KR20060094037A - Process for preparing plasma display panel and transfer film - Google Patents

Abstract

The present invention is a component of a PDP (eg, dielectric layer, barrier rib, electrode, resistor, phosphor) that has high sensitivity, excellent workability, and excellent pattern shape so that a pattern can be formed even by a direct imaging method. Provided are a production method of a PDP capable of forming a color filter, a black matrix), and a transfer film preferably used in the production method.

The transfer film of this invention uses the resist film and the inorganic powder containing resin layer which contain a specific photosensitizer.

Plasma display panel, transfer film, resist film, inorganic powder

Description

Process for Preparing Plasma Display Panel and Transfer Film

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel.

<Brief description of symbols for the main parts of the drawings>

1, 2 glass substrate

3 bulkhead

4 transparent electrodes

5 bus electrode

6 address electrode

7 fluorescent material

8, 9 dielectric layers

10 protective layer

[Patent Document 1] Japanese Patent Laid-Open No. 6-67425

[Patent Document 2] Japanese Patent Laid-Open No. 2000-305262

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

In recent years, a plasma display attracts attention as a flat fluorescent display. 1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel (hereinafter also referred to as "PDP"). In the same figure, 1 and 2 are the glass substrates arrange | positioned opposingly, 3 is a partition, and the cell is partitioned 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 lowering the resistance of the transparent electrode 4, 6 is an address electrode fixed to the glass substrate 2 7 is a fluorescent material retained in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 to cover the transparent electrode 4 and the bus electrode 5, and 9 is a glass substrate to cover the address electrode 6 ( The dielectric layer 10 formed on the surface of 2) is a protective film made of, for example, magnesium oxide. Moreover, in a color PDP, in order to obtain a high contrast image, a color filter (red, green, blue), a black matrix, etc. may be provided between a glass substrate and a dielectric layer.

In such a method of manufacturing a dielectric, partition, electrode, phosphor, color filter, and black stripe (matrix) of the PDP, a photosensitive inorganic powder-containing resin layer is formed on a substrate, and ultraviolet rays are formed on the film corresponding to the portion forming the pattern. The photolithographic method of leaving a pattern on a board | substrate and baking it by developing after irradiating and developing is preferable. In this process, the irradiation of ultraviolet-ray was performed by passing a photomask using a high pressure mercury lamp to a light source (henceforth a collective exposure method). However, in recent PDP production lines, the direct imaging exposure method (henceforth "DI method") which uses a laser as a light source and does not use a mask is examined for the enlargement of a glass substrate. The DI method is suitable for the exposure of a large-size glass substrate as compared to the batch exposure method, such that an expensive and difficult to manage mask is unnecessary, and the panel design can be easily changed.

However, the laser used in the DI method is not only a single wavelength, but also has a very low exposure energy compared to ultraviolet rays or the like, which are conventionally used. Thus, the DI method does not have sufficient sensitivity to expose the photosensitive inorganic powder-containing resin layer, so that a pattern cannot be formed. there is a problem. In addition, even if exposure is possible, the amount of exposure must be increased, so there is a problem in that the throughput in manufacturing is low because scanning takes time.

This invention is made | formed based on the above circumstances.

The first object of the present invention is a component of a PDP (eg, a dielectric layer, a partition, an electrode, a resistor, a phosphor, high sensitivity, excellent workability, and excellent pattern shape so that a pattern can be formed even by the DI method). It is an object of the present invention to provide a method for producing a PDP capable of preferably forming a color filter and a black matrix).

The 2nd object of this invention is to provide the transfer film which can form the component of the PDP which is highly sensitive, is excellent in workability, and is excellent in pattern shape.

Another object of the present invention will become apparent from the following description.

A method for producing a first PDP of the present invention (hereinafter also referred to as "manufacturing method I") forms an inorganic powder-containing resin layer on a substrate, and a compound represented by the following formula (1) on the inorganic powder-containing resin layer And a resist film containing at least one compound selected from " compound (1) ") and a compound represented by the following formula (2) (hereinafter also referred to as " compound (2) "), and the resist film is subjected to exposure treatment to After forming a latent image of the resist pattern, developing the resist film to present the resist pattern, and etching the inorganic powder-containing resin layer to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern. A panel material having an inorganic pattern is formed by a method including a step of firing.

In the formula,

Q ¹ is a heterocyclic containing group having 3 to 17 carbon atoms or -CO-Z (where Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3'-kumarino group),

Q ² to Q ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms.

The method for producing a second PDP of the present invention (hereinafter also referred to as "manufacturing method II") comprises a laminated film of a resist film containing at least one selected from compound (1) and compound (2) and an inorganic powder-containing resin layer. After forming on the supporting film, transferring the laminated film on the substrate, the resist film constituting the laminated film is exposed to light to form a latent image of the resist pattern, and the resist film is developed to present the resist pattern to present the inorganic powder. The containing resin layer is etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern, and a panel material having an inorganic pattern is formed by a method including a step of baking the pattern.

In addition, the transfer film of the present invention comprises a laminated film of a resist film containing at least one selected from compound (1) and compound (2) and an inorganic powder-containing resin layer containing an inorganic powder and a binder resin on a support film. It is characterized by having.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<Production Method of PDP I>

In the manufacturing method I of this invention, [1] the inorganic powder containing resin layer formation process, [2] resist film formation process, [3] resist film exposure process, [4] resist film development process, [5] inorganic powder containing The panel material which has an inorganic pattern is formed by the etching process of a resin layer, and the baking process of [6] an inorganic powder containing resin layer pattern. Here, the panel material having an inorganic pattern is not particularly limited as long as it is a component of the PDP, and examples thereof include a partition wall, 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 applying the inorganic powder-containing resin composition by various methods such as a screen printing method, a roll coating method, a rotary coating method, a flexible coating method, and then drying the coating film. Although it is possible to use it, it is preferable to use the transfer film especially, and to form the inorganic powder containing resin layer which comprises this transfer film by the method of transferring to the surface of a board | substrate.

The transfer film here has a support film and the inorganic powder containing resin layer formed on this support film, and the protective film layer may be provided in the surface of this inorganic powder containing resin layer. The specific structure of a transfer film is mentioned later.

