JPH11228901A - Inorganic pigment paste composition, transfer film and plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which is excellent in dispersion stability of an inorganic pigment and in storing stability by blending an inorganic pigment, a binder resin and a fatty acid. SOLUTION: As an inorganic pigment, a red pigment such as Fe2 O3 or the like, a green pigment such as Cr2 O3 or the like, and a blue pigment such as 2(Al2 Na2 Si3 O10 ).Na2 S4 or the like can be used in addition to an inorganic pigment for color correction like a yellow pigment such as PbCrO4 -PbSO4 or the like, an orange pigment such as Pb(Cr-Mo-S)O4 and a purple pigment such as Co3 (PO4 )2 or the like. As a binder resin, although various resins can be used, an acrylic resin is desirable. As the acrylic resin, a copolymer of a monomer (e.g. acrylic acid) and another monomer (e.g. methyl acrylate) or the like is desirable. The composition ratio is 1-50 pts.wt. of the resin to 100 pts.wt. of the inorganic pigment. As a fatty acid, one with 8-30 carbon atoms such as octanoic acid is desirable. The formulation ratio is 0.001-10 pts.wt. of the fatty acid to 100 pts.wt. of the inorganic pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an inorganic pigment paste composition, and more particularly, to an inorganic pigment paste composition that can be suitably used for forming a color filter of 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 TVs of 20 inches or more. Color PDP
The color display can be performed 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 MgO as a protective film is formed thereon. Here, in order to improve the contrast of the plasma display panel, R, G, B color filters 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, partition walls are provided between the electrodes, and phosphors are formed on the side and bottom surfaces of the partition walls. The sustain electrodes on the front substrate and the signal electrodes on the rear substrate are bonded and sealed so as to be vertical, and a mixed gas of Ne and Xe 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 stripes on the front substrate glass. Here, in order to improve the contrast of the plasma display panel, R, G, B color filters and a black matrix may be provided on the front substrate. On the other hand, electrode terminals and leads for 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 phosphors are formed on the side surfaces of the partition walls and on the bottom surface excluding the anode terminals. The cathode on the front substrate, the display on the rear substrate, and the auxiliary anode are attached and sealed so that they are perpendicular to each other.
A mixed gas of e and Xe is introduced.

[0005] As a method for producing such a color filter for a plasma display panel, there are (1) a screen printing method in which a non-photosensitive inorganic pigment paste composition is formed on a substrate by screen printing; There is known a photolithography method in which an inorganic pigment paste composition is formed, irradiated with ultraviolet rays through a photomask, and then developed to leave a pattern on a substrate.

However, all of the above-described methods for forming a color filter require multiple printing by screen printing or the like when forming a film of the inorganic pigment paste composition on a substrate. The applied coating has a sufficiently uniform film thickness (for example, tolerance within 5%)
Does not have When a coating film having insufficient film thickness uniformity is formed, there is a problem in that a color filter causes uneven transmittance. Further, in the screen printing method, the mesh shape of the screen plate may be transferred to the surface of the film forming material layer, and may be transferred to the surface of such a film forming material layer. The color filter may be transferred to the surface of the layer, and the color filter formed by firing such a film forming material layer has poor surface smoothness.

As a means for solving the above-mentioned problems in the case where the inorganic pigment paste layer is formed by screen printing, the present inventors have formed a laminate of a photosensitive resist composition layer and an inorganic pigment paste layer, The photosensitive resist composition layer constituting the laminated film is exposed to light to form a latent image of a resist pattern, the photosensitive resist composition layer is developed to reveal a resist pattern, and an inorganic pigment paste layer is formed. Forming a pattern of a color filter by a method including a step of forming an inorganic pigment paste layer pattern corresponding to the resist pattern by etching, and baking the pattern to form an inorganic pigment pattern; A method for manufacturing a display panel is proposed. (See Japanese Patent Application No. 9-340514)

The binder resin used for the transfer film as described above includes (1) easy combustibility (2) flexibility (3)
It is necessary to satisfy performance such as transferability (4) affinity with inorganic pigment (5) alkali solubility, and acrylic resin is generally preferred. In particular, imparting affinity to the inorganic pigment to the binder resin stabilizes the dispersed state of the inorganic pigment, agglomeration of the inorganic pigment in the composition, sedimentation, phase separation and cake-like at the bottom of the storage container. Generation of deposits can be suppressed.

