JP2000007872A - Composition containing inorganic powder, transfer film, and production of plasma display panel using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which can give a transfer film whose film-making material layer is excellent in flexibility and transferability by including an inorganic powder, specific acrylic resin and solvent. SOLUTION: This composition is obtained by incorporating (A) 100 pts.wt. of an inorganic powder with (B) an acrylic resin containing, as the polymerization component, a monomer shown by the formula [R is H or methyl; X is a divalent organic group shown by the formula COO or OCO; and (m) and (n) are each 1 to 8, and (l) is 1 to 5], e.g. [2-(meth)acryloyloxyethyl] succinate, preferably at 5 to 200 pts.wt. and (C) a solvent, e.g. diethyl ketone, preferably at 50 to 500 pts.wt The component A is low-melting glass or the like, when the composition is used as a material for a diaphragm or dielectric. The component A preferably has an average particle size of 0.2 to 5 μm The monomer for the component B is contained in the acrylic resin preferably at 5 to 50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a high-definition pattern in the formation of electrodes, partition walls, resistors, dielectrics, phosphors, color filters and black matrices constituting display cells of a plasma display panel. TECHNICAL FIELD The present invention relates to an inorganic powder-containing composition that can be suitably used for a liquid crystal display, a transfer film obtained by using the same, and a method for producing a plasma display panel.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Has been attracting attention in flat panel display technology because of its ease of manufacturing process despite its large size, wide viewing angle, and high display quality with its self-luminous type. Display panels are expected to become mainstream in the future as display devices for wall-mounted televisions of 20 inches or more. Color PD
For P, color display becomes possible by irradiating the phosphor with ultraviolet rays generated by gas discharge. In general, in a color PDP, a phosphor portion for red light emission, a phosphor portion for green light emission, and a phosphor portion for blue light emission are formed on a substrate, so that the light emitting display cells of each color are entirely formed. It is configured in a uniformly mixed state. Specifically, a partition wall made of an insulating material called a barrier rib is provided on the surface of a substrate made of glass or the like, and a large number of display cells are partitioned by the partition walls. Become space. By providing a phosphor region in the plasma working space and providing an electrode for causing plasma to act on the phosphor region, a plasma display panel having each display cell as a display unit is constructed.

FIG. 1 shows an example of the structure of an AC type PDP.
On the front substrate glass, a plurality of pairs of sustain electrodes are formed in a stripe shape, the upper portion is covered with a dielectric layer, and an MgO film serving as a protective film is deposited thereon. Further, in order to improve the contrast of the plasma display panel, a red, green, blue color filter or a black matrix may be provided below the dielectric layer. On the other hand, on the rear substrate glass, a plurality of signal electrodes are formed in a stripe shape,
A partition is provided between the signal electrodes, and a phosphor layer is formed on the side and bottom surfaces of the partition. The sustain electrodes on the front substrate and the signal electrodes on the rear substrate are attached and sealed so as to be vertical, and a mixed gas of neon and xenon is introduced into the interior.

FIG. 2 shows an example of the structure of a DC PDP.
A plurality of cathode electrodes are formed in a stripe shape on the front substrate glass. On the other hand, electrode terminals and leads of the display anode and the auxiliary anode are formed on the rear substrate glass, and a resistor is provided between the anode terminal and the anode lead and between the auxiliary anode terminal and the auxiliary anode lead. Except for the display anode terminal and the auxiliary anode terminal on the rear substrate, they are insulated by a dielectric. Next, partition walls are provided in a grid pattern to divide the discharge space, and a phosphor layer is formed on the side surfaces of the partition walls and on the bottom surface excluding the anode terminals. The cathode of the front substrate and the display anode and the auxiliary anode of the rear substrate are vertically adhered and sealed, and a mixed gas of neon and xenon is introduced therein.

[0005] The method of manufacturing the electrodes, partition walls, resistors, dielectrics, phosphors, color filters and black matrices of such a plasma display panel includes:
(1) A screen printing method in which a pattern is obtained by screen-printing a non-photosensitive inorganic powder-containing composition on a substrate to obtain a pattern and bake the pattern; There is known a photolithography method in which a pattern is left on a substrate by irradiating the film with ultraviolet rays through a photomask and then developed, and the pattern is baked.