An example of the transfer process is as follows. After peeling the protective film layer of the transfer film used as needed, after laminating | stacking a transfer film so that the surface of an inorganic powder containing resin layer may contact the surface of a glass substrate, and heat-compression-bonding this transfer film with a heating roller etc., The support film is peeled off from an inorganic powder containing resin layer. Thereby, the inorganic powder-containing resin layer is transferred to and adhered to the surface of the glass substrate. As transfer conditions here, the surface temperature of a heating roller can show 80-140 degreeC, the roll line pressure by a heating roller is 1-5 kg / cm, and the moving speed of a heating roller is 0.1-10.0 m / min, for example. have. In addition, the glass substrate may be preheated, and preheating temperature can be 40-100 degreeC, for example.

In the manufacturing method of this invention, it is preferable to transfer-form on the board | substrate the laminated body containing the some inorganic powder containing resin layer from which solubility differs with respect to etching liquid. By etching the laminate, since anisotropy in the depth direction with respect to etching occurs, the material layer remaining portion having a spherical shape or a preferable cross-sectional shape close to a spherical shape can be formed.

Moreover, the lamination number of an inorganic powder containing resin layer is 10 or less normally, Preferably it is 2-5. Here, as a method of forming the laminated body containing an n-layer inorganic powder containing resin layer on a board | substrate, (1) The method of transferring the inorganic powder containing resin layer (1 layer) formed on the support film n times. , (2) Any method of collectively transferring a laminate including an n-layer inorganic powder-containing resin layer may be used, but the method of (2) above is preferable from the viewpoint of simplification of the transfer step.

[2] formation process of resist film

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 its specific composition will be described later.

The resist film can be formed by drying the coating film after applying the resist by various methods such as a screen printing method, a roll coating method, a rotation coating method, a flexible coating method, and the like.

Moreover, it can also 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 formation method, not only the process improvement (high efficiency) in the formation process of a resist film can be aimed at, but also the film thickness uniformity of the inorganic powder pattern formed can be aimed at.

The film thickness of a resist film is 0.1-40 micrometers normally, Preferably it is 0.5-20 micrometers.

[3] exposure step of resist film

In this step, a latent image of the resist pattern is formed by a method of scanning laser light on the surface of the resist film formed on the inorganic powder-containing resin layer. The exposure amount in the case of irradiation with a laser is usually 0.01 to 50 mJ / cm 2, preferably 0.5 to 20 mJ / cm 2 in consideration of productivity and the like. As the laser used, a solid laser, a gas laser, a semiconductor laser, a liquid laser, or the like may be used, and the wavelength may be from 350 nm in ultraviolet region light to 600 nm in visible region. Commonly used wavelengths in this region are 405 nm, 442 nm, 488 nm, 532 nm and the like.

In addition, this process can also be performed by the conventional method of selectively irradiating (exposure) radiation, such as an ultraviolet-ray, through the exposure mask. It does not specifically limit as an ultraviolet irradiation device used by this method, The exposure apparatus etc. which are used at the time of manufacture of the ultraviolet irradiation device, the semiconductor, and the liquid crystal display device which are generally used by the photolithographic method are mentioned.

[4] developing process of resist film

In this step, the resist pattern (latent image) is present by developing the exposed resist film.

As the development treatment conditions here, the type, composition, and concentration of the developer, the development time, the development temperature, the development method (for example, the immersion method, the rocking method, the shower method, the spray method, the paddle method), and the developing device, depending on the type of the resist film, etc. Etc. can be selected as appropriate.

By this developing step, a resist pattern composed of a resist remaining portion and a resist removing portion is formed.

This resist pattern acts as an etching mask in a subsequent step (etching step), and the constituent material of the resist remaining portion (photocured resist) needs to have a lower dissolution rate in the etching solution than the constituent material of the inorganic powder-containing resin layer. .

[5] etching process of inorganic powder-containing resin layer

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, the part corresponding to the resist removal part of a resist pattern among an inorganic powder containing resin layer melt | dissolves in an etching liquid, and is selectively removed. Further, if the etching process is continued, the surface of the glass substrate is exposed at the portion corresponding to the resist removing portion in the inorganic powder-containing resin layer. Thereby, the inorganic powder containing resin layer pattern comprised from a material layer remainder part and a material layer removal part is formed.

As etching process conditions here, according to the kind of inorganic powder containing resin layer, etc., the kind, composition, and concentration of etching liquid, processing time, processing temperature, processing method (for example, immersion method, rocking method, shower method, spray method, paddle method) ), The 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 that used in the developing step can be used as the etching solution, the developing step and the etching step can be carried out continuously, and the production is simplified by the process. The efficiency can be improved.

Here, it is preferable that the resist residual part which comprises a resist pattern is melt | dissolved gradually at the time of performing an etching process, and is completely removed at the stage (at the end of an etching process) in which an inorganic powder containing resin layer pattern is formed.

In addition, even if some or all of the resist remaining portion remains after the etching treatment, the resist remaining portion is removed in the next firing step.

[6] firing process of the inorganic powder-containing resin layer pattern

In this step, the inorganic powder-containing resin layer pattern is calcined to form dielectrics, barrier ribs, electrodes, resistors, phosphors, color filters, or black matrices. As a result, the organic material is lost in the remaining portion of the material layer to form an inorganic layer such as a glass layer, a metal layer, a phosphor layer, and a dielectric, partition, electrode, resistor, phosphor, color filter, or black matrix on the surface of the glass substrate. A panel material in which a pattern is formed can be obtained.

The baking treatment temperature here needs to be a temperature at which the organic substance in the material layer remaining portion disappears and the inorganic powder is fused, and is usually 400 to 600 ° C. In addition, baking time is 10 to 90 minutes normally.

<Production Method of PDP II>

As manufacturing method II in this invention, the formation method by the process of following (1)-(3) is mentioned.

(1) After forming a resist film on a support film, an inorganic powder containing resin layer is laminated | stacked and formed on this resist film. Here, when forming a resist film and an inorganic powder containing resin layer, a roll coater etc. can be used and a laminated film excellent in the uniformity of a film thickness can be formed on a support film by this.

