. Can be used.
The content ratio of the solvent in the inorganic powder-containing resin composition can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) can be obtained.

  Inorganic powder-containing resin compositions include, as optional components, plasticizers, development accelerators, adhesion assistants, antihalation agents, storage stabilizers, antifoaming agents, antioxidants, ultraviolet absorbers, fillers, low melting glass And various other additives may be contained.

(4) Resist film (resist composition)
The resist composition used for the transfer film of the present invention usually contains (A) a resin, (B) a polyfunctional monomer, (C) a photopolymerization initiator, and (C ′) a photosensitizer. , (C ′) It is essential to have at least one selected from the compound (1) and the compound (2) as a photosensitizer.
In the manufacturing method of the present invention, a resist film may be formed on the inorganic powder-containing resin layer transferred onto the substrate. By subjecting the resist film to exposure processing and development processing, a resist pattern is formed on the inorganic powder-containing resin layer.

(A) Resin The resin (A) used in the resist composition needs to be an alkali-soluble resin in the case of an alkali development type, and has an ethylenically unsaturated monomer having at least one carboxyl group in the molecule. A carboxyl group-containing copolymer obtained by polymerizing a polymer and a copolymerizable monomer copolymerizable with the monomer is preferable. More preferred is a polymer having an unsaturated double bond in the side chain. Examples of the polymer include a copolymer obtained by polymerizing the monomer having a carboxyl group and an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule. ) A copolymer obtained by reacting acryloyloxyalkyl isocyanate is preferable.

  Specific examples of the monomer having a carboxyl group include carboxyl group-containing monomers among the monomers having an alkali-soluble functional group used as a constituent monomer of the binder resin of the above-described inorganic powder-containing resin composition. . These can be used alone or in combination of two or more.

The copolymer containing the structural unit derived from the carboxyl group-containing monomer has alkali solubility, and the copolymer obtained by using the monomer in particular in the proportions described below is an alkali development. Therefore, the photosensitive resist composition using this as a resin component has substantially less generation of undissolved material in an alkaline developer, and the substrate in the development process It is difficult for background stains and film residue to occur in places other than the resist pattern forming portion.
In addition, since the resist pattern obtained when this copolymer is used as a resin component does not excessively dissolve in an alkali developer and has excellent adhesion to the inorganic powder paste layer, the inorganic powder It is hard to fall off from the paste layer.

  Specific examples of the copolymerizable monomer copolymerizable with the carboxyl group-containing monomer include other copolymerizable monomers used as a constituent monomer of the binder resin of the above-described inorganic powder-containing resin composition. Is mentioned. These can be used alone or in combination of two or more.

Preferred examples of the resin (A) obtained by copolymerizing the carboxyl group-containing monomer and the copolymerizable monomer include methacrylic acid / benzyl methacrylate / 2-hydroxypropyl methacrylate, methacrylic acid / Examples include benzyl methacrylate / hydroxyethyl methacrylate, methacrylic acid / benzyl methacrylate / cyclohexyl methacrylate / 2-hydroxypropyl methacrylate, methacrylic acid / methyl methacrylate / cyclohexyl methacrylate / 2-hydroxypropyl methacrylate, and the like.
Moreover, as a specific example of the monomer having a hydroxyl group used for obtaining a polymer having an unsaturated double bond in the side chain, as a constituent monomer of the binder resin of the above-described inorganic powder-containing resin composition Among monomers having an alkali-soluble functional group to be used, hydroxyl group-containing monomers are exemplified. These can be used alone or in combination of two or more.
As a preferred specific example of a resin having a photopolymerizable unsaturated double bond in the side chain, 2-methacryloyloxyethyl ethyl isocyanate or 2-acryloyloxy is added to a base polymer of methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate. Those obtained by reacting ethyl isocyanate are preferred.