[0006]

However, in the screen printing method, the demand for the positional accuracy of the pattern becomes very severe with the increase in the size and definition of the panel.
There is a problem that normal printing cannot cope. Also,
In the photolithography method, when a pattern having a thickness of 10 to 100 μm is formed in a single exposure and development process, the sensitivity in the depth direction of the film forming material layer is insufficient, and the edge is not necessarily sharp. A high-definition pattern was not obtained.

[0007] A new electrode, partition, resistor, dielectric, phosphor, color filter and black matrix are formed on a support film as a forming method with high dimensional accuracy and improved workability as compared with the conventional manufacturing method. Forming a film forming material layer composed of an inorganic powder-containing composition, transferring to a substrate, forming a resist film on the film forming material layer transferred to the substrate, exposing the resist film to an exposure treatment, A latent image is formed, the resist film is developed to develop a resist pattern, the film forming material layer is etched to form a pattern of the film forming material layer corresponding to the resist pattern, and the pattern is baked. A method for forming at least one of an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix. Are (Japanese Patent Application No. 9-34051
No. 4). According to such a manufacturing method, a pattern with high definition and excellent surface uniformity can be formed, and a film forming material layer composed of an inorganic powder-containing composition is formed on a support film. Composite film (hereinafter, referred to as
Also called "transfer film". ) Is also advantageous in that it can be wound up in a roll and stored. However, the conventional transfer film has a problem that the flexibility of the film forming material layer and the transferability to the substrate are insufficient.

The present invention has been made based on the above circumstances. A first object of the present invention is to provide an inorganic powder-containing composition capable of producing a transfer film excellent in flexibility and transferability of a film-forming material layer (heat adhesion of the film-forming material layer to a glass substrate). And a transfer film. A second object of the present invention is to provide a method of manufacturing a plasma display panel which can form a pattern with high dimensional accuracy and is excellent in workability.

[0009]

Means for Solving the Problems The inorganic powder-containing composition of the present invention comprises (A) an inorganic powder, and (B) a monomer represented by the following formula (1) (hereinafter also referred to as "specific monomer"). Acrylic resin containing as a polymerization component and

[0010]

Embedded image

(Wherein, R represents a hydrogen atom or a methyl group, X represents a divalent organic group represented by —COO— or —OCO—, and m and n each independently represent an integer of 1-8. And l represents an integer of 1 to 5.)

(C) It is characterized by containing a solvent.
The transfer film of the present invention is characterized in that a film-forming material layer obtained from the above-mentioned inorganic powder-containing composition is formed on a support film. In the method of manufacturing a plasma display panel according to the present invention, a film forming material layer is transferred onto a substrate, a resist film is formed on the film forming material layer, and the resist film is exposed to light to form a latent image of a resist pattern. Developing the resist film to reveal a resist pattern, etching the film-forming material layer to form a pattern of the film-forming material layer corresponding to the resist pattern, and firing the pattern. By the method, the partition,
At least one of an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix is formed.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the inorganic powder-containing composition of the present invention will be described in detail. The inorganic powder-containing composition of the present invention contains an inorganic powder, an acrylic resin and a solvent as essential components.

<Inorganic powder> Inorganic powder dispersion pace of the present invention
The inorganic powder used in the printing composition depends on the type of forming material.
Is different. Used for partition and dielectric forming materials
Examples of the machine powder include low melting point glass and the like.
Contains a mixture of zinc oxide, boron oxide and silicon oxide
(ZnO-B_TwoO_Three-SiO_TwoSystem), lead oxide, boron oxide, ke oxide
A mixture of iodine (PbO-B_TwoO_Three-SiO_Two), Lead oxide, oxide
A mixture of iodine, silicon oxide and aluminum oxide (PbO-B_Two
O_Three-SiO_Two-Al_TwoO_ThreeSystem), lead oxide, zinc oxide, borane oxide
Mixture of silicon and silicon oxide (PbO-ZnO-B_TwoO_Three-SiO_TwoSystem)
Can be mentioned. Inorganic used for electrode forming materials
As powder, Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr
And so on. Used for resistor forming material
As inorganic powder, RuO_TwoAnd the like. firefly
The inorganic powder used for the light body forming material is
Y_TwoO_Three:EU³⁺, Y_TwoSiO_Five:EU³⁺, Y_ThreeAl_FiveO₁₂:EU³⁺, YVO_Four:EU³⁺,
(Y, Gd) BO_Three:EU³⁺, Zn_Three(PO_Four)_Two: Mn etc. for green color
Is Zn_TwoSiO_Four: Mn, BaAl₁₂O₁₉: Mn, BaMgAl₁₄O_{twenty three}: Mn, LaPO_Four:
(Ce, Tb), Y _Three(Al, Ga)_FiveO₁₂: Y for blue color such as Tb
_TwoSiO_Five: Ce, BaMgAl_TenO₁₇:EU²⁺, BaMgAl ₁₄O_{twenty three}:EU²⁺, (C
a, Sr, Ba)_Ten(PO_Four)₆Cl_Two:EU²⁺, (Zn, Cd) S: Ag
I can do it. Used for color filter forming material
The inorganic powder used is Fe for red_TwoO_Three, Pb_ThreeO_FourGreen
Cr for color_TwoO_ThreeSuch as 2 (Al_TwoNa_TwoSi_ThreeO
_Ten) ・ Na_TwoS _FourAnd the like. Black mato
Inorganic powders used for the Rix-forming material include Mn,
Fe, Cr and the like can be mentioned.