(2) The laminated film of the resist film and inorganic powder containing resin layer formed on the support film is transferred on a board | substrate. The transfer conditions here may be the same as those in the "transfer process of inorganic powder containing resin layer".

(3) Operations similar to those of the above-described "exposure process of resist film", "development process of resist film", "etching process of inorganic powder-containing resin layer" and "firing process of inorganic powder-containing resin layer pattern" are performed.

According to the above method, since the inorganic powder containing resin layer and the resist film are collectively transferred on a board | substrate, manufacturing efficiency by the simplification of a process can be improved further.

Below, the material used for each said process, various conditions, etc. are demonstrated.

<Substrate>

As a board | substrate material, it is a plate-shaped member containing insulating materials, such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide, for example. About the surface of this plate-shaped member, Chemical treatment with a silane coupling agent etc. as needed; Plasma treatment; Suitable pretreatment such as thin film formation treatment by ion plating method, sputtering method, vapor phase reaction method, vacuum deposition method, or the like may be performed.

<Transfer film>

The transfer film used for the manufacturing method of this invention has a support film and the inorganic powder containing resin layer formed on this support film, and a protective film layer may be provided in the surface of this inorganic powder containing resin layer.

Moreover, as a transfer film used for the manufacturing method of this invention, the transfer film of this invention which has a laminated film of a resist film mentioned later and an inorganic powder containing resin layer on a support film is used especially preferably. Hereinafter, the component of the transfer film of this invention is explained in full detail.

(1) support film:

It is preferable that the support film which comprises a transfer film is a resin film which has heat resistance and solvent resistance, and has flexibility. When a support film has flexibility, a paste composition can be apply | coated with a roll coater, and it can supply, preserving an inorganic powder containing resin layer in the state wound up to roll shape. 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. Etc. can be mentioned. The thickness of a support film is 20-100 micrometers, for example.

Moreover, it is preferable that a mold release process is given to the surface of a support film. Thereby, peeling operation of a support film can be performed easily in the transfer process mentioned later.

(2) Inorganic powder-containing resin layer:

The inorganic powder-containing resin layer constituting the transfer film is a paste-like inorganic powder-containing resin composition (for example, a partition forming composition, an electrode forming composition, a dielectric forming composition) containing an inorganic powder, a binder resin, and a solvent as essential components. , 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) can be formed on the supporting film and dried to remove part or all of the solvent by drying the coating film.

(3) inorganic powder-containing resin composition

The inorganic powder containing resin composition used in order to manufacture a transfer film is a paste-like composition containing (a) inorganic powder, (b) binder resin, and (c) solvent.

(a) inorganic powder

The inorganic powder used for the inorganic powder containing resin composition of this invention changes with kinds of formation material.

For example, as an inorganic powder used for a partition formation material and a dielectric formation material, glass powder, Preferably the glass powder whose softening point is 400-600 degreeC is mentioned.

Specific examples of preferred glass powders include: 1. a mixture of lead oxide, boron oxide, silicon oxide (PbO-B ₂ O ₃ -SiO ₂ based), 2. zinc oxide, boron oxide, 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 0 ₃ system), 4. lead oxide, zinc oxide, Mixture of boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ), 5. mixture of bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ -B ₂ O ₃ -SiO _{2 type} ), 6. A mixture of zinc oxide, phosphorus oxide and silicon oxide (ZnO-P ₂ O ₅ -SiO ₂ based), 7. A mixture of zinc oxide, boron oxide and potassium oxide (ZnO-B ₂ O ₃ -K ₂ O based) 8. A mixture of phosphorus oxide, boron oxide and aluminum oxide (P ₂ O ₅ -B ₂ O ₃ -Al ₂ O ₃ based), 9. zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO-P ₂ O ₅ -SiO ₂ -Al ₂ O ₃ system), 10. zinc oxide, phosphorus oxide, a mixture of titanium oxide (ZnO-P ₂ O ₅ -TiO ₂ system), 11. zinc oxide, boron oxide, silicon oxide, mountain Potassium _{(ZnO-B 2 O 3 -SiO} 2 based -K ₂ O-based) was added, 12 of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium (ZnO-B ₂ O ₃ -SiO ₂ -K ₂ oxidation of O-CaO system), 13. Zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, aluminum oxide (ZnO-B ₂ O ₃ -SiO ₂ -K ₂ O-CaO-Al ₂ O _{3 type} ) And mixtures thereof may be exemplified.

Examples of the inorganic powder used for the electrode forming material include Ag, Au, Al, Ni, Ag-Pd alloys, Cu, Cr, Co, and the like.

Examples of the inorganic powder used for the resistor forming material include RuO ₂ .

Inorganic powders used in the phosphor material forming the _{^{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; Green phosphors such as 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 : Tb; _{Y 2 SiO 5: Ce, BaMgAl} 10 O 17: Eu 2 +, BaMgAl 14 O 23: Eu 2 +, (Ca, Sr, Ba) 10 (PO 4) 6 Cl 2: Eu 2+, (Zn, Cd) Blue phosphors, such as S: Ag, are mentioned.

Inorganic powders used for the color filter forming materials include red pigments such as Fe ₂ O ₃ , Pb ₃ O ₄ , CdS, CdSe, PbCrO ₄ , PbSO ₄ , Fe (NO ₃ ) _3, and the like. Green pigments such as Cr ₂ O ₃ , 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) · Na 2 S 4, in addition to Al ₂ O ₃ such as blue-CoO pigment for color correction of an inorganic pigment _{PbCrO 4 -PbSO 4, PbCrO 4,} PbCrO 4 -PbO, CdS, Yellow pigments such as TiO ₂ -NiO-Sb ₂ O ₃ ; Orange pigments such as Pb (Cr-Mo-S) O ₄ ; And 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 complex oxides thereof.

In addition, the glass powder used for a partition formation material and a dielectric formation material can be used together for the formation material of an electrode, a resistor, fluorescent substance, a color filter, and a black matrix in addition to the inorganic powder mentioned above. In this case, it is preferable that the content rate of glass powder is 70 mass% or less with respect to inorganic powder whole quantity.

(b) binder resin

Although various resin can be used as binder resin used for the inorganic powder containing resin composition of this invention, it is especially preferable to use the binder resin which contains alkali-soluble resin in the ratio of 30-100 mass%.