[0009]

However, imparting an affinity to an inorganic pigment to a binder resin may cause the following problems. (1) During storage of the inorganic pigment paste composition in a paste state, the adsorption gradually proceeds between the binder resin and the inorganic pigment, and the viscosity increases. (2) During storage of the inorganic pigment paste layer in the form of a film, adsorption gradually proceeds between the binder resin and the inorganic pigment, and as a result, organic substances cannot be completely decomposed and removed under predetermined firing conditions. Color purity decreases. (3) During storage of the inorganic pigment paste layer in a film state, adsorption gradually proceeds between the binder resin and the inorganic pigment, and as a result, the flexibility of the film is gradually lost and the film becomes a brittle material. Or the transferability is reduced.

[0010] In response to such a problem, the present inventors:
As a method of preventing the binder resin from gradually adsorbing to the surface of the inorganic pigment, it is necessary to prepare an inorganic pigment paste composition containing a fatty acid to exhibit stable performance in a paste state or a film state. I found it. That is,
A first object of the present invention is to provide an inorganic pigment paste composition having excellent dispersion stability of an inorganic pigment. A second object of the present invention is to provide an inorganic pigment paste composition that does not contain an aggregate of inorganic pigment and does not generate the aggregate over time. A third object of the present invention is to provide an inorganic pigment paste composition having excellent storage stability that does not generate cake-like deposits at the bottom of a storage container. A fourth object of the present invention is to provide an inorganic pigment paste composition and a transfer film which do not cause film defects such as streaky coating marks, craters and pinholes on a film forming material layer. A fifth object of the present invention is to provide a transfer film in which the transferability of the film-forming material layer (the adhesiveness of the film-forming material layer to the glass substrate by heating) does not change over time. A sixth object of the present invention is to provide a plasma display panel having a color filter with high dimensional accuracy and high color reproducibility.

[0011]

The inorganic pigment paste composition of the present invention is characterized by containing (A) an inorganic pigment, (B) a binder resin, and (C) a fatty acid.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The inorganic pigment paste composition of the present invention, an inorganic pigment,
It contains a binder resin and a fatty acid as essential components.

<Inorganic Pigment> The inorganic pigment used in the inorganic pigment paste composition of the present invention includes Fe ₂ O ₃ , Pb ₃ O ₄ , CdS and CdS.
e, red pigments such as PbCrO ₄ , PbSO ₄ , Fe (NO ₃ ) ₃ ; Cr
₂ O ₃ , TiO ₂ -CoO-NiO-ZnO, CoO-CrO-TiO ₂ -Al ₂ O ₃ , Co ₃ (PO
4) Green pigments such as ₂ and CoO-ZnO; 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) ・ Na ₂
Blue pigments such as S ₄ ) and CoO—Al ₂ O ₃ can be mentioned. Other inorganic pigments for color correction include PbCrO ₄ -PbSO ₄ ,
Yellow pigments such as PbCrO ₄ , PbCrO ₄ -PbO, CdS, TiO ₂ -NiO-Sb ₂ O ₃ ; orange pigments such as Pb (Cr-Mo-S) O ₄ ; purple pigments such as Co ₃ (PO ₄ ) ₂ Can be mentioned.

<Binder Resin> As the binder resin used in the inorganic pigment paste composition of the present invention, various resins can be used, and it is particularly preferable to use an acrylic resin as the binder resin. Among the acrylic resins, particularly preferred are the following copolymers of monomer (a) and monomer (b) or copolymers of monomer (a), monomer (b) and monomer (c). Can be mentioned.

Monomers (a): acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Carboxyl group-containing monomers such as citraconic acid, mesaconic acid, and cinnamic acid; hydroxyl group-containing such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate Alkali-soluble functional group-containing monomers represented by monomers and the like. Monomer (b): methyl (meth) acrylate, (meth)
Representative of (meth) acrylates other than monomer (a) such as ethyl acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate Monomers copolymerizable with the monomer (a) to be used. Monomer (c): A polymerizable polymer such as a (meth) acryloyl group is attached to one end of a polymer chain such as polystyrene, poly (methyl) methacrylate, ethyl poly (meth) acrylate, and benzyl poly (meth) acrylate. Macromonomers represented by macromonomers having a saturated group:

The content ratio of the binder resin in the inorganic pigment paste composition is based on 100 parts by weight of the inorganic pigment.
Usually, it is 1 to 50 parts by weight, preferably 1 to 40 parts by weight.