The average particle size of these inorganic powders is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm.
μm. When the average particle size of the inorganic powder is less than 0.1 μm, the specific surface area of the inorganic powder increases, so that aggregation of the particles easily occurs in the inorganic powder-containing composition, and a stable dispersion state is obtained. It becomes difficult. On the other hand, when the average particle size of the inorganic powder is 10 μm or more, it is difficult to obtain a high definition pattern.

<Acrylic Resin> The acrylic resin used in the inorganic powder-containing composition of the present invention functions as a binder resin, and it is preferable to use an alkali-soluble acrylic resin. Here, "alkali soluble"
The term refers to a property of being dissolved by an alkaline etching solution and having such solubility that an intended etching process is performed. As such an acrylic resin, an acrylic resin having a specific monomer represented by the above formula (1) as a polymerization component is used. The specific monomer has a homopolymer having a Tg of 150 ° C. or lower. By using the specific monomer as a polymerization component, an inorganic powder-containing composition having excellent flexibility and transferability can be obtained, and a film-forming material layer can be obtained. At low temperature. Specific examples of the specific monomer include succinic acid (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth)
An acrylate, an acrylic acid dimer, etc. can be mentioned. The polymerization ratio of the specific monomer in the alkali-soluble acrylic resin is preferably 2 to 70% by weight, particularly preferably 5 to 50% by weight. The acrylic resin is preferably a copolymer of the specific monomer, another monomer having a (meth) acryloyl group, and if necessary, another monomer having a polymerizable unsaturated group. The acrylic resin may be any of a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer.

Specific examples of other monomers having a (meth) acryloyl group include methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth)
Acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth)
Acrylate, isooctyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, nonyl (meth)
Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate Alkyl (meth) acrylates such as; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 3-hydroxybutyl (meth) acrylate, 4-
Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate And alkoxyalkyl (meth) acrylates such as 2-methoxybutyl (meth) acrylate; acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Examples thereof include carboxyl group-containing monomers such as citraconic acid, mesaconic acid, and cinnamic acid.

Specific examples of the other monomers having a polymerizable unsaturated group include aromatic vinyl monomers such as styrene and α-methylstyrene; and conjugated diene monomers such as butadiene and isoprene.

The molecular weight of the acrylic resin is GP
The weight average molecular weight in terms of polystyrene by C (hereinafter, simply referred to as “weight average molecular weight”) is 4,000 to 4,000.
It is preferably 1,000,000, and more preferably 10,000 to 500,000. The binder resin constituting the composition of the present invention may include a resin other than the acrylic resin. As such other resin, an alkali-soluble resin such as a hydroxystyrene resin, a novolak resin, or a polyester resin is preferably used. The content of these other resins is preferably less than 70% by weight based on the total amount of the binder resin, and the content of the repeating unit obtained from the specific monomer in the entire binder resin is preferably 1 to 70% by weight. ,
More preferably, it is 5 to 50% by weight.

The content of the binder resin in the composition of the present invention is 1 to 10 parts by weight based on 100 parts by weight of the inorganic powder.
00 parts by weight, more preferably 5 parts by weight.
To 200 parts by weight. If the ratio of the binder resin is too small, the inorganic powder particles cannot be bound and held reliably. On the other hand, if this ratio is excessive, it takes a long time for the firing step, and the shapes of the electrodes, partition walls, resistors, dielectrics, phosphors, color filters and black matrix to be formed are uniform. Or not.