"Alkali-soluble" here means the property which has solubility to the extent that a target etching process will be performed when it melt | dissolves with the alkaline etching liquid mentioned later.

As a specific example of such alkali-soluble resin, (meth) acrylic-type resin, hydroxy styrene resin, a novolak resin, polyester resin, etc. are mentioned, for example. Among these, (meth) acrylic resin is 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 is mentioned.

As a monomer which has 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 group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; and hydroxyl group-containing monomers such as o-hydroxy styrene, m-hydroxy styrene and p-hydroxy styrene.

As another copolymerizable monomer, for example

(Meth), such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate ) Acrylic acid esters;

Aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene;

Conjugated dienes such as butadiene and isoprene;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile;

Macromonomers, such as a macromonomer which has a polymerizable unsaturated group, such as a (meth) acryloyl group, in one terminal of a polymer chain, such as polystyrene, methyl poly (meth) acrylate, poly (meth) acrylate, benzyl poly (meth) acrylate, etc. Etc. can be mentioned.

These can be used individually or in combination of 2 or more types.

As a particularly preferable composition as a binder resin used for the composition of this invention, methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid n-butyl copolymer or methacrylic acid / succinic acid mono (2-methacrylo) Monooxyethyl) / methacrylic acid 2-hydroxypropyl / methacrylic acid n-butyl copolymer.

The binder resin content ratio in an inorganic powder containing resin composition is 1-200 mass parts normally with respect to 100 weight part of inorganic powders, Preferably it is 5-150 mass parts, Especially preferably, it is 10-120 mass parts.

(c) solvent

The solvent which comprises an inorganic powder containing resin composition is contained in order to provide moderate fluidity | liquidity, plasticity, and favorable film formation property to the said inorganic powder containing resin composition.

The solvent constituting the inorganic powder-containing resin composition is not particularly limited, but examples thereof include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, and sulfoxy. Drew, sulfones, hydrocarbons, halogenated hydrocarbons, etc. are mentioned.

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 and acetic acid 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 acid esters, pyruvic acid esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, Dialkyl sulfoxides, dialkyl sulfones, terpineol, N-methyl-2-pyrrolidone and the like Number, and these may be used alone or in combination of two or more.

The solvent content ratio in an inorganic powder containing resin composition can be suitably selected within the range from which favorable film formation property (fluidity or plasticity) is obtained.

The inorganic powder-containing resin composition may contain various additives such as a plasticizer, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a filler, and a low melting point glass as an optional component.

(4) resist film (resist composition)

The resist composition used for the transfer film of the present invention usually contains (A) resin, (B) polyfunctional monomer, (C) photoinitiator and (C ') photosensitizer, wherein (C') photosensitizer As an agent, what has 1 or more types chosen from a compound (1) and a compound (2) is essential.

Moreover, in the manufacturing method of this invention, a resist film can also be formed and used on the inorganic powder containing resin layer transferred on the board | substrate. The resist pattern is formed on the said inorganic powder containing resin layer by performing exposure process and image development process to this resist film.

(A) resin

Resin (A) used for a resist composition needs to be alkali-soluble resin in the case of alkali developing type, and is obtained by superposing | polymerizing the ethylenically unsaturated monomer which has at least 1 or more carboxyl groups in a molecule | numerator, and the copolymerizable monomer copolymerizable with this monomer. It is preferable that it is a carboxyl group-containing copolymer. As a more preferable thing, the polymer which has an unsaturated double bond in a side chain is mentioned. As said polymer, the copolymer which made 2- (meth) acryloyloxyalkyl isocyanate react with the copolymer obtained by superposing | polymerizing the monomer which has the said carboxyl group, and the ethylenically unsaturated monomer which has at least 1 or more hydroxyl group in a molecule | numerator It is mentioned as a preferable thing.

Specific examples of the monomer having a carboxyl group include carboxyl group-containing monomers among monomers having alkali-soluble functional groups used as constituent monomers of the binder resin in the inorganic powder-containing resin composition described above. These can be used individually or in combination of 2 or more types.

The copolymer containing the structural unit derived from the above-mentioned carboxyl group-containing monomer has alkali solubility, and since the copolymer obtained when using this monomer at the ratio mentioned later especially has excellent solubility with respect to alkaline developing solution, this is used as a resin component. The photosensitive resist composition used has essentially no generation of undissolved matters to the alkaline developer, and is difficult to generate scum, film residues, etc. in portions other than the resist pattern forming portion of the substrate during development. .

Moreover, the resist pattern obtained when this copolymer is used as a resin component has the outstanding adhesiveness with respect to an inorganic powder paste layer, even if it does not melt | dissolve in an alkaline developing solution too much, and does not fall easily from an inorganic powder paste layer.

As a specific example of the copolymerizable monomer copolymerizable with the said carboxyl group-containing monomer, the other copolymerizable monomer used as a structural monomer of a binder resin in the above-mentioned inorganic powder containing resin composition is mentioned. These can be used individually or in combination of 2 or more types.

As a preferable specific example of resin (A) obtained by copolymerizing the said carboxyl group-containing monomer and a copolymerizable monomer, methacrylic acid / benzyl methacrylate / 2-hydroxypropyl methacrylate, methacrylic acid / benzyl methacrylate / Hydroxyethyl methacrylate, methacrylic acid / benzyl methacrylate / cyclohexyl methacrylate / 2-hydroxypropyl methacrylate, methacrylic acid / methyl methacrylate / cyclohexyl methacrylate / methacrylic acid 2 -Hydroxypropyl, etc. are mentioned.

Moreover, as a specific example of the monomer which has a hydroxyl group used in order to obtain the polymer which has an unsaturated double bond in a side chain, a hydroxyl group is contained in the monomer which has an alkali-soluble functional group used as a structural monomer of a binder resin in the inorganic powder containing resin composition mentioned above. Containing monomers are mentioned. These can be used individually or in combination of 2 or more types.

As a preferable specific example of resin which has a photopolymerizable unsaturated double bond in a side chain, 2-methacryloyloxyethyl ethyl isocyanate or a methacrylic acid / benzyl methacrylate / 2-hydroxyethyl base polymer is a base polymer. It is preferable that it is obtained by making 2-acryloyloxyethyl isocyanate react.