  The copolymerization ratio of the carboxyl group-containing monomer in the resin (A) is preferably 5 to 50% by mass, particularly 10 to 40% by mass, based on the total amount of monomers. When the copolymerization ratio of the carboxyl group-containing monomer is less than 5% by mass, the resulting resist composition tends to be less soluble in an alkali developer. On the other hand, when the copolymerization ratio of the carboxyl group-containing monomer exceeds 50% by mass, the resist pattern tends to drop off from the inorganic powder paste layer during development.

Such a resin (A) has a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC, carrier: tetrahydrofuran) of 3,000 to 300, 000, particularly 5,000 to 200,000.
By using a resin having such a molecular weight, a resist composition having high developability can be obtained, whereby a resist pattern having sharp pattern edges can be formed.

(B) Multifunctional monomer As the polyfunctional monomer (B), polyfunctional (meth) acrylate is preferably used. Preferable specific examples include two or more functionalities such as polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. And polyfunctional acrylates thereof, oligomers thereof, ethylene oxide modification, and propylene oxide modification.
Among these, polypropylene glycol diacrylate, trimethylolpropane ethylene oxide-modified triacrylate, and pentaerythritol triacrylate are particularly strong in that the resist pattern has high strength and is less likely to cause soiling or film residue in areas other than the pattern formation area. preferable.

The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.
The proportion of the polyfunctional monomer (B) used is usually 5 to 100 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the resin (A). When this ratio is less than 5 parts by weight, the resist pattern strength tends to be insufficient. On the other hand, when this ratio exceeds 100 parts by weight, there is a tendency that the alkali resolution is lowered, or background contamination other than the resist pattern forming part, film residue, and the like are generated.

(C) Photopolymerization initiator As the photopolymerization initiator in the present invention, a known photopolymerization initiator can be used. In particular, a compound represented by the following formula (i) (hereinafter referred to as “compound (i)” ), A compound represented by the following formula (ii) (hereinafter also referred to as “compound (ii)”) and a compound represented by the following formula (iii) (hereinafter also referred to as “compound (iii)”) Are preferably used in combination. By using these compounds in combination, a resist film with higher sensitivity and suitable for use in the DI exposure method can be obtained.

[Wherein, R ^{1 to} R ⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms. However, the case where all of R ^{1 to} R ⁵ are hydrogen atoms is excluded. ]

[In formula, R < ⁶ > -R < ⁹ > is a C1-C4 alkyl group each independently. ]

[Wherein, R ¹⁰ represents —S—, —O— or —NR— (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). ]

  Compound (i) has a structure in which two imidazole units are bonded to each other at the 1-position or 2-position, and specifically, compounds of the following formulas (i-1) to (i-3) It is a single or a mixture of two or more.

[Wherein, X represents a group represented by the following formula (a), and Y represents a phenyl group.

^(Wherein, R 1 to R ⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group having a carbon number of 6 to 9 containing 1 to 4 carbon atoms. ^However, R 1 to R Except when all ⁵ are hydrogen atoms)]]

In the above formula (i), examples of the halogen atom represented by R ^{1 to} R ⁵ include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group and an ethyl group. Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group and the like. Examples of the aryl group having 6 to 9 carbon atoms include phenyl group, o- A tolyl group, m-tolyl group, p-tolyl group and the like can be mentioned. However, all of R ^{1 to} R ⁵ are not hydrogen atoms, and a plurality of them may be substituted. Moreover, when multiple substitution is carried out, a different substituent may be sufficient.

  As the compound (i), 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tri Chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dicyanophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-Dimethylphenyl) -4,4 ', 5,5' Tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (2,4-diphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) ) -4, 4 ', 5, 5 - can be given tetraphenyl biimidazole.

Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromo) Phenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole is preferred.
The proportion of compound (i) used in the present invention is usually 0.5-100 parts by weight, preferably 1-50 parts by weight, particularly preferably 3-30 parts per 100 parts by weight of the polyfunctional monomer (B). Parts by weight. In this case, if the total use ratio of these compounds is less than 0.5 parts by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that the pattern is missing, deficient or undercut. The formed pattern is easily dropped from the substrate during development. Moreover, when baking without peeling off a resist layer, a baking residue becomes easy to generate | occur | produce.