<Solvent> As the solvent used in the composition of the present invention, it has good affinity with inorganic powder and good solubility of binder resin and imparts appropriate viscosity to the composition containing inorganic powder. It is preferable that the material can be easily evaporated and removed by drying. Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; alkyl saturated aliphatic monocarboxylates such as n-butyl acetate and amyl acetate Esters;
Lactic acid esters such as ethyl lactate and n-butyl lactate;
Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ether esters such as ethyl-3-ethoxypropionate, pyrrolidones, and the like, and these can be used alone or in combination of two or more. Can be used.

The content of the solvent in the composition of the present invention is from 5 to 1,000 parts by weight based on 100 parts by weight of the inorganic powder from the viewpoint of maintaining the viscosity of the composition in a suitable range. And more preferably 50 to 5
00 parts by weight.

The inorganic powder-containing composition of the present invention contains, in addition to the above essential components, a dispersant, a tackifier, a plasticizer, a surface tension regulator, a stabilizer, an antifoaming agent, a dispersant, and the like. Various additives may be contained as optional components. The composition of the present invention can be prepared by kneading the above-mentioned inorganic powder, binder resin, solvent and optional components using a kneader such as a roll kneader, a mixer or a homomixer. The composition of the present invention prepared as described above is usually a paste composition having fluidity suitable for application.

<Transfer Film> The composition of the present invention can be particularly preferably used for producing a transfer film. This transfer film is composed of a support film and a film-forming material layer formed on the support film and comprising the inorganic powder-containing composition of the present invention. Here, the viscosity of the inorganic powder-containing composition of the present invention to be subjected to the step of coating the support film is 1,000 to 20,000 cP.
It is preferred that

The supporting film constituting the transfer film includes:
It is preferable that the resin film has heat resistance and solvent resistance and is flexible. When the support film has flexibility, the composition of the present invention can be applied by a roll coater, and the film-forming material layer can be stored and supplied in a rolled state. 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. As the thickness of the support film, for example, 20 to
100 μm.

The film forming material layer constituting the transfer film includes:
The composition can be formed by applying the composition of the present invention on the support film, drying the coating film and removing a part or all of the solvent. The method of applying the composition of the present invention on a support film is preferably a method capable of efficiently forming a coating film having excellent uniformity in film thickness, and specifically, coating by a roll coater. Preferred examples include a method, a coating method using a blade coater, a coating method using a curtain coater, and a coating method using a wire coater. In addition, it is preferable that the surface of the support film to which the composition of the present invention is applied is subjected to a release treatment as necessary. Thereby, in the step of transferring to the glass substrate, the operation of peeling the support film can be easily performed. Further, the transfer film may be provided with a protective film layer on the surface of the film forming material layer. As such a protective film layer, polyethylene terephthalate film, polyethylene film,
Examples thereof include a polyvinyl alcohol-based film and the like, and it is preferable that a release treatment is performed as necessary.

As described above, the composition of the present invention can be particularly preferably used in producing a transfer film by forming a film-forming material layer on a support film, but is not limited to these uses. Instead, a conventionally known method for forming a film-forming material layer, that is, the composition is directly applied to the surface of a glass substrate by a screen printing method or the like, and the film is dried to form a film-forming material layer. The method can also be suitably used. Here, the viscosity of the inorganic powder-containing composition of the present invention to be subjected to the coating step on the glass substrate by the screen printing method is 10,000,
It is preferably from 0 to 200,000 cP.

<Method of Manufacturing Plasma Display Panel> The method of manufacturing the present invention will be described in detail below. In the manufacturing method of the present invention, [1] a film forming material layer transferring step, [2] a resist film forming step, [3] a resist film exposing step, [4] a resist film developing step, and [5] a film An electrode, a resistor, a dielectric, a phosphor, a color filter or a black matrix is formed by the etching step of the forming material layer and the baking step of [6] pattern.

[1] Step of Transferring Film-Forming Material Layer Using the transfer film of the present invention, a film-forming material layer formed from the inorganic powder-containing layer of the present invention is transferred to the surface of a substrate. An example of the transfer step is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film is superimposed on the surface of the substrate so that the surface of the film forming material layer is in contact with the substrate, and the transfer film is heated with a heating roller or the like. After thermocompression bonding, the support film is peeled off from the film forming material layer. As a result, the film-forming material layer is transferred onto the surface of the substrate and brought into close contact therewith.
Here, as the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C., and the roll pressure by the heating roller is 1
５5 kg / cm ² , the moving speed of the heating roller is 0.1０．１1
0.0 m / min. The substrate may be preheated, and the preheating temperature is, for example, 40 to 100.
° C.