It is preferable that the copolymerization ratio of the carboxyl group-containing monomer in resin (A) is 5-50 mass% with respect to monomer whole quantity especially 10-40 mass%. When the copolymerization ratio of a carboxyl group-containing monomer is less than 5 mass%, the resist composition obtained tends to become low in the solubility to alkaline developing solution. On the other hand, when the copolymerization ratio of a carboxyl group-containing monomer exceeds 50 mass%, there exists a tendency for a resist pattern to separate from an inorganic powder paste layer at the time of image development.

Such a resin (A) has a polystyrene reduced weight average molecular weight (hereinafter referred to simply as "weight average molecular weight") measured by gel permeation chromatography (GPC, carrier: tetrahydrofuran) of 3,000 to 300,000, especially 5,000 to 200,000. It is preferable.

By using the resin having such a molecular weight, a highly developable resist composition can be obtained, whereby a resist pattern having a distinct pattern edge can be formed.

(B) polyfunctional monomer

As a polyfunctional monomer (B), polyfunctional (meth) acrylate is used preferably. Preferred specific examples include polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, And bifunctional or higher polyfunctional acrylates such as dipentaerythritol hexaacrylate, oligomers thereof, ethylene oxide modified substances, and propylene oxide modified substances.

Among them, polypropylene glycol diacrylate, trimethylolpropane ethylene oxide modified triacrylate, and pentaerythritol triacrylate have high strength of resist pattern and are difficult to cause background contamination or film residues other than the pattern formation portion. Particularly preferred.

It is preferable that the molecular weight of the said polyfunctional (meth) acrylate is 100-2,000.

The use ratio of a polyfunctional monomer (B) is 5-100 weight part normally with respect to 100 weight part of resin (A), Preferably it is 10-70 weight part. If 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, alkali resolution tends to decrease, or background contamination other than the resist pattern forming portion, film residues, and the like tend to occur.

(C) photoinitiator

As a photoinitiator in this invention, although a well-known photoinitiator can be used, the compound represented by following formula (i) (hereinafter also called "compound (i)"), the compound represented by following formula (ii) It is preferable to use a combination of "compound (ii)") and a compound represented by the following formula (iii) (hereinafter also referred to as "compound (iii)"). By using these compounds together, the resist film used suitably with high sensitivity for DI exposure method can be obtained.

<Formula i>

<Formula ii>

<Formula iii>

In the formula,

R ¹ to R ⁵ each independently represent 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, except that all of R ¹ to R ⁵ are hydrogen atoms;

R ⁶ to R ⁹ are each independently an alkyl group having 1 to 4 carbon atoms;

R ¹⁰ is —S—, —O— or —NR— (R is 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 one or two positions, and specifically, are compounds alone or as a mixture of two or more thereof.

<Formula i-1>

<Formula i-2>

<Formula i-3>

In the formula, X represents a group represented by the following formula a, and Y represents a phenyl group.

<Formula a>

In the formula, each of R ¹ to R ⁵ 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, but when all of R ¹ to R ⁵ are hydrogen atoms Is excluded.

Examples of the halogen atom represented by R ¹ to R ⁵ in Chemical Formula i include a chlorine atom, a boron atom, an iodine atom, and the like. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, and i-propyl group. Group, n-butyl group, i-butyl group, t-butyl group, etc. are mentioned, As an example of a C6-C9 aryl group, a phenyl group o-tolyl group, m-tolyl group, p-tolyl group, etc. are mentioned. Can be. Provided that R ¹ to R ⁵ Not all are hydrogen atoms, and two or more may be substituted. In addition, when more than one substituent is substituted, another substituent may be sufficient.

Examples of the compound (i) include 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4,6- Trichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl Biimidazole, 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'-tetra Phenylbiimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-tri Methylphenyl) -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'-tetraphenylbiimidazole, etc. are mentioned. have.

Among them, 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-dibromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole is preferred.

The use ratio of the compound (i) in this invention is 0.5-100 weight part normally with respect to 100 weight part of polyfunctional monomers (B), Preferably it is 1-50 weight part, Especially preferably, it is 3-30 weight part. . In this case, when the total use ratio of these compounds is less than 0.5 parts by weight, curing by irradiation is insufficient, and there is a possibility that a missing, missing or undercut may occur in the pattern. It becomes easy to fall off from a board | substrate. Moreover, when baking without peeling a resist layer, a baking residue will generate easily.

Examples of the compound (ii) include 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 And 4,4'-bis (di-t-butylamino) benzophenone. Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

The use ratio of the compound (ii) in this invention is 0.5-50 weight part normally with respect to 100 weight part of polyfunctional monomers (B), Preferably it is 1-30 weight part, Especially preferably, it is 1-20 weight part. . In this case, when the total use ratio of these compounds is less than 0.5 parts by weight, curing by irradiation is insufficient, and there is a possibility that a pattern may be missing, missing or undercut. It becomes easy to fall off from a board | substrate. Moreover, when baking without peeling a resist layer, a baking residue will generate easily.

2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, etc. are mentioned as a compound (iii). Among these, 2-mercaptobenzothiazole is preferable.

The use ratio of the compound (iii) in this invention is 0.01-30 weight part normally with respect to 100 weight part of polyfunctional monomers (B), Preferably it is 0.5-20 weight part, Especially preferably, it is 1-10 weight part. . In this case, when the total use ratio of these compounds is less than 0.01 part by weight, curing by irradiation is insufficient, and there is a possibility that the pattern may be missing, missing or undercut. It becomes easy to fall off from a board | substrate. Moreover, when baking without peeling a resist layer, a baking residue will generate easily.

Further, the ratio of compound (i), compound (ii) and compound (iii) is 0.5 to 2: 0.5 to 2: 0.5 to 2 as molar ratio, particularly preferably 1: 1: 1.