As the compound (ii), 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (di-n-propylamino) benzophenone, 4,4 ′ -Bis (di-i-propylamino) benzophenone, 4,4'-bis (di-n-butylamino) benzophenone, 4,4'-bis (di-i-butylamino) benzophenone, 4,4'-bis And (di-t-butylamino) benzophenone. Of these, 4,4′-bis (diethylamino) benzophenone is preferred.
The proportion of compound (ii) used in the present invention is usually 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts per 100 parts by weight of the polyfunctional monomer (B). Parts by weight. In this case, if the total use ratio of these compounds is less than 0.5 parts by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that the pattern may be missing, missing or undercut. The formed pattern is easily dropped from the substrate during development. Moreover, when baking without peeling off a resist layer, a baking residue becomes easy to generate | occur | produce.

Examples of the compound (iii) include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like. Of these, 2-mercaptobenzothiazole is preferred.
The proportion of compound (iii) used in the present invention is usually 0.01 to 30 parts by weight, preferably 0.5 to 20 parts by weight, particularly preferably 1 to 100 parts by weight of the polyfunctional monomer (B). -10 parts by weight. In this case, if the total use ratio of these compounds is less than 0.01 parts by weight, curing by radiation irradiation becomes insufficient, and there is a possibility that the pattern is missing, deficient or undercut, while if it exceeds 50 parts by weight. The formed pattern is easily dropped from the substrate during development. Moreover, when baking without peeling off a resist layer, a baking residue becomes easy to generate | occur | produce.
The ratio of compound (i), compound (ii) and compound (iii) is 0.5-2: 0.5-2: 0.5-2 as a molar ratio, particularly preferably 1: 1: 1. It is.

  In the resist composition, a photopolymerization initiator other than the compound (i), the compound (ii), and the compound (iii) may be used. Specific examples of other photopolymerization initiators include benzyl, benzoin, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2. -Phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Azo compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; organosulfur compounds such as mercaptan disulfide; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, Cumene Hydroper Organic peroxides such as xoxide and p-menthane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) Ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuranyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- [2- (3,4 dimethoxyphenyl)]-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-methoxyphenyl-4,6-bis (trichloromethyl) -1 , 3,5-triazine, trihalomethanes such as 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like. These can be used alone or in combination of two or more. Moreover, when using these photoinitiators, it is preferable to use together with compound (i)-(iii), and the content rate of the said photoinitiator in that case is compound (i)-(iii). ) To 80% by mass or less.

(C ′) Photosensitizer In the present invention, at least one selected from compound (1) and compound (2) (hereinafter also referred to as “specific photosensitizer”) is used as the photosensitizer. Is required. By adding the specific photosensitizer, it is possible to obtain a resist film that is highly sensitive and can be suitably used in the DI exposure method, and has an effect that the shape of the resulting pattern becomes favorable.

Examples of the heterocyclic group containing 3 to 17 carbon atoms represented by Q ¹ in the above formulas (1) and (2) include a benzothiazol group, a benzoimidazoloyl group, an N-methylbenzoimidazoloyl group, and a benzoxazoyl group. Can be mentioned. Of these, N-methylbenzimidazolyl and the like are particularly preferable.