[2] Step of forming resist film In this step, a resist film is formed on the surface of the transferred film forming material layer. The resist constituting the resist film may be either a positive resist or a negative resist. 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 method, and then drying the coating film. Further, the resist film may be formed by transferring a resist film formed on the support film to the surface of the film forming material layer. According to such a forming method, the number of steps in the resist film forming step can be reduced, and the uniformity of the film thickness of the formed pattern can be achieved. As the thickness of the resist film,
Usually, 0.1 to 40 μm, preferably 0.5 to 20 μm
It is.

[3] Step of exposing resist film In this step, the surface of the resist film formed on the film forming material layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask. Thus, a latent image of the resist pattern is formed. Here, the radiation irradiating apparatus is not particularly limited, such as an ultraviolet irradiating apparatus used in the photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device.

[4] Step of Developing Resist Film In this step, the resist pattern (latent image) is exposed by developing the exposed resist film. Here, the developing conditions include the type, composition, and concentration of the developing solution, the developing time, the developing temperature, and the developing method (for example, immersion method, rocking method, shower method, spray method, Paddle method), a developing device, and the like can be appropriately selected. By this developing step, a resist pattern composed of a resist remaining portion and a resist removing portion is formed. This resist pattern serves as an etching mask in the next step (etching step), and the constituent material of the remaining resist portion (photocured resist) dissolves in the etchant more slowly than the constituent material of the film forming material layer. Needs to be small.

[5] Step of Etching Film Forming Material Layer In this step, the film forming material layer is etched to form a pattern corresponding to the resist pattern.
That is, a portion of the film forming material layer corresponding to the resist-removed portion of the resist pattern is dissolved in the etchant and selectively removed. Then, the substrate surface is exposed at a portion corresponding to the resist removed portion in the film forming material layer. As a result, a pattern composed of the material layer remaining portion and the material layer removed portion is formed. Here, as the etching processing conditions, depending on the type of the film forming material layer and the like,
The type, composition and concentration of the etching solution, processing time, processing temperature, processing method (for example, immersion method, rocking method, shower method, spray method, paddle method), and processing apparatus can be appropriately selected. In addition, by selecting the type of the resist film and the film forming material layer so that the same solution as the developing solution used in the developing process can be used as the etching solution, the developing process and the etching process are continuously performed. The manufacturing efficiency can be improved by simplifying the process. Here, it is preferable that the resist remaining portion constituting the resist pattern is gradually dissolved during the etching process and completely removed at the stage when the pattern is formed (at the end of the etching process). Even if part or all of the remaining resist remains after the etching process, the remaining resist is removed in the next baking step.

[6] Step of firing pattern In this step, the pattern is fired to form an electrode, a resistor, a dielectric, a phosphor, a color filter or a black matrix. As a result, the organic substance in the remaining portion of the material layer is burned off, an inorganic layer such as a metal layer and a phosphor layer is formed, and an electrode, a resistor, a dielectric,
A panel material having a phosphor, a color filter, or a black matrix pattern formed thereon can be obtained. Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the remaining portion of the material layer is burned off, and is usually 400 to 600 ° C. The firing time is usually set to 10 to 90 minutes.

[0035]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” indicates “parts by weight”.

<Example 1> (1) Preparation of composition containing inorganic powder (conductive paste composition): 200 parts of propylene glycol monomethyl ether acetate, 30 parts of 2-hydroxypropyl methacrylate, 20 parts of methacrylic acid, n- A monomer composition comprising 40 parts of butyl methacrylate, 10 parts of 2-acryloyloxyethyl succinic acid and 1 part of azobisisobutyronitrile was charged into an autoclave equipped with a stirrer, and the mixture was made uniform at room temperature under a nitrogen atmosphere. After stirring, 8
Polymerization was carried out at 0 ° C. for 3 hours, polymerization was continued at 100 ° C. for 1 hour, and then cooled to room temperature to obtain a polymer solution. Here, the polymerization rate was 95%, and the weight average molecular weight (Mw) of the copolymer (hereinafter, referred to as “polymer (A)”) precipitated from the polymer solution was 250,000.