As a resist composition, photoinitiators other than a compound (i), a compound (ii), and a compound (iii) can also be used. Specific examples of other photopolymerization initiators include benzyl, benzoin, 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-mor Carbonyl compounds such as polynophenyl) -butan-1-one; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azide benzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butylhydroperoxide, cumene hydroperoxide and p-mentane 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 (trichloro Trihalo methanes such as rhomethyl) -1,3,5-triazine and 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine Can be mentioned. These can be used individually or in combination of 2 or more types. In addition, when using these photoinitiators, it is preferable to use in combination with compound (i)-(iii), and in this case, the content rate of the said photoinitiator is the total amount of compounds (i)-(iii). It is 80 mass% or less with respect to.

(C ') photosensitizer

In addition, in this invention, it is essential to use 1 or more types (hereinafter also called "specific photosensitizer") chosen from compound (1) and compound (2) as a photosensitizer. By adding a specific photosensitizer, the resist film used suitably with high sensitivity in DI exposure method can be obtained, and it has the effect that the shape of the pattern obtained becomes favorable.

Examples of the heterocyclic containing group having 3 to 17 carbon atoms represented by Q ¹ in the general formulas (1) and (2) include a benzothiazole group, a benzoimidazoyl group, an N-methylbenzoimidazoyl group, and a benzooxazoyl group. Among these, N-methylbenzoimidazoyl etc. are especially preferable.

Specific examples of the specific photosensitizer include 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3- (2-benzothiazole) -7-dimethylaminocoumarin, 3- (2 -Benzoimidazoyl) -7-dimethylaminocoumarin, 3- (2-N-methylbenzoimidazoyl) -7-dimethylaminocoumarin, 3- (benzooxazoyl) -7-dimethylaminocoumarin, 3-acetyl -4-methyl-7-dimethylaminocoumarin, 3-benzoyl-4-methyl-7-dimethylaminocoumarin, 3- (2-benzothiazole) -4-methyl-7-dimethylaminocoumarin, 3- (2- Benzoimidazoyl) -4-methyl-7-dimethylaminocoumarin, 3- (2-N-methylbenzoimidazoyl) -4-methyl-7-dimethylaminocoumarin, 3- (benzooxazoyl) -4- Methyl-7-dimethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-benzothiazole) -7-diethylaminocoumarin, 3- ( 2-benzoimidazoyl) -7-diethylaminocoumarin, 3- (2-N-methylbenzoimidazoyl) -7-diethylaminocoumarin, 3 -(Benzooxazoyl) -7-diethylaminocoumarin, 3-acetyl-4-methyl-7-diethylaminocoumarin, 3-benzoyl-4-methyl-7-diethylaminocoumarin, 3- (2-benzo Thiazole) -4-methyl-7-diethylaminocoumarin, 3- (2-benzoimidazoyl) -4-methyl-7-diethylaminocoumarin, 3- (2-N-methylbenzoimidazoyl) 4-methyl-7-diethylaminocoumarin, 3- (benzooxazoyl) -4-methyl-7-diethylaminocoumarin, 2,3,5,6-1H, 4H-tetrahydro-9-acetylqui Nolidino [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-benzothiazole) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (2-benzoimida Crude) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (2-N-methylbenzoimidazoyl) quinolidino [9,9a, 1 gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (benzooxazoyl) quinolidino [9,9a, 1 gh] 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-benzothiazole) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6 -1H, 4H-tetrahydro-8-methyl-9- (2-benzoimidazoyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8 -Methyl-9- (2-N-methylbenzoimidazoyl) quinolidino [9,9a, 1gh] coumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methyl-9-benzo And oxazoyl) quinolidino [9,9a, 1gh] coumarin, 3,3'-carbonylbis (7-diethylamino) coumarin and the like.

The said specific photosensitizer can be suitably selected and used according to the wavelength and intensity of the light source used for exposure, and can also be used individually or in mixture of 2 or more types. Moreover, although addition amount also changes with kinds of the other component and polyfunctional monomer to combine, it is normally used in 0.00001-50 mass% with respect to a photoinitiator, More preferably, it is used in 0.0005-30 mass%. When the addition amount is less than 0.00001 mass%, improvement in sensitivity is not recognized. Moreover, when more than 50 mass%, since absorption is too strong, only the surface of a film | membrane hardens | cures and the deep part of a resist film will become the uncured state, and a defect of a pattern will become easy to generate | occur | produce. Moreover, when baking without peeling a resist layer, a baking residue will generate easily.

(D) solvent

The resist composition used by this invention contains a solvent normally, in order to provide moderate fluidity | liquidity, plasticity, and favorable film formation property.

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, 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 and acetic acid 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, alkoxy acetic acid esters Cyclic ketones, acyclic ketones, acetoacetic acid esters, pyruvic acid esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, Dialkyl sulfoxides, dialkyl sulfones, terpineol, N-methyl-2-pyrrolidone and the like Number, and these may be used alone or in combination of two or more.

The solvent content ratio in this resist composition can be suitably selected within the range from which favorable film formation property (fluidity or plasticity) is obtained.

The resist composition used in the present invention may contain various additives such as a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, a UV absorber, a filler, a phosphor, a pigment, and a dye as an optional component.

(5) Manufacturing Method of Transfer Film

In the transfer film of this invention, a resist composition is apply | coated on a support film, a resist film is formed, an inorganic powder containing resin composition is apply | coated on this resist film, and an inorganic powder containing resin layer is formed. The transfer film of the present invention is also preferably formed by a method of forming an inorganic powder-containing resin layer on a support film, forming a resist film on a protective film, and overlapping and compressing the inorganic powder-containing resin layer surface and the resist film surface. Can be formed. Moreover, 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 apply | coating a resist composition and an inorganic powder containing resin composition, it is necessary to be able to form the coating film excellent in the uniformity of film thickness, and thick (for example, 10 micrometers or more) efficiently, specifically, The application method by a roll coater, the application method by a doctor blade, the application method by a curtain coater, the application method by a wire coater, etc. are mentioned as a preferable thing.

Moreover, it is preferable that a mold release process is given to the surface of a support film. Thereby, peeling operation of a support film can be performed easily in the transfer process mentioned later.

Drying conditions of a coating film are about 0.5 to 30 minutes at 50-150 degreeC, for example, and the residual ratio (content in an inorganic powder containing resin layer) of a solvent after drying is normally 2 mass% or less.

