JPH10208625A - Thick film pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a thick film pattern with a high accuracy at a high productivity. SOLUTION: A female die 13 formed on a base film 11 is transferred to a substrate 10, and a pattern forming material 14 is filled to the female die 13 on the substrate 10, or the female die 13 formed on the base film 11, and the pattern forming material 14 filled to the female die 13 are transferred to the substrate 10 at a time. While the pattern forming material 14 is sintered by baking, the female die 13 is removed. This method has the fewer processing number and a higher productivity compared with the conventional method such as a screen printing method or a sand blast method. Since only a film in which the quality check of the female die 13 formed beforehand is finished can be used, the nondefective rate can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a plasma display panel (PDP), a field emission display (FED), a liquid crystal display (LCD), a fluorescent display, a hybrid integrated circuit, etc. More particularly, the present invention relates to a method for forming a thick film pattern suitable for a method for forming a PDP barrier.

[0002]

2. Description of the Related Art Conventionally, as a method of forming a thick film pattern of this kind, a paste for a conductor or an insulator is applied in a pattern on a glass or ceramic substrate by a screen printing method and then adhered to the substrate through a firing step. A method for forming a patterned pattern is known. In this method, for example, in order to form a thin line having a line width of 100 μm and a height of 100 μm, overprinting needs to be repeated a plurality of times. Another method is to form a pattern forming layer on the front surface of the substrate, form a sandblast mask with a photosensitive resist on the pattern forming layer, and then spray an abrasive to pattern the pattern forming layer. A so-called sand blast method for performing the above is known.

[0003]

However, in the screen printing method, as described above, since the film thickness that can be formed by one printing is small, it is necessary to perform overprinting to obtain a desired film thickness. Has the disadvantage of being bad. In addition, the printing position is slightly shifted each time overprinting is performed due to elongation of the screen plate or the like, which deteriorates the pattern shape. Further, since the paste has fluidity, the hem spreads. As a result, there is also a problem that a thick film pattern having a high aspect ratio cannot be formed. In addition, the sandblasting method has a problem in processing speed. For example, in the case of a large substrate having one side of 50 cm or more, the processing time per one substrate requires several tens of minutes. In order to increase the grinding speed of the pattern forming layer, the impact force of the abrasive may be increased. However, doing so increases the damage to the photosensitive resist and causes defects in the pattern.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for forming a thick film pattern capable of forming a highly accurate thick film pattern with high productivity. Is to do.

[0005]

In order to achieve the above object, a first method for forming a thick film pattern according to the present invention comprises forming a negative photosensitive resin layer on a base film, After forming the female mold of the pattern by pattern exposure and development of the resin layer, the female mold is transferred to the substrate, and then the female mold is filled with the pattern forming material on the substrate, and the pattern forming material is baked by firing. It is characterized by tying and removing the female mold.

A second method of forming a thick film pattern according to the present invention comprises forming a negative photosensitive resin layer on a base film, exposing the photosensitive resin layer to a pattern, and developing the pattern. After forming the female mold, fill the female mold with the pattern forming material, transfer the female mold and the pattern forming material to the substrate simultaneously, sinter the pattern forming material by firing, and remove the female mold. I do.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The specific procedure of the first method for forming a thick film pattern is as shown in FIG. 1, which will be described below.

First, as shown in FIG. 1A, a photosensitive resin layer 12 is formed by applying a negative photosensitive resin on a base film 11 and drying it. next,
As shown in FIG. 1B, the photosensitive resin layer 12 is subjected to pattern exposure through a mask M, and subsequently developed,
A female die 13 having a pattern is formed as shown in FIG. Next, as shown in FIG. 1 (d), a sheet having a female mold 13 provided on a base film 11 is placed on the base film 11.
The female die 13 is transferred to the substrate 10 by superimposing the substrate 10 on the substrate 10 in the direction toward the 0 side and then peeling off the base film 11. Then, as shown in FIG. 1 (e), after filling the pattern forming material 14 into the female mold 13 on the substrate 10, baking is performed to sinter the pattern forming material 14 and remove the female mold. Thus, a thick film pattern 15 made of a pattern forming material is formed on the substrate 10 as shown in FIG.

The specific procedure of the second thick film pattern forming method is as shown in FIG. 2, which will be described below.