Next, the conductive particles have an average particle size of 1.0
100 parts of silver powder of μm, polymer (A) as binder resin
By kneading 25 parts and 100 parts of propylene glycol monomethyl ether acetate as a solvent, an inorganic powder-containing composition for forming an electrode (hereinafter, referred to as “conductive paste composition”) was prepared. The viscosity at 25 ° C. was 5,000 cP.

(2) Preparation of radiation-sensitive resist composition:
Polymer A obtained in (1) using a monomer composition comprising 200 parts of ethyl-3-ethoxypropionate, 85 parts of n-butyl methacrylate, 15 parts of methacrylic acid and 1 part of azobisisobutyronitrile A polymer solution was obtained in the same manner as in the synthesis procedure. Here, the polymerization rate is 98
%, And the weight average molecular weight (Mw) of the copolymer (hereinafter, referred to as “polymer (B)”) precipitated from the polymer solution was 20,000.

Next, 50 parts of the polymer (B) as an alkali-soluble resin and a polyfunctional monomer (radiation-sensitive component)
As pentaerythritol tetraacrylate 40
Parts, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as a photopolymerization initiator (radiation-sensitive component) and 5 parts as a solvent, and ethyl-3-ethoxypropionate as a solvent By kneading 150 parts, a paste-like alkali-developable radiation-sensitive resist composition (hereinafter, referred to as “resist composition”) was prepared.

(3) Production of transfer film: PE obtained by subjecting the conductive paste composition prepared in the above (2) to release treatment in advance
It is applied on a support film (width: 200 mm, length: 30 m, thickness: 38 μm) using a roll coater. The coating film is dried at 100 ° C. for 5 minutes to completely remove the solvent, and the thickness is reduced to 20 μm. Was formed on a support film (hereinafter, referred to as “transfer film (1)”). The conductive paste layer formed on the support film layer was excellent in flexibility, and did not crack when bent.

Next, the resist composition was subjected to a supporting film (200 m wide) made of a PET film that had not been subjected to a release treatment.
m, length 30 m, thickness 38 μm) using a roll coater, drying the coating at 100 ° C. for 5 minutes to completely remove the solvent, and forming a 5 μm thick resist film on the supporting film. (Hereinafter, referred to as “transfer film (2)”).

(4) Evaluation of transfer film: The surface state of the conductive paste layer of the transfer film produced in the above (3) was observed using a microscope. Aggregates of conductive particles, streaky coating marks were observed. No film defects such as craters and pinholes were found. Even when the transfer film was bent, the transfer film (1) had good flexibility without cracks (bending cracks) occurring on the surface of the conductive paste layer.

(5) Film transfer step: A transfer film (1) is superimposed on the surface of a glass substrate for a 6-inch panel so that the surface of the conductive paste layer is in contact with the surface, and the transfer film (1) is It was thermocompression bonded to a heating roller. Here, as the pressure bonding condition, the surface temperature of the heating roller is set to 120
C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. After the completion of the thermocompression treatment, the support film was peeled off. As a result, the conductive paste layer was transferred to the surface of the glass substrate and brought into close contact therewith.
When the film thickness of this conductive paste layer was measured,
m ± 1 μm.

Next, the transfer film (2) was overlaid on the conductive paste layer so that the surface of the resist film was in contact with the conductive paste layer, and the transfer film (2) was thermocompression-bonded to a heating roller. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 120 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. After the completion of the thermocompression treatment, the support film was peeled off. As a result, the resist film was transferred onto the conductive paste layer and was brought into close contact therewith. When the thickness of this resist film was measured, it was found to be 5 μm ±
It was in the range of 1 μm.

(6) Exposure and development steps of the resist film:
For the resist film formed on the conductive paste layer,
An i-line (ultraviolet light having a wavelength of 365 nm) was irradiated from an extra-high pressure mercury lamp through an exposure mask (a stripe pattern having a width of 50 μm). Here, the irradiation amount is 200 mJ / cm
^{And 2} . Next, the exposed resist film was subjected to a developing process by a shower method using a 0.2% by weight aqueous solution of potassium hydroxide (25 ° C.) for 20 seconds. Next, a water washing treatment with ultrapure water was performed, whereby the uncured resist not irradiated with the ultraviolet rays was removed, and a resist pattern was formed.