Although the thickness of the inorganic powder containing resin layer formed on a support film as mentioned above also changes with content rate of an inorganic powder, the kind and size of a member, etc., it is 10-100 micrometers, for example.

Moreover, as a protective film which can be provided in the surface of an inorganic powder containing resin layer, a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned. Moreover, when providing a protective film, it is preferable that the peeling force of a support film is small (easy to peel) among a support film and a protective film.

<Exposure pattern>

Although the exposure pattern formed at the exposure process of a resist film changes with a material, it is a stripe form of 10-200 micrometers width generally.

<Development amount>

In the present invention, an alkali developer is generally used in the development step of the resist film.

As an active ingredient of alkaline developing solution, 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, for example Inorganic alkaline compounds such as lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and ammonia; Tetramethylammonium Hydroxide, Trimethylhydroxyethylammonium Hydroxide, Monomethylamine, Dimethylamine, Trimethylamine, Monoethylamine, Diethylamine, Triethylamine, Monoisopropylamine, Diisopropylamine, Ethanolamine Organic alkaline compounds, such as these, etc. are mentioned.

The alkaline developer used in the development step of the resist film can be adjusted by dissolving one or two or more kinds of the alkaline compounds in water or the like. Here, the density | concentration of the alkaline compound in alkaline developing solution is 0.001-10 mass% normally, Preferably it is 0.01-5 mass%. In addition, after the image development process by alkaline developing solution is performed, the water washing process is normally performed.

<Etching liquid>

It is preferable that the etching liquid used at the etching process of an inorganic powder containing resin layer is an alkaline solution. Thereby, alkali-soluble resin contained in an inorganic powder containing resin layer can be easily dissolved and removed.

In addition, since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the alkali-soluble resin, the inorganic powder is also removed simultaneously by dissolving and washing the alkali-soluble resin as the binder in the alkaline solution.

Here, as alkaline solution used as etching liquid, the solution of the same composition as a developing solution is mentioned.

In the case where the etching solution is the same solution as the alkaline developing solution used in the developing step, the developing step and the etching step can be carried out continuously, and thus the manufacturing efficiency can be improved by simplifying the step.

In addition, after the etching process by alkaline solution is performed, the water washing process is performed normally.

Moreover, the organic solvent which can melt | dissolve the binder of an inorganic powder containing resin layer can also be used as an etching liquid. As such an organic solvent, the solvent illustrated as what comprises an inorganic powder containing resin composition is mentioned.

In addition, after the etching process with an organic solvent is performed, the rinse process with a poor solvent is performed as needed.

<Example>

Hereinafter, although the Example of this invention is described, this invention is not limited by these. In addition, "part" represents a "mass part" below.

[Mw of Binder Resin]

The weight average molecular weight of polystyrene conversion was measured by the gel permeation chromatography (GPC) (brand name HLC-802A) by the Tosoh Corporation.

Synthesis Example

(1) Synthesis of binder resin of inorganic powder-containing resin composition:

180 parts of propylene glycol monomethyl ether acetate, 20 parts of benzyl methacrylate, 15 parts of methacrylic acid-n-butyl, 20 parts of methacrylic acid 2-hydroxypropyl, monosuccinic acid in a flask equipped with a thermometer, a stirrer and a reflux cooler 35 parts of (2-methacryloyloxyethyl), 10 parts of methacrylic acid, 0.5 part of azobisisobutyronitrile and 3.5 parts of 2,4-diphenyl-4-methyl-1-pentene were added, and a room temperature was placed under a nitrogen atmosphere. Stir until uniform at. 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, and then cooled to room temperature to obtain a solution of the polymer (polymer A). The polymer solution obtained had a polymerization rate of 97%, and a Mw of this polymer was 100,000.

(2) Synthesis of Resin for Resist 1:

200 parts of propylene glycol monomethyl ether acetate, 60 parts of benzyl methacrylate, 20 parts of methacrylic acid 2-hydroxypropyl, 20 parts of methacrylic acid, azobisisobutyronitrile in a flask equipped with a thermometer, a stirrer and a reflux cooler 0.5 part and 2.5 parts of 2, 4- diphenyl-4-methyl-1- pentenes were added, and it stirred until it became uniform at room temperature under nitrogen atmosphere. 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, and then cooled to room temperature to obtain a solution of the polymer (polymer B). The polymer solution obtained had a polymerization rate of 97%, and a Mw of this polymer was 35,000.

(3) Synthesis of Resin for Resist 2:

Into a flask equipped with a thermometer, a stirrer, a dropping lot, and a reflux condenser, 90 g of a propylene glycol monomethyl ether acetate solution (solid content 33% by mass) of the polymer B obtained in the above (2) was placed and maintained at 45 ° C. 9.7 g of 2-methacryloyloxyethyl isocyanate was dripped at this over 10 minutes from the dropping lot. Thereafter, the mixture was kept at 45 DEG C for 3 hours and then cooled to synthesize a polymer having an unsaturated double bond in the side chain (polymer C).

<Example 1>

(1) Preparation of Inorganic Powder-Containing Resin Composition:

As the inorganic powder, 10 parts of Ag powder having a specific surface area of 0.5 m 2 / g, an average particle diameter of 2.3 μm, and 10 parts of a Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ -based glass frit having an average particle diameter of 3 μm (an amorphous, softening point of 520 ° C.), Stainless steel mesh (400 mesh, 38 micrometer diameter) after kneading with 30 parts of polymer A as a binder resin, 1 part of oleic acid as a dispersing agent, 10 parts of pentaerythritol triacrylate as a plasticizer, and 100 parts of propylene glycol monomethyl ether as a solvent. The inorganic powder-containing resin composition (conductive paste composition) was produced by filtering with.

(2) Preparation of Resist Composition:

60 parts of polymer B, 40 parts of trimethylolpropane triacrylate as a polyfunctional monomer, 2,2'-bis-2-chlorophenyl-4,4 ', 5,5'- tetraphenylbiimidazole as a photoinitiator ( Compound (i)) 6 parts, 4,4'-bis (diethylamino) benzophenone (compound (ii)) 3 parts, 2-mercaptobenzothiazole (compound (iii)) 1.5 parts, as a photosensitizer Alkali-developed radiation-sensitive property by kneading 0.5 part of 3,3'-carbonylbis (7-diethylamino) coumarin and 100 parts of propylene glycol monomethyl ether acetate as a solvent and then filtering with a cartridge filter (2 탆 diameter). A resist composition (hereinafter referred to as "resist composition") was prepared.