<Fatty Acid> The inorganic pigment paste composition of the present invention is characterized in that a fatty acid is contained as a dispersant for the inorganic pigment. By using the fatty acid,
An inorganic pigment paste composition having excellent inorganic pigment dispersion stability can be obtained. The fatty acid used in the present invention preferably has 8 to 30 carbon atoms. When a fatty acid having less than 8 carbon atoms is contained, sufficient flexibility is hardly exhibited in the film-forming material layer formed by the obtained inorganic pigment paste composition. On the other hand, fatty acids having more than 30 carbon atoms are less likely to decompose, and organic substances remain in the firing step of the film-forming material, which may cause a reduction in the color purity of the color filter.

Preferred specific examples of the above fatty acids include octanoic acid, undecylic acid, lauric acid, myristic acid,
Saturated fatty acids such as palmitic acid, pentadecanoic acid, stearic acid, and arachinic acid; unsaturated fatty acids such as elaidic acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid; Can be used in combination.

The content ratio of the fatty acid in the composition of the present invention is 0.001 to 100 parts by weight of the inorganic pigment.
The amount is preferably from 10 to 10 parts by weight, more preferably from 0.01 to 5 parts by weight. When the proportion of the fatty acid is too small, the effect of improving the dispersion stability of the inorganic pigment and the effect of improving the flexibility of the formed film-forming material layer may not be sufficiently exhibited. On the other hand, when this ratio is excessive, the viscosity increases with time when the obtained inorganic pigment paste composition is stored, or does not sufficiently burn during firing, and may cause organic residues to remain. May be.

<Solvent> The inorganic pigment paste composition of the present invention usually contains a solvent. As the solvent, the affinity with the inorganic pigment, the solubility of the binder resin is good, it can impart a suitable viscosity to the inorganic pigment paste composition, and can be easily evaporated and removed by drying. Preferably, there is. Specific examples of such a solvent include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates,
Alkoxy acetates, propionates,
Hydroxypropionic acid esters, alkoxypropionic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxyacetic esters, cyclic ketones, acyclic ketones, acetoacetic acid Esters, pyruvates, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones,
Examples thereof include dialkyl sulfoxides, dialkyl sulfones, terpineol, N-methyl-2-pyrrolidone, and the like, and these can be used alone or in combination of two or more. The content ratio of the solvent in the inorganic pigment paste composition can be appropriately selected within a range in which good film-forming properties (fluidity or plasticity) can be obtained.

The inorganic pigment paste composition of the present invention contains, in addition to the above essential components, a plasticizer, a development accelerator, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, and an ultraviolet ray. Various additives such as an absorbent, a filler, a low-melting glass, and a thermosetting resin may be contained.

The composition of the present invention is prepared by kneading the above-mentioned inorganic pigment, binder resin, fatty acid and optional components using a kneader such as a roll kneader, a mixer, a homomixer, a ball mill, a bead mill, or the like. Can be.
The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for application, and has a viscosity of usually 1,000 to 30,000 cp, preferably 3,0 cp. 000 to 10,000 cp.

<Transfer Film> The transfer film of the present invention comprises a support film and an inorganic pigment paste layer of the present invention formed on the support film, and a protective film is provided on the surface of the inorganic pigment paste layer. A layer may be provided.

The support film is preferably a resin film having heat resistance and solvent resistance and having flexibility. When the support film has flexibility, the paste composition can be applied by a roll coater, and the inorganic pigment paste layer can be stored and supplied in a rolled state. As the resin forming the support film, for example, polyethylene terephthalate, polyester, polyethylene, polypropylene,
Examples thereof include fluorine-containing resins such as polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
As the thickness of the support film, for example, 20 to 100 μm
It is said.

As a method of applying the inorganic pigment paste composition on the support film, it is necessary that the composition can efficiently form a large coating film having excellent uniformity in film thickness. Specifically, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a wire coater, and the like can be mentioned as preferable examples. In addition, it is preferable that the surface of the support film to which the inorganic pigment paste composition is applied is subjected to a release treatment. Thereby, in the transfer step described later, the operation of peeling the support film can be easily performed.

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

The thickness of the inorganic pigment paste layer formed on the support film as described above varies depending on the content of the inorganic pigment, the type and size of the member, and is, for example, 1 to 50 μm. In addition, as a protective film layer which may be provided on the surface of the inorganic pigment paste layer, a polyethylene film, a polyvinyl alcohol-based film, or the like can be used.