  Specific examples of the specific photosensitizer include 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3- (2-benzothiazol) -7-dimethylaminocoumarin, 3- (2- Benzimidazolyl) -7-dimethylaminocoumarin, 3- (2-N-methylbenzimidazolyl) -7-dimethylaminocoumarin, 3- (benzoxazoyl) -7-dimethylaminocoumarin, 3-acetyl-4- Methyl-7-dimethylaminocoumarin, 3-benzoyl-4-methyl-7-dimethylaminocoumarin, 3- (2-benzothiazol) -4-methyl-7-dimethylaminocoumarin, 3- (2-benzimidazoloyl)- 4-methyl-7-dimethylaminocoumarin, 3- (2-N-methylbenzimidazolyl) -4-methyl-7- Methylaminocoumarin, 3- (benzoxazoyl) -4-methyl-7-dimethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-benzothiazol) -7- Diethylaminocoumarin, 3- (2-benzimidazolyl) -7-diethylaminocoumarin, 3- (2-N-methylbenzimidazolyl) -7-diethylaminocoumarin, 3- (benzoxazoyl) -7-diethylaminocoumarin, 3 -Acetyl-4-methyl-7-diethylaminocoumarin, 3-benzoyl-4-methyl-7-diethylaminocoumarin, 3- (2-benzothiazol) -4-methyl-7-diethylaminocoumarin, 3- (2-benzimidazoloyl) ) -4-Methyl-7-diethylaminocoumarin , 3- (2-N-methylbenzimidazolyl) -4-methyl-7-diethylaminocoumarin, 3- (benzoxazoyl) -4-methyl-7-diethylaminocoumarin, 2,3,5,6-1H, 4H-tetrahydro-9-acetylquinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9-benzoylquinolidino [9,9a, 1gh] coumarin, 2, 3,5,6-1H, 4H-tetrahydro-9- (2-benzothiazol) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (2-benzimidazo Yl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (2-N-methylbenzimidazolyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (benzoxazoyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8 -Methyl-9-acetylquinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methyl-9-benzoylquinolidino [9,9a, 1gh] coumarin 2,3,5,6-1H, 4H-tetrahydro-8-methyl-9- (2-benzothiazol) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro- 8-methyl-9- (2-benzimidazoyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methyl-9- (2-N-methylbenzoy) Dazoyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methyl-9-benzoxazoyl) quinolidino [9,9a, 1gh] coumarin, -Carbonyl bis (7-diethylamino) coumarin etc. can be mentioned.

  The specific photosensitizer may be appropriately selected and used depending on the wavelength and intensity of the light source used for exposure, and may be used alone or in combination of two or more. Moreover, although it changes with kinds of the other component and polyfunctional monomer which addition amount also combines, it is 0.00001-50 mass% normally with respect to a photoinitiator, More preferably, in the range of 0.0005-30 mass%. Used. When the addition amount is less than 0.00001% by mass, no improvement in sensitivity is observed. On the other hand, when the amount is more than 50% by mass, since the absorption is too strong, only the surface of the film is cured, and the deep part of the resist film is in an uncured state and the pattern is likely to be chipped. Moreover, when baking without peeling off a resist layer, a baking residue becomes easy to generate | occur | produce.

(D) Solvent The resist composition used in the present invention usually contains a solvent in order to impart appropriate fluidity or plasticity and good film forming properties.
The solvent contained in the resist 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 solvents include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetate esters, hydroxyacetic acid esters, alkoxyacetic acid. Esters, propionic acid esters, hydroxypropionic acid esters, alkoxypropionic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetic acid esters, cyclic ketones, Acyclic ketones, acetoacetic esters, pyruvates, N, N-dialkylformamides, N, N- Examples include alkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineol, N-methyl-2-pyrrolidone, etc., either alone or in combination of two or more. Can be used.
The content ratio of the solvent in the resist composition can be appropriately selected within a range where good film formability (fluidity or plasticity) is obtained.

  The resist composition used in the present invention includes, as optional components, a development accelerator, an adhesion assistant, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a filler, a phosphor, a pigment, Various additives such as dyes may be contained.