First, as shown in FIG. 2A, a photosensitive resin layer 12 is formed by applying a negative photosensitive resin on a base film 11 and drying it. next,
As shown in FIG. 2B, the photosensitive resin layer 12 is subjected to pattern exposure through a mask M, and is subsequently developed, thereby
A female die 13 having a pattern is formed as shown in FIG. Next, as shown in FIG. 2D, after filling the female mold 13 with the pattern forming material 14, the base film 11 is overlaid on the substrate 10 so that the female mold 13 on the base film 11 faces the substrate 10. By peeling off the base film 11, the female mold 13 and the pattern forming material 14 are simultaneously transferred to the substrate 10 as shown in FIG. Then, sintering is performed to sinter the pattern forming material 14, and
Is removed. As a result, as shown in FIG.
A thick film pattern 25 made of a pattern forming material is formed thereon.

As the base film, a PET film, a polyethylene film, a polyester film, a polyimide film, a polyamide film, a polytetrafluoroethylene film and the like can be used. Among them, a PET film is preferable in terms of cost.

[0012] Negative-type photosensitive resins include cyclized rubber resins such as polyvinyl alcohol, polyvinyl cinnamate, cyclized polyisoprene, cyclized cis 1,4-polybutadiene, polyvinyl-p-acidbenzal, and acid acrylate polymers. Resins having a diazo group or an azide group introduced into a polymer side chain such as a methacrylic or acrylic resin such as polymethyl methacrylate or polymethyl acrylate as a binder resin, and pentaerythritol triacrylate as a monomer.
A system to which trimethylolpropane triacrylate or tetraethylene glycol diacrylate is added can be used.

As the substrate, a glass plate, a ceramic plate, a silicon plate or the like is used depending on the application.

In order to improve the transferability of the female mold, a release layer may be provided on the surface of the base film as necessary, and the release layer may be formed in the base film or the photosensitive resin forming the female mold. The agent may be kneaded.

The release agent is, for example, polyethylene wax,
Amides wax, Teflon powder, silicone wax, carbana wax, acrylic wax, wax such as paraffin wax, fluorine resin, melamine resin, polyolefin resin, ionizing radiation curable polyfunctional acrylate resin, polyester resin, epoxy resin, Examples thereof include amino-modified, epoxy-modified, OH-modified, COOH-modified, catalyst-curable, photocurable, and thermosetting silicone oils or silicone resins. When a release layer is formed, the thickness is 10 to 3000 μm.

Negative-type photosensitive resins are usually cured by light and lose their tackiness. However, by controlling the crosslinking density, it is possible to use a material that gives rise to tackiness by heating and transfer the material with a thermocompression roll. it can. Also,
In the case of a material that does not have sufficient adhesiveness, an adhesive layer that can be removed by baking may be formed on the transfer-receiving substrate side before transferring.

When the pattern forming material is used for a resistor layer or a barrier layer, it is composed of at least an inorganic component having a glass frit and a resin component removed by firing.

The glass frit has a softening point of 3
At 50 ° C. to 650 ° C., the coefficient of thermal expansion α ₃₀₀ is 60 × 10 ⁻⁷
/ ° C to 100 × 10 ^-7 / ° C. If the softening point of the glass frit exceeds 650 ° C., it is necessary to increase the firing temperature, and depending on the lamination object, it is not preferable because it is thermally deformed. It is not preferable because glass frit is fused and voids and the like are generated in the layer. Further, the coefficient of thermal expansion α ₃₀₀ is 60 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ / ° C.
Is out of the range, the difference from the coefficient of thermal expansion of the glass substrate is large, and distortion or the like is generated, which is not preferable.

As the inorganic component, two or more kinds of inorganic powders and inorganic pigments may be mixed in addition to the glass frit.

The inorganic powder is an aggregate and is added as needed. The inorganic powder is intended to prevent casting during firing and to improve the compactness, and has a higher softening point than glass frit. For example, inorganic powders such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, and calcium carbonate can be used, and the average particle size is 0.1 to 20 μm.
m. The use ratio of the inorganic powder is preferably 0 to 30 parts by weight with respect to 100 parts by weight of the glass frit.

The inorganic pigment is added as necessary to reduce external light reflection and improve practical contrast. In the case of darkening, Co-Cr-Fe, Co-Mn-Fe, Co-
Fe-Mn-Al, Co-Ni-Cr-Fe, Co-N
i-Mn-Cr-Fe, Co-Ni-Al-Cr-F
e, Co-Mn-Al-Cr-Fe-Si and the like. Examples of the fire-resistant white pigment include titanium oxide, aluminum oxide, silica, and calcium carbonate.

The resin component removed by firing is a thermoplastic resin, which is contained as a binder for the inorganic component and for the purpose of improving transferability. Examples of the thermoplastic resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n
-Propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, te
rt-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
Examples thereof include polymers or copolymers of one or more of hydroxypropyl methacrylate, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, etc., cellulose derivatives such as ethyl cellulose, and polybutene derivatives.