The transfer film of the present invention may be one in which a laminated film of a resist layer and a film forming material layer is formed on a support film. By transferring the laminated film to a glass substrate, a composite film in which a resist film is formed on a film forming material layer can be obtained. As a resist composition used to form a resist film, an alkali developing type,
Radiation-sensitive resist compositions such as a solvent development type and a water development type can be exemplified, and among them, an alkali development type radiation-sensitive resist composition is preferably used. Hereinafter, the alkali-developable radiation-sensitive resist composition will be described.

<Alkali-developing radiation-sensitive resist composition> The alkali-developing radiation-sensitive resist composition contains an alkali-soluble resin and a radiation-sensitive component as essential components. Examples of the alkali-soluble resin constituting the alkali-developable radiation-sensitive resist composition include the alkali-soluble resins exemplified as constituting the binder component of the inorganic pigment paste composition. Examples of the radiation-sensitive component constituting the alkali-developable radiation-sensitive resist composition include, for example, (a) a combination of a polyfunctional monomer and a photopolymerization initiator, and (b) a melamine resin and an acid by irradiation with a radiation. Preferred examples include a combination with a photoacid generator, and the above (a)
Of the combinations, a combination of a polyfunctional (meth) acrylate and a photopolymerization initiator is particularly preferred.

Specific examples of the polyfunctional (meth) acrylate constituting the radiation-sensitive composition include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyalkylenes such as polyethylene glycol and polypropylene glycol. Glycol di (meth) acrylates; both ends hydroxypolybutadiene, both ends hydroxypolyisoprene,
Di (meth) acrylates of hydroxyl-terminated polymers such as hydroxypolycaprolactone at both ends; tri- or higher valents such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, dipentaerythritol, etc. Poly (meth) acrylates of polyhydric alcohols; poly (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols; cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol Poly (meth) acrylates; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, spirane resin (meth) acrylate, etc. (Meth) acrylates and the like can be mentioned, which may be used alone or in combination of two or more kinds.

Specific examples of the photopolymerization initiator constituting the radiation-sensitive component include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4′-
(Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-
Carbonyl compounds such as (4-morpholinophenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; organic sulfur compounds such as mercaptan disulfide; benzoyl peroxide; tret-butyl peroxide, tret-butyl hydroperoxide,
Organic peroxides such as cumene hydroperoxide and paramethane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,
3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,
Trihalomethanes such as 3,5-triazine; 2,2 ′
Imidazole dimers such as -bis (2-chlorophenyl) 4,5,4 ', 5'-tetraphenyl1,2'-biimidazole; and the like, alone or in combination of two or more. Can be used.

The content ratio of the radiation-sensitive component in the alkali-developable radiation-sensitive resist composition is usually 1 to 300 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the alkali-soluble resin. . Further, the alkali-developable radiation-sensitive resist composition contains an organic solvent as appropriate in order to impart good film-forming properties. Examples of such organic solvents include the solvents exemplified as constituents of the inorganic pigment paste composition.

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

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

<Developer> An alkali developer can be used as the developer used in the step of developing the resist film with the alkali-developable radiation-sensitive resist composition.
Examples of the effective component of the alkali developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and ammonium dihydrogen phosphate. , Potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate,
Lithium borate, sodium borate, potassium borate,
Inorganic alkaline compounds such as ammonia; organic alkaline compounds such as tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. Can be mentioned. The alkali developer used in the resist film developing step can be adjusted by dissolving one or more of the above alkaline compounds in water or the like. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
5% by weight. After the development processing with an alkali developing solution, a washing treatment is usually performed.

<Etching Treatment> The etching solution used in the etching step of the inorganic pigment paste layer is preferably an alkaline solution. Thereby, the alkali-soluble resin contained in the inorganic pigment paste layer can be easily dissolved and removed. In addition, since the inorganic pigment contained in the inorganic pigment paste layer is uniformly dispersed in the alkali-soluble resin, when the alkali-soluble resin is dissolved and removed with the alkaline solution, the inorganic pigment is also removed. Here, examples of the alkaline solution used as the etching solution include a solution having the same composition as the developer. When the etching solution is the same solution as the alkali developing solution used in the developing step, the developing step and the etching step can be performed continuously, and the manufacturing efficiency is reduced by simplifying the steps. Improvement can be achieved. After the etching treatment with the alkaline solution is performed, a water washing treatment is usually performed.