(7) Etching step of conductive paste layer: Continuing with the above steps, an etching treatment by a shower method using a 0.2% by weight aqueous solution of potassium hydroxide as an etching solution is performed at 25 ° C. for 2 minutes. Was. Next, a washing treatment and a drying treatment with ultrapure water were performed. Thereby, a pattern of the conductive paste layer composed of the material layer remaining portion and the material layer removed portion was formed.

(8) Firing Step of Conductive Paste Layer: The glass substrate on which the pattern of the conductive paste layer was formed was fired in a firing furnace at a temperature of 600 ° C. for 30 minutes. As a result, a panel material having electrodes formed on the surface of the glass substrate was obtained.

(9) Evaluation of electrode pattern: The cross-sectional shape of the electrode in the obtained panel material was observed with a scanning electron microscope, and the width and height of the bottom surface of the cross-sectional shape were measured. ± 2μm, height 10μ
m ± 1 μm, and the dimensional accuracy was extremely high.

<Examples 2 to 3> The conductive paste composition of the present invention was prepared in the same manner as in Example 1 except that the alkali-soluble acrylic resin (constituent monomer) was changed according to the formulation shown in Table 1. Prepared. Next, a transfer film was manufactured in the same manner as in Example 1 except that each of the obtained conductive paste compositions was used. Thereafter, the transfer of the conductive paste layer and the resist film, and the exposure, development, and firing treatments were performed in the same manner as in Example 1 except that each of the obtained transfer films was used.

For each of the compositions according to Examples 2 and 3, in the same manner as in Example 1, the coating properties on the support film, the surface condition of the conductive paste layer formed by the composition, and the conductive paste layer , The transferability of the conductive paste layer (heat adhesion to a glass substrate), and the electrode pattern strength during development were evaluated. Here, the coating properties on the support film were determined to be "good" when the composition could be formed on the entire surface of the support film without repelling the composition on the surface of the support film. The surface state of the conductive paste layer was determined to be “good” when there were no film defects such as aggregates of conductive particles, streaky coating marks, craters and pinholes. The flexibility of the conductive paste layer was determined to be “good” when no crack occurred when the conductive paste layer was bent. The transferability of the conductive paste layer was determined to be “good” when all of the conductive paste layer was transferred to and adhered to the surface of the glass substrate. Further, when the electrode pattern was adhered without peeling from the glass substrate at the time of development, it was judged as “good”. Table 1 shows the above results.

Comparative Example 1 A monomer composition comprising 200 parts of propylene glycol monomethyl ether acetate, 60 parts of n-butyl methacrylate, 20 parts of 2-hydroxypropyl methacrylate, 20 parts of methacrylic acid and 1 part of azobisisobutyronitrile. The product was charged in an autoclave equipped with a stirrer, and stirred at room temperature under a nitrogen atmosphere until uniform, then polymerized at 80 ° C. for 3 hours, further continued at 100 ° C. for 1 hour, and then cooled to room temperature. A polymer solution ("Polymer B") was obtained. Here, the polymerization rate was 97%, and the weight average molecular weight (Mw) of the copolymer precipitated from this polymer solution was 300,0.
00.

Next, the conductive particles have an average particle size of 1.0
100 parts of silver powder of μm, polymer (B) as binder resin
A transfer film was produced in the same manner as in Example 1, except that 25 parts and 250 parts of propylene glycol monomethyl ether acetate as a solvent were kneaded to prepare a conductive paste composition for forming an electrode. When the conductive paste layer formed on the support film was bent, cracks occurred.

Next, the transfer film was superimposed on a glass substrate for a 6-inch panel so that the surface of the conductive paste layer was in contact with the transfer film, and then thermocompression-bonded with a heating roll under the same compression conditions as in Example 1. did. After completion of the thermocompression bonding process,
The support film was peeled off from the film forming material layer. As a result, most were transferred to the glass substrate, but were partially transferred and peeled from the glass substrate. Next, after transferring a resist film on the conductive paste layer in the same manner as in Example 1,
Exposure, development and baking were performed to form an electrode pattern. When the cross-sectional shape of the electrode in the obtained panel material was observed with a scanning electron microscope and the width and height of the bottom surface of the cross-sectional shape were measured, the width of the bottom surface was 50 μm ± 5 μm and the height was 10 μm ± 1 μm. However, the dimensional accuracy was not good. In addition, since the transferability of the conductive paste layer was insufficient, the electrode pattern tended to peel off during development. Table 1 summarizes the above results.