(3) Preparation of the transfer film:

By the operation of following (i) to (iii), the transfer film for electrode formation of this invention in which the laminated film which laminates a resist film and an inorganic powder containing resin layer in this order is formed on a support film was manufactured.

(i) The resist composition prepared in (2) was applied onto a support film (I) made of a PET film having 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, A resist film having a thickness of 8 탆 was formed on the support film.

(ii) The inorganic powder-containing resin composition prepared in (1) was applied onto a support film (II) made of a PET film having a film thickness of 38 μm using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes to provide a solvent. It removed and the inorganic powder containing resin layer of thickness 12micrometer was formed on the support film.

(iii) Each film was overlapped so that the surface of the resist film formed in (i) and the inorganic powder containing resin layer formed in (ii) could be contacted, and it was thermocompression-bonded with the heating roller. In the crimping conditions here, 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. This produced the transfer film in which the laminated | multilayer film which has a resist film and an inorganic powder containing resin layer is formed between support films.

(4) Transfer process of the laminated film:

The transfer film was superposed so that the surface of the inorganic powder containing resin layer of the transfer film manufactured by (3) could contact the surface of a glass substrate, and this transfer film was thermocompression-bonded on the heating roller. In the crimping conditions here, 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, the transfer film was transferred and adhered to the surface of the glass substrate.

(5) Exposure process and development process of resist film:

The laser beam of 405 nm of wavelength was irradiated to the part which forms a pattern from a support film with respect to the resist film among the laminated | multilayer film formed on the glass substrate in said (4). The laser beam irradiation energy amount at this time was 10 mJ / cm <2>. After the irradiation, the support film on the resist film was peeled off, and then the development process of the resist film by a shower method using 0.3 mass% aqueous sodium carbonate solution (30 ° C) as a developer was performed for 120 seconds with respect to the exposed resist film.

As a result, the uncured resist not irradiated with ultraviolet light was removed to form a resist pattern. The resist pattern was of a good shape having a uniform pattern shape and excellent linearity of the pattern edges.

(6) Etching Process of Inorganic Powder-Containing Resin Layer:

Subsequently to the above process, the etching process of the inorganic powder containing resin layer by the shower method which makes 0.3 mass% aqueous sodium carbonate aqueous solution (30 degreeC) an etching liquid was performed for 60 second.

Subsequently, washing with water and drying treatment with ultrapure water were performed. As a result, an inorganic powder-containing resin layer pattern was formed.

(7) firing process of the pattern:

The glass substrate in which the pattern of the inorganic powder containing resin layer was formed was baked at 560 degreeC for 10 minutes in the atmospheric atmosphere in a kiln. As a result, an electrode pattern having a thickness of 4 μm was formed on the surface of the glass substrate.

(8) Evaluation of the pattern:

The obtained electrode pattern had no cracks or defects and was excellent in shape.

<Example 2>

In Example 1 (2), the production of the transfer film and the electrode in the same manner as in Example 1 except that the polymer C was used instead of the polymer B, and the exposure dose was 5 mJ / cm 2 in Example 1 (5). The pattern was formed and evaluated. As a result, the obtained electrode pattern was excellent in shape, without a crack and a defect.

Comparative Example

In Example 1 (2), a resist composition was prepared in the same manner as in Example 1 except that 3,3'-carbonylbis (7-diethylamino) coumarin was not used, to prepare a transfer film, and to form an electrode pattern. Was formed and evaluated. As a result, the resist of the exposure part was dissolved at the time of development, and a pattern could not be formed.

According to the present invention, there is provided a method for producing a PDP capable of forming a component of the PDP having a high sensitivity enough to form a pattern even by the DI method and excellent workability and excellent pattern shape. There is provided a transfer film capable of preferably forming a component of a PDP having excellent properties and excellent pattern shape.

Claims (5)

An inorganic powder-containing resin layer is formed on the substrate, and a resist film containing at least one compound 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 exposed to light to form a latent image of the resist pattern. The resist film is developed to render the resist pattern present, and then 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 forming a panel material having an inorganic pattern by a method including a step of forming and firing the pattern. <Formula 1>

<Formula 2>

In the formula, Q ¹ is a heterocyclic containing group having 3 to 17 carbon atoms or -CO-Z (where Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3'-kumarino group), Q ² to Q ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms. A laminated film of a resist film and an inorganic powder-containing resin layer containing at least one compound selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) is formed on a support film, and the laminated film is transferred onto a substrate. The resist film constituting the laminated film is exposed to light to form a latent image of the resist pattern, the resist film is developed to render the resist pattern present, and the inorganic powder-containing resin layer is etched to form an inorganic powder corresponding to the resist pattern. A method of manufacturing a plasma display panel, wherein a panel material having an inorganic pattern is formed by a method including forming a pattern of the containing resin layer and firing the pattern. <Formula 1>

<Formula 2>

In the formula, Q ¹ is a heterocyclic containing group having 3 to 17 carbon atoms or -CO-Z (where Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3'-kumarino group), Q ² to Q ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms. The manufacturing method of the plasma display panel of Claim 1 or 2 in which the exposure process of a resist film is performed by the direct-imaging exposure method using a laser beam. The manufacturing method of the plasma display panel of Claim 1 or 2 whose material obtained is 1 or more types chosen from a partition, an electrode, a fluorescent substance, a color filter, and a black stripe (matrix). On a support film, it has a laminated film of the resist film containing the compound represented by following formula (1), and the compound represented by following formula (2), and the inorganic powder containing resin layer containing inorganic powder and binder resin. A transfer film, characterized in that. <Formula 1>

<Formula 2>

In the formula, Q ¹ is a heterocyclic containing group having 3 to 17 carbon atoms or -CO-Z (where Z is an alkyl group having 1 to 4 carbon atoms, an aryl group or a 3'-kumarino group), Q ² to Q ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms.

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