[0037]

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

Example 1 (1) Preparation of Inorganic Pigment Paste Composition: 20 parts of Fe ₂ O ₃ as a red inorganic pigment, butyl methacrylate (50% by weight) and methyl methacrylate (30%) as a binder resin
Wt.) And methacrylic acid (20 wt.%), 20 parts of an acrylic resin (weight average molecular weight in terms of polystyrene by GPC: 100,000, hereinafter referred to as "polymer A"), 20 parts, and stearic acid as a fatty acid 1
_{Parts, PbO-SiO 2 -B 2 O} 3 as the low melting point glass -
An inorganic pigment paste composition of the present invention having a viscosity of 5,000 cp was prepared by kneading 80 parts of a ZnO-based glass and 15 parts of propylene glycol monomethyl ether as a solvent using a disperser. Next, a green inorganic pigment paste composition was prepared in the same manner as the red inorganic pigment paste composition, except that Cr ₂ O ₃ was used as the green inorganic pigment. The viscosity was 6,000 cp. Then except for using CoO-Al ₂ O ₃ as the inorganic pigment blue was prepared a blue inorganic pigment paste composition similar to the red inorganic pigment paste composition. The viscosity is 5,500 cp
Met.

(2) Evaluation of storage stability of composition: The composition of the present invention prepared in the above (1) was housed in a container, and the container was left in a thermostat at 25 ° C for 30 days.
Next, when the bottom of the container was observed, no cake-like deposits were observed at all, and the viscosity was 5,200 for red.
cp, 6,500 cp for green, and 5,600 cp for blue, and this composition was excellent in storage stability.

(3) Preparation of radiation-sensitive resist composition:
Same as Polymer A except that a monomer composition comprising 200 parts of ethyl 3-ethoxypropionate, 85 parts of n-butyl methacrylate, 15 parts of methacrylic acid, and 1 part of azobisisobutyronitrile was charged into an autoclave. A polymer solution was obtained. Here, the polymerization rate is 98%,
Copolymer precipitated from this polymer solution [hereinafter referred to as “polymer B”. ] Has a weight average molecular weight (Mw) of 5
It was 0000.

Next, 50 parts of polymer B as an alkali-soluble resin, 40 parts of pentaerythritol tetraacrylate as a polyfunctional monomer (radiation-sensitive component), and 2-benzyl-2 as a photopolymerization initiator (radiation-sensitive component).
-Dimethylamino-1- (4-morpholinophenyl)
5 parts of butan-1-one and 150 parts of ethyl 3-ethoxypropionate as a solvent are kneaded to form a paste-like alkali-developable radiation-sensitive resist composition [hereinafter referred to as “resist composition”. ] Was prepared.

The transfer film (R) having the laminated film of the inorganic pigment paste layer for red color and the resist layer formed on the support film was operated by the following operations (a) to (b). (A) A support film (200 mm wide, 30 m long,
A film having a thickness of 38 μm) was applied using a roll coater, the coating was dried at 100 ° C. for 5 minutes to completely remove the solvent, and a resist film having a thickness of 5 μm (hereinafter referred to as “resist film”). ]
Was formed on a supporting film. (B) The inorganic pigment paste for red color is applied on the resist film using a roll coater, and the coating film is dried at 100 ° C. for 5 minutes to completely remove the solvent. A layer was formed on the resist film to prepare a transfer film (R). Subsequently, a transfer film (G) having a paste layer for green and a transfer film (B) having a paste layer for blue were produced in the same manner as in the operations (a) to (b).

(5) Evaluation of Transfer Film: The surface state of the film-forming material layer of each of the transfer films produced in the above (4) was observed using a microscope. No film defects such as paint marks, craters and pinholes were found. Further, even when the transfer film was bent, no cracks (bending cracks) occurred on the surface of the film forming material layer, and the film forming material layer had good flexibility.

(6) Transferring the laminated film: The transfer film (R) produced in the above (4) is overlaid so that the surface of the inorganic pigment paste layer is in contact with the surface of the glass substrate for a 6-inch panel. Then, the transfer film 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 bonding, the support film was peeled off from the laminated film [the surface of the photosensitive resist composition layer]. Thereby, the laminated film was transferred to the surface of the glass substrate and brought into close contact therewith. When the film thickness of this laminated film [laminated film of the inorganic pigment paste layer and the photosensitive resist film] was measured, it was 25 μm ± 1 μm.
m.