(5) Transfer Film Production Method In the transfer film of the present invention, a resist composition is applied onto a support film to form a resist film, and an inorganic powder-containing resin composition is applied onto the resist film. An inorganic powder-containing resin layer is formed. In addition, the transfer film of the present invention is formed by forming an inorganic powder-containing resin layer on a support film, forming a resist film on a protective film, and laminating the surface of the inorganic powder-containing resin layer and the resist film surface for pressure bonding. It can form suitably also by the method to do. In addition, the transfer film which apply | coated the inorganic powder containing resin composition on the support film, and formed the inorganic powder containing resin layer can also be used for the manufacturing method of this invention.
As a method of applying the resist composition and the inorganic powder-containing resin composition, it is possible to efficiently form a coating film having a large film thickness (for example, 10 μm or more) excellent in film thickness uniformity. Specifically, 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 the like can be mentioned as preferable examples.
In addition, it is preferable that the mold release process is performed to the surface of the support film. Thereby, peeling operation of a support film can be easily performed in the transfer process mentioned later.

  As drying conditions of a coating film, it is set as about 0.5 to 30 minutes, for example at 50-150 degreeC, and the residual ratio (content rate in an inorganic powder containing resin layer) after drying is 2 mass% normally. It is assumed to be within.

The thickness of the inorganic powder-containing resin layer formed on the support film as described above varies depending on the content of the inorganic powder, the type and size of the member, and is, for example, 10 to 100 μm.
Examples of the protective film that may be provided on the surface of the inorganic powder-containing resin layer include a polyethylene film and a polyvinyl alcohol film. Moreover, when providing a protective film, it is preferable that a support film is a thing with a smaller peeling force (it is easy to peel) with a support film and a protective film.

<Exposure pattern>
The exposure pattern formed in the resist film exposure step is generally a stripe having a width of 10 to 200 μm, although it varies depending on the material.

<Developer>
In the present invention, an alkali developer is generally used in the resist film developing step.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.
The alkaline developer used in the resist film development step can be adjusted by dissolving one or more of the alkaline compounds in water. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

<Etching solution>
The etching solution used in the etching process of the inorganic powder-containing resin layer is preferably an alkaline solution. Thereby, the alkali-soluble resin contained in the inorganic powder-containing resin layer can be easily dissolved and removed.
Since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the alkali-soluble resin, the inorganic powder is dissolved by washing the alkali-soluble resin as a binder with an alkaline solution and washing. Are also removed at the same time.
Here, examples of the alkaline solution used as the etching solution include a solution having the same composition as the developer.
When the etching solution is the same solution as the alkaline developer used in the development process, the development process and the etching process can be performed continuously, and the manufacturing efficiency can be improved by simplifying the process. It is preferable because improvement can be achieved.
In addition, after the etching process with an alkaline solution is performed, a washing process is usually performed.

Moreover, the organic solvent which can melt | dissolve the binder of an inorganic powder containing resin layer can also be used as etching liquid. Examples of the organic solvent include the solvents exemplified as those constituting the inorganic powder-containing resin composition.
In addition, after the etching process with an organic solvent is performed, the rinse process with a poor solvent is performed as needed.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.
[Mw of binder resin]
The weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) (trade name HLC-802A) manufactured by Tosoh Corporation.

<Synthesis example>
(1) Synthesis of binder resin of inorganic powder-containing resin composition:
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 180 parts of propylene glycol monomethyl ether acetate, 20 parts of benzyl methacrylate, 15 parts of methacrylate-n-butyl, 20 parts of 2-hydroxypropyl methacrylate, succinic acid Nitrogen atmosphere charged with 35 parts mono (2-methacryloyloxyethyl), 10 parts methacrylic acid, 0.5 part azobisisobutyronitrile and 3.5 parts 2,4-diphenyl-4-methyl-1-pentene Under stirring at room temperature until homogeneous. After stirring, the polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer (polymer A) solution. The obtained polymer solution had a polymerization rate of 97%, and the Mw of this polymer was 100,000.

(2) Resist resin synthesis 1:
In a flask equipped with a thermometer, stirrer, and reflux condenser, 200 parts of propylene glycol monomethyl ether acetate, 60 parts of benzyl methacrylate, 20 parts of 2-hydroxypropyl methacrylate, 20 parts of methacrylic acid, azobisisobutyronitrile 0.5 part and 2.5 parts of 2,4-diphenyl-4-methyl-1-pentene were charged and stirred in a nitrogen atmosphere at room temperature until uniform. After stirring, the polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer (polymer B) solution. The obtained polymer solution had a polymerization rate of 97%, and the Mw of this polymer was 35,000.