[0054]

[Table 1] In the formula, abbreviations in the acrylic resin composition indicate the following monomers. BMA: n-butyl methacrylate HPMA: 2-hydroxypropyl methacrylate EHMA: 2-ethylhexyl methacrylate MA: methacrylic acid HO-MS: succinic acid (2-methacryloyloxyethyl) HOA-MS: (2-acryloyloxyethyl succinate) )

[0055]

According to the composition of the present invention, the following effects can be obtained. (1) Since the composition of the present invention contains an alkali-soluble acrylic resin having excellent affinity for inorganic powder particles, the composition has excellent dispersion stability of inorganic powder particles. Therefore, no aggregate of inorganic powder particles is generated. (2) It is possible to form a uniform film forming material layer without film defects. (3) A film-forming material layer having excellent adhesion to a glass substrate can be formed. (4) A high definition pattern can be formed. (5) It can be suitably used for the production of a transfer film. (6) A transfer film having excellent flexibility of the film forming material layer can be manufactured. (7) Transferability of film forming material layer (transferability to glass substrate)
It is possible to produce a transfer film excellent in quality. (8) It is possible to manufacture a transfer film in which a formed pattern is not peeled off during development.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing a general AC type PDP.

FIG. 2 is an explanatory sectional view showing a general DC-type PDP.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Front board 2 Back board 3 Dielectric 3A Mg
O layer 4 Phosphor 5 Barrier 6A Sustain electrode 6B Signal electrode 6a Cathode 6b Display anode 6b 'Display anode lead 6c Anode 6c' Anode lead 7 Resistance 8 Display cell 9 Auxiliary cell 10 Bus line

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 9/02 H01J 9/02 F 5C028 9/20 9/20 A 5C040 9/227 9/227 E 17 / 49 17/49 Z (72) Inventor Setsuko Noma 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (reference) 2H025 AA00 AB13 AB17 AC01 AD01 AD03 CC08 DA40 EA03 EA04 FA15 FA29 FA40 4J002 BC071 BG011 BG041 BG051 BG071 DE096 DE106 DE146 DE156 DH046 DJ006 DJ016 DK006 DL006 EC037 ED027 EE037 EH037 EH157 EU027 GP03 4J038 CG141 CH151 CH161 CJ021 CJ131 CJ201 HA066 HA216 HA346 HA386 HA446 HA476 HA06 JA03 JA17 MA03 JA06 JA17 JA33 JA03 JA17 AJ08Q AJ09Q AL03Q AL04Q AL05Q AL08P AL09Q AS02Q AS03Q BA04Q BA05Q BA06Q BA15P BA16P CA04 DA01 JA38 5C027 AA01 AA05 AA09 5C028 AA01 AA07 AA10 FF16 5C040 DD03 DD07 DD09 DD13

Claims (4)

[Claims] (A) an inorganic powder; (B) an acrylic resin containing a monomer represented by the following formula (1) as a polymerization component: (Wherein, R represents a hydrogen atom or a methyl group, and X represents -C
OO- or -OCO- represents a divalent organic group, m and n each independently represents an integer of 1 to 8,
l represents an integer of 1 to 5. (C) An inorganic powder-containing composition comprising a solvent. 2. A transfer film, wherein a film-forming material layer obtained from the composition containing an inorganic powder according to claim 1 is formed on a support film. 3. Using the transfer film according to claim 2,
The film-forming material layer is transferred onto a substrate, a resist film is formed on the film-forming material layer, the resist film is exposed to light, a latent image of a resist pattern is formed, and the resist film is developed to form a resist. The pattern is exposed, the film-forming material layer is etched to form a pattern of the film-forming material layer corresponding to the resist pattern, and the method includes a step of baking the pattern. Body, phosphor, characterized by forming at least one of a color filter and a black matrix,
A method for manufacturing a plasma display panel. 4. A laminated film of a resist film and a film-forming material layer comprising the inorganic powder-containing composition according to claim 1 is formed on a support film, and the laminated film is transferred onto a substrate. The resist film constituting the film is exposed to light to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the film forming material layer is etched to form a film corresponding to the resist pattern. Forming a pattern of a forming material layer and forming at least one of a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix by a method including a step of baking the pattern; , Plasma display panel manufacturing method.