(7) Exposure and development steps of the resist film:
The resist film formed on the inorganic pigment paste layer was exposed to an i-line (wavelength 365) by an ultra-high pressure mercury lamp through an exposure mask (a stripe pattern having a width of 300 μm).
nm ultraviolet light). Here, the irradiation amount is 100 m
J / cm ² . Then, a 0.2% by weight aqueous solution of potassium hydroxide (25 wt.
(° C.) as a developing solution by a shower method over 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.

(8) Etching step of inorganic pigment 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 (25 ° C.) as an etching solution is performed for 1 minute. I went. Next, a washing treatment and a drying treatment with ultrapure water were performed. Thereby, a pattern of the inorganic pigment paste layer composed of the material layer remaining portion and the material layer removed portion was formed. Thereafter, post-baking was performed in an oven at 200 ° C. for 30 minutes.

(9) Green and Blue Laminating Step On the pattern of the formed inorganic pigment paste layer for red,
Using the transfer film (G) and the transfer film (B), the above operations (6) to (8) were performed in the same manner to form a stripe pattern composed of a red, green, and blue inorganic pigment paste layer.

(10) Step of firing inorganic pigment paste layer:
The glass substrate on which the pattern of the red, green, and blue inorganic pigment paste layers was formed was subjected to a baking treatment in a baking furnace at a temperature of 520 ° C. for 30 minutes. As a result, a panel material having the color filter pattern formed on the surface of the glass substrate was obtained. After the above-mentioned processing operation, when observed by an optical microscope, no undissolved matter remained on the substrate. Further, the residual film ratio of the formed resist pattern was as good as 90%. When the cross section of the resist pattern was observed with a scanning electron microscope (SEM), no undercut was observed.

(11) Evaluation of Storage Stability of Transfer Film The transfer film produced in the above (4) was left in a thermostat at 25 ° C. for 30 days. Next, the same operations as in the above (6) to (10) were performed using this transfer film, and the flexibility, transferability, developability, and dimensional accuracy of the transfer film were at levels at which there was no problem. The above results are summarized in Table 1.

Comparative Example 1 A comparative inorganic pigment paste composition was prepared in the same manner as in Example 1 except that no fatty acid was used, and a transfer film was produced using the composition. A color filter was formed on the surface of a glass substrate for a 6-inch panel by transferring, exposing, developing and baking the film forming material layer using the transfer film. When the storage stability of the inorganic pigment paste composition was evaluated in the same manner as in Example 1, a cake-like hard deposit was observed at the bottom of the storage container, and the paste viscosity was 6,000 cp to 2
The composition had an inferior storage stability. In addition, when the surface state of the film-forming material layer formed by the composition was observed using a microscope, aggregates of inorganic pigments of about 20 to 100 μm and a large number of craters having the aggregates as nuclei were recognized.
Further, the transfer film had sufficient initial flexibility, but the transfer film after 30 days at 25 ° C. had poor flexibility. When the transfer film was folded, cracks were formed on the surface of the film-forming material layer. Bending cracks) occurred, and the film forming material layer did not have good flexibility. According to the transfer film of Comparative Example 1, the film forming material layer constituting the transfer film could be transferred to the surface of the glass substrate, and the development time after exposure was 1 minute. On the other hand, after 30 days, the transferability was inferior, and the developing time was as long as 5 minutes. The above results are summarized in Table 1.

[0051]

[Table 1]

[0052]

According to the composition of the present invention, the following effects can be obtained. (1) The inorganic pigment paste composition of the present invention is excellent in the dispersion stability of the inorganic pigment, and does not generate aggregates of the inorganic pigment. (2) The inorganic pigment paste composition of the present invention is excellent in storage stability. Even when the composition of the present invention is stored for a long time, the inorganic pigment does not settle and deposit on the bottom of the container. . (3) A uniform film forming material layer without film defects can be formed. (4) A film-forming material layer having excellent adhesion to a glass substrate can be formed. (5) It can be suitably used for the production of a transfer film. (6) A film-forming material layer having excellent flexibility can be formed on a support film. (7) Transferability of film forming material layer (transferability to glass substrate)
It is possible to produce a transfer film excellent in quality. (8) A PDP color filter having high definition and excellent transparency can be formed.

[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 MgO
Layer 3B Color filter / black matrix 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

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

Claims (3)

[Claims] An inorganic pigment paste composition comprising (A) an inorganic pigment, (B) a binder resin, and (C) a fatty acid. 2. A transfer film, wherein a film-forming material layer comprising the inorganic pigment paste composition according to claim 1 is formed on a support film. 3. A plasma display panel wherein a color filter is formed using the inorganic pigment paste composition according to claim 1.