JP2001176402A - Resin composition and resin composition element for molding barrier ribs, and manufacturing method of barrier rib using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin composition for molding barrier ribs, superior in moldability and preservation stability of barrier ribs for plasma display panel, resin composition elements for molding barrier rib superior in moldability, preservation stability and workability, and manufacturing method for barrier ribs that can shorten manufacturing process and mold barrier ribs having superior shape with good workability. SOLUTION: This resin composition for molding barrier ribs contains an organic material having a binder polymer, an organic silicon compound and a compound having carboxyl radical, as well as an inorganic material. On a substrate provided with a resin composition element for molding barrier ribs having that layer on a support film and removable relief pattern, the element is disposed, so that its resin composite layer for molding barrier ribs faces the substrate side. The resin composite element for molding barrier ribs is laminated as a layer on the substrate and embedded in the gap of the relief pattern, and then baked by removing the relief pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for forming a barrier rib of a plasma display panel, a resin composition element for forming a barrier rib, and a method for producing a barrier rib using the same.

[0002]

2. Description of the Related Art In general, barrier ribs of a plasma display panel are disclosed in, for example, IEICE Technical Report Vol.89 No.377 P.69, IEICE Technical Report Vol.91 No.407 P.49, JP-A-2-301934 and the like. As described in the above, it is formed by a thick film screen printing method or a sand blast method. However, in the case of the screen printing method, while having the feature of being excellent in mass productivity, (1) a plasma display panel requires a large number of repeated printings to obtain a high barrier rib of 100 μm or more. When forming a large screen panel of 40 inches or more, which is expected to have a market share, there are drawbacks such as a decrease in positional accuracy due to expansion and contraction of a screen mesh, and (3) it is difficult to increase the definition of a pixel density.

[0003] On the other hand, in the sand blast method, a resist pattern is usually formed on a barrier rib material layer uniformly formed on a substrate, and a blast material is sprayed on the upper surface of the substrate to cut out portions other than the resist pattern covering portion to form a barrier rib. To form For this reason, the pixel density depends on the resolution of the resist pattern, and high definition can be achieved. However, on the other hand, (1) the expensive barrier rib material is cut out and discarded, resulting in a very high cost.
(2) In addition, the barrier rib material generally contains a lead compound, and there is a problem of environmental pollution due to disposal of the shaved barrier rib material. (3) In the case of a thick film, the bottom of the barrier rib is widened and a rectangular shape is formed. There are drawbacks such as difficulty in obtaining a shaped barrier rib.

[0004] In order to solve the above-mentioned disadvantages,
As a method different from these methods, a method of manufacturing a barrier rib by manufacturing a thick film relief pattern and embedding a barrier rib material serving as a barrier in a gap (photo embedding method).
Has been proposed. In the case of this manufacturing method, there are features such as (1) excellent positioning accuracy of the barrier ribs, (2) excellent shape of the barrier ribs, and (3) low cost and low pollution due to an extremely small amount of extra barrier rib material. Becomes possible.

[0005] However, in the case of the photo embedding method,
In the step of forming the barrier rib, it is necessary to ensure sufficient adhesion between the barrier rib before firing and the substrate. In order to improve the adhesion between the barrier ribs before firing and the substrate (formation of the barrier ribs before firing), it has been proposed to add an organosilicon compound such as a silane coupling agent to the barrier rib material. However, depending on the type of the organosilicon compound, there is a problem in that it reacts with an inorganic material for forming a barrier rib mainly composed of glass contained in the barrier rib material, and the storage stability of the barrier rib material is reduced.

[0006]

An object of the present invention is to provide a barrier rib-forming resin composition which is excellent in barrier rib-forming properties and storage stability of a plasma display panel. The second aspect of the present invention is to provide a barrier rib-forming resin composition element which is excellent in barrier rib-forming properties and storage stability of a plasma display panel and is excellent in workability. The invention according to claim 3 is
An object of the present invention is to provide a method for manufacturing a barrier rib, which can shorten a barrier rib manufacturing process of a plasma display panel and can form a barrier rib having an excellent shape with good workability.

[0007]

The present invention comprises (A) an organic material containing a binder polymer, (B) an organic silicon compound and (C) a compound having a carboxyl group, and (D) an inorganic material. The present invention relates to a resin composition for forming a barrier rib. The present invention also relates to a barrier rib-forming resin composition element having the above-described barrier rib-forming resin composition layer on a support film. Further, the present invention provides a method for manufacturing a semiconductor device, comprising: disposing the barrier rib-forming resin composition element on a substrate provided with a removable relief pattern such that the barrier rib-forming resin composition layer faces the substrate side; By applying pressure to the forming resin composition layer,
On the substrate provided with the relief pattern, after laminating the barrier rib forming resin composition layer and embedding the barrier rib forming resin composition in the gaps of the relief pattern, the relief pattern is removed and the barrier rib forming resin composition is formed. The present invention relates to a method for manufacturing a barrier rib, comprising forming a pattern and firing the pattern.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin composition for forming a barrier rib according to the present invention comprises (A) an organic material containing a binder polymer, (B) an organic silicon compound and (C) a compound having a carboxyl group, and (D) an inorganic material for a barrier rib. And materials.

The binder polymer (A) constituting the barrier rib-forming resin composition of the present invention is not particularly limited in composition, and includes, for example, a vinyl copolymer, and a vinyl copolymer used in the vinyl copolymer. Examples of the monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, Iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid
iso-butyl, iso-butyl methacrylate, acrylic acid
sec-butyl, sec-butyl methacrylate, te acrylate
rt-butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate,
Hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, acrylic acid Dodecyl, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, Cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, methacryl Cycloheptyl acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxy methacrylate Dipropylene glycol,
Methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, acrylic acid 2-
Hydroxyethyl, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, Methacrylic acid 2
-Chloroethyl, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-
Examples include methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like. These are used alone or in combination of two or more.

The weight average molecular weight of the binder polymer (A) in the present invention is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000. This weight average molecular weight is 5,000
If it is less than 3, the film formability and flexibility tend to be reduced when the resin composition element is used as a barrier rib-forming resin composition. If it exceeds 300,000, the barrier rib-forming resin composition layer described below is applied to a relief pattern substrate. The embedding property tends to decrease. The weight average molecular weight is
This is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The binder polymer (A) in the present invention includes a vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an oxirane ring, and an acid anhydride, and at least one ethylene copolymer. Unsaturated unsaturated group, oxirane ring, isocyanate group, hydroxyl group,
A polymerizable vinyl copolymer obtained by subjecting a compound having one functional group such as a carboxyl group to an addition reaction can be used.

Examples of the vinyl monomer used in the vinyl copolymer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an oxirane ring, and an acid anhydride include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. , Itaconic acid, cinnamic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, ethyl isocyanate methacrylate, glycidyl acrylate, glycidyl methacrylate, and maleic anhydride.

At least one ethylenically unsaturated group;
Examples of the compound having one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, a carboxyl group, an amino group, and an acid anhydride include, for example, glycidyl acrylate, glycidyl methacrylate, ethyl isocyanate methacrylate, 2-hydroxyethyl acrylate, Examples include 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, acrylamide, methacrylamide, and maleic anhydride. These are used alone or in combination of two or more.

In the present invention, the glass transition temperature