(3) Resin resin synthesis 2:
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 90 g of the propylene glycol monomethyl ether acetate solution (solid content 33% by mass) of polymer B obtained in (2) above, and heated to 45 ° C. Kept. Thereto, 9.7 g of 2-methacryloyloxyethyl isocyanate was dropped from a dropping funnel over 10 minutes. Then, after hold | maintaining at 45 degreeC for 3 hours, it cooled and synthesize | combined the polymer (polymer C) which has an unsaturated double bond in a side chain.

<Example 1>
(1) Preparation of resin composition containing inorganic powder:
As the inorganic powder, 100 parts of Ag powder having a specific surface area of 0.5 m2 / g, an average particle size of 2.3 μm, Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ glass frit having an average particle size of 3 μm (amorphous, After kneading with a bead mill 10 parts of a softening point of 520 ° C., 30 parts of polymer A as a binder resin, 1 part of oleic acid as a dispersant, 10 parts of pentaerythritol triacrylate as a plasticizer, and 100 parts of propylene glycol monomethyl ether as a solvent Then, an inorganic powder-containing resin composition (conductive paste composition) was prepared by filtering with a stainless mesh (400 mesh, 38 μm diameter).
(2) Preparation of resist composition:
60 parts of polymer B, 40 parts of trimethylolpropane triacrylate as a multifunctional monomer, 2,2′-bis-2-chlorophenyl-4,4 ′, 5,5′-tetraphenylbiimidazole (compound ( i)) 6 parts, 4,4′-bis (diethylamino) benzophenone (compound (ii)) 3 parts, 2-mercaptobenzothiazole (compound (iii)) 1.5 parts, 3,3 ′ as photosensitizer -Alkali-developable radiation-sensitive resist composition by kneading 0.5 parts of carbonylbis (7-diethylamino) coumarin and 100 parts of propylene glycol monomethyl ether acetate as a solvent and then filtering with a cartridge filter (2 μm diameter) (Hereinafter referred to as “resist composition”).

(3) Preparation of transfer film:
By the operations (a) to (c) below, a transfer film for forming an electrode of the present invention was produced, in which a laminated film formed by laminating a resist film and an inorganic powder-containing resin layer in this order was formed on a support film. .
(A) The resist composition prepared in (2) was applied onto a support film (I) made of a PET film with a film thickness of 38 μm using a blade coater, and the coating film was dried at 100 ° C. for 3 minutes to remove the solvent. Then, a resist film having a thickness of 8 μm was formed on the support film.
(B) The inorganic powder-containing resin composition prepared in (1) was applied on a support film (II) made of a PET film having a thickness of 38 μm using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes. The solvent was removed to form an inorganic powder-containing resin layer having a thickness of 12 μm on the support film.
(C) The transfer film was overlaid so that the surfaces of the resist film produced in (a) and (b) and the inorganic powder-containing resin layer were brought into contact with each other, and thermocompression bonded with a heating roller. Here, as pressure bonding conditions, the surface temperature of the heating roller was 90 ° C., the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. Thereby, a transfer film in which a laminated film having a resist film and an inorganic powder-containing resin layer was formed between support films was produced.

(4) Transfer process of laminated film:
The transfer film was superposed on the surface of the glass substrate so that the surface of the inorganic powder-containing resin layer of the transfer film prepared in (3) was in contact, and this transfer film was thermocompression bonded to a heating roller. Here, as pressure bonding conditions, the surface temperature of the heating roller was 90 ° C., the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. As a result, the transfer film was transferred to and closely adhered to the surface of the glass substrate.