Particularly, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert -Butyl acrylate,
Preferred are polymers or copolymers of one or more of tert-butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc., ethyl cellulose, and polybutene derivatives.

The proportion of the inorganic component to the resin component is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the inorganic component. When the amount of the resin component is less than 3 parts by weight, a problem arises in that the pattern shape retention is poor and the production of PDP or the like is hindered. On the other hand, if the amount exceeds 50 parts by weight, carbon remains in the film after sintering, and the quality is undesirably deteriorated.

If necessary, a plasticizer, a thickener, a dispersant, an antisettling agent, an antifoaming agent, a release agent, a leveling agent and the like are added.

The plasticizer is added for the purpose of improving transferability and fluidity of the ink. For example, normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate, di-n-octyl phthalate and bis-2-ethylhexyl phthalate are used. Phthalic acid esters such as di-2-ethylhexyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethyl phthalethyl glycolate and butyl phthalyl butyl glycolate; tri-2-ethylhexyl trimellitate; tri-n- Trimellitate such as alkyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, dimethyl adipate,
Dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl acetate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate,
Acetyl-tri- (2-ethylhexyl) citrate,
Aliphatic dibasic acid esters such as acetyl-tri-n-butyl citrate and acetyl tributyl citrate, glycol derivatives such as polyethylene glycol benzoate, triethylene glycol di- (2-ethylhexoate) and polyglycol ether Glycerol derivatives such as glycerol triacetate and glycerol diacetyl monolaurate, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., molecular weight 3
Low molecular weight polyether of 00 to 3,000, low molecular weight poly-α-styrene, low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, orthophosphoric acid esters such as 2-ethylhexyl diphenyl phosphate, ricinoleic acid esters such as methyl acetyl ricinoleate,
Examples thereof include polyesters such as poly-1,3-butanediol adipate and epoxidized soybean oil, epoxidized esters, and acetic esters such as glycerin triacetate and 2-ethylhexyl acetate.

The thickener is added as needed for the purpose of increasing the viscosity of the ink. Known thickeners can be used, for example, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, sodium alginate, casein , Sodium caseinate, xanthan gum, polyvinyl alcohol, modified polyether warren, polyacrylates, polymethacrylates, monmotalonite, aluminum stearate, zinc stearate, aluminum octylate, water-added castor oil, castor oil esters, fatty acids Amide, polyethylene oxide, dextrin fatty acid ester, dibenzylidene sorbitol, vegetable oil-based polymerized oil, surface-treated calcium carbonate, organic bentonite, silica, titania, zirconia, Fine powder such as alumina and the like.

The dispersant and the anti-settling agent are intended to improve the dispersibility of the inorganic component and the anti-settling property, respectively.
For example, phosphate ester type, silicone type, castor oil ester type, various surfactants and the like are exemplified.
For example, silicone-based, acrylic-based, various surfactants and the like are exemplified, and as the release agent, for example, silicone-based, fluorine oil-based, paraffin-based, fatty acid-based, fatty acid ester-based,
Castor oil-based, wax-based, and compound types are exemplified. Examples of the leveling agent include fluorine-based, silicone-based, and various surfactants, and each is added in an appropriate amount.

The pattern forming material is methanol,
Anones such as ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, methylene chloride, 3-methoxybutyl acetate, ethylene glycol monoalkyl ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl Dissolve or disperse in terpenes such as ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates, α- or β-terpineol Let it be ink. A non-sol type ink that does not use such a solvent may be used.

When the pattern forming material is for forming an electrode, the electrode forming paste comprises at least an inorganic component made of glass frit, a resin component removed by firing, and a conductive powder.

As the inorganic component, the glass frit, the inorganic powder, and the inorganic pigment described in the section of the pattern forming material such as the barrier layer described above can be used. The amount of the inorganic powder is preferably 0 to 10 parts by weight based on 100 parts by weight of the glass frit.

As the resin component removed by firing, the thermoplastic resin described in the section of the pattern forming material for the barrier layer or the like can be used, and the resin component contained in the electrode forming paste can be used. The amount is 3-60% by weight,
Preferably it is 5 to 30% by weight.

As the conductive powder, gold, silver, copper,
Metal powders such as nickel and aluminum are mentioned, and spherical metal powders having an average particle size of 0.1 to 5 μm are preferable. The usage ratio of the conductive powder to the glass frit is such that the glass frit is 2 to 20 parts by weight based on 100 parts by weight of the conductive powder.