(5) Exposure process / development process of resist film:
With respect to the resist film in the laminated film formed on the glass substrate in the above (4), a laser beam having a wavelength of 405 nm was irradiated onto the portion where the pattern was formed from the support film. At that time, the irradiation energy amount of the laser beam was set to 10 mJ / cm ² . After irradiation, the support film on the resist film is peeled off, and then the resist film is developed by a shower method using a 0.3% by mass sodium carbonate aqueous solution (30 ° C.) as a developing solution for the exposed resist film. Processing was carried out for 120 seconds.
Thereby, the uncured resist that was not irradiated with ultraviolet rays was removed to form a resist pattern. The resist pattern had a uniform pattern shape and a good shape with excellent pattern edge linearity.

(6) Etching process of inorganic powder-containing resin layer:
The inorganic powder-containing resin layer was etched for 60 seconds by the shower method using a 0.3% by mass sodium carbonate aqueous solution (30 ° C.) as an etching solution, following the above steps.
Next, washing with ultrapure water and a drying treatment were performed. Thereby, an inorganic powder-containing resin layer pattern was formed.

(7) Pattern firing step:
The glass substrate on which the pattern of the inorganic powder-containing resin layer was formed was fired at 560 ° C. for 10 minutes in an air atmosphere in a firing furnace. Thereby, an electrode pattern with a film thickness of 4 μm was formed on the surface of the glass substrate.
(8) Pattern evaluation:
The obtained electrode pattern had no cracks or chips and was excellent in shape.

<Example 2>
A transfer film was prepared in the same manner as in Example 1 except that the polymer C was used in place of the polymer B in Example 1 (2), and the exposure amount was 5 mJ / cm ² in Example 1 (5). The electrode pattern was formed and evaluated. As a result, the obtained electrode pattern was free from cracks and chips and was excellent in shape.

<Comparative example>
A resist composition was prepared in the same manner as in Example 1 except that 3,3′-carbonylbis (7-diethylamino) coumarin was not used in Example 1 (2). Formation and evaluation were performed. As a result, the resist in the exposed area was dissolved during development and a pattern could not be formed.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer 10 Protective layer

Claims (5)

An inorganic powder-containing resin layer is formed on a substrate, and at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) is formed on the inorganic powder-containing resin layer. The resist film is formed, the resist film is exposed to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the inorganic powder-containing resin layer is etched. Forming a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern, and forming a panel material having the inorganic pattern by a method including a step of baking the pattern. .

[In the formula, Q ¹ is a heterocyclic group having 3 to 17 carbon atoms or —CO—Z (wherein Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3′-coumarin group); Q ^{2 to} Q ⁶ are each independently an alkyl group having 1 to 4 carbon atoms. ] A laminated film of a resist film containing at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) and an inorganic powder-containing resin layer is formed on a support film. The laminated film is transferred onto the substrate, the resist film constituting the laminated film is exposed to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the inorganic powder A body material-containing resin layer is etched to form a pattern of an inorganic powder-containing resin layer corresponding to a resist pattern, and a panel material having an inorganic pattern is formed by a method including a step of baking the pattern. A method for manufacturing a plasma display panel.

[In the formula, Q ¹ is a heterocyclic group having 3 to 17 carbon atoms or —CO—Z (wherein Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3′-coumarin group); Q ^{2 to} Q ⁶ are each independently an alkyl group having 1 to 4 carbon atoms. ] The method for manufacturing a plasma display panel according to claim 1, wherein the resist film is exposed by a direct imaging exposure method using laser light. The method for producing a plasma display panel according to claim 1, wherein the obtained material is at least one selected from partition walls, electrodes, phosphors, color filters, and black stripes (matrix). On the support film, a resist film containing at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2), an inorganic powder and an inorganic powder containing a binder resin A transfer film comprising a laminated film with a body-containing resin layer.

[In the formula, Q ¹ is a heterocyclic group having 3 to 17 carbon atoms or —CO—Z (wherein Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3′-coumarin group); Q ^{2 to} Q ⁶ are each independently an alkyl group having 1 to 4 carbon atoms. ]

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