The electrode forming paste may contain a plasticizer, a dispersant, an anti-settling agent, an antifoaming agent, a release agent, and a leveling agent, if necessary. Those described in the section of the forming material can be used.
To form an electrode forming paste, the above constituent materials are mixed with a solvent, if necessary, in the same manner as described in the section of the pattern forming material such as the barrier, and kneaded by a roll mill, a bead mill or the like. Coating liquid or kneaded by a ball mill or the like to obtain a slurry coating liquid. As a method of filling the above-mentioned ink into the female mold transferred onto the substrate or the female mold on the base film, a doctor method may be used, or the ink may be filled under reduced pressure.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a case where a PDP barrier is formed as a thick film pattern will be described with reference to embodiments.

(Example 1) A negative photosensitive resin paste of the following composition A was applied on a PET film having a thickness of 50 μm and dried to form a photosensitive resin layer, and pattern exposure was performed through a mask. Subsequently, development was performed to create a female mold of the barrier pattern.

<Composition A> 100 parts by weight of polyvinyl alcohol 100 parts by weight of hydroxyethyl methacrylate 5 parts by weight of ethylene glycol dimethacrylate 2.5 parts by weight of benzoyl propyl ether 0.2 parts by weight of P-methoxyphenol

Next, the PET film is laminated on a glass substrate such that the female mold side is in contact with the glass substrate,
The PET film was peeled off, and the female mold was transferred to a glass substrate. Specifically, the glass substrate is heated to 80 ° C.
Thermocompression bonding was performed at a speed of 50 mm / s using a roll having a temperature of 100 ° C. The female mold transferred to the glass substrate was filled with a barrier material paste having the following composition B using a doctor blade.

<Composition B> 65 parts by weight of glass frit (“MB-008” manufactured by Matsunami Glass Industry) 10 parts by weight of α-alumina (“RA-40” manufactured by Iwatani Chemical Industry) Black pigment (“Dipiroki” manufactured by Dainichi Seika) Side black # 9510 ") 10 parts by weight n-butyl methacrylate / 2-hydroxyethyl methacrylate copolymer 8 parts by weight Bis (2-ethylhexyl) phthalate 5 parts by weight Dimethyl phthalate 5 parts by weight Propylene glycol monomethyl ether 12 parts by weight

After filling the female mold with the barrier material paste as described above, drying at 120 ° C. for 5 minutes,
Sintering the barrier material paste and burning off the female mold. This formed a barrier on the glass substrate. When n-butyl methacrylate / 2-hydroxyethyl methacrylate copolymer is mixed with bis (2-ethylhexyl) phthalate and dimethyl phthalate, these phthalate esters not only act as a plasticizer but also have a defoaming effect. Was also preferred.

(Embodiment 2) As in Embodiment 1, the thickness 50
A female mold of a barrier pattern was formed on a μm PET film using the negative photosensitive resin paste of the composition A. Then, the female material was filled with the barrier material paste of the composition B using a doctor blade. After drying at 120 ° C. for 5 minutes, the PET film is thermocompression-bonded to a glass substrate,
The female mold and the barrier material paste were simultaneously transferred to a glass substrate. Specifically, the glass substrate is heated to 80 ° C.
Thermocompression bonding was performed at a speed of 50 mm / s using a roll having a temperature of 100 ° C. Then, by firing at a temperature of 580 ° C., the barrier material paste was sintered and the female mold was burned off. This formed a barrier on the glass substrate.

[0042]

As described above, according to the method for forming a thick film pattern of the present invention, the female mold formed on the base film is transferred to the substrate, and the female mold is filled with the pattern forming material on the substrate. Alternatively, since the step of simultaneously transferring the female mold formed on the base film and the pattern forming material filled in the female mold to the substrate is employed, the number of steps is smaller than that of a conventional method such as a screen printing method or a sand blast method. High productivity.

Further, since only a pre-formed female film whose quality has been checked can be used, the yield rate can be improved.

[Brief description of the drawings]

FIG. 1 is a process chart showing a procedure of a first thick film pattern forming method according to the present invention.

FIG. 2 is a process chart showing a procedure of a second thick film pattern forming method according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Glass substrate 11 Base film 12 Photosensitive resin layer 13 Female type 14 Pattern forming material 15 Thick film pattern

Claims (2)

[Claims] 1. A negative type photosensitive resin layer is formed on a base film, and the photosensitive resin layer is subjected to pattern exposure and development to form a pattern female mold, and then the female mold is transferred to a substrate. A method of forming a thick film pattern, comprising: filling a female mold with a pattern forming material on a substrate, sintering the pattern forming material by firing, and removing the female mold. 2. A negative type photosensitive resin layer is formed on a base film, and the photosensitive resin layer is subjected to pattern exposure and development to form a pattern female mold. A method for forming a thick film pattern, comprising: simultaneously transferring a female mold and a pattern forming material to a substrate after filling, sintering the pattern forming material by firing, and removing the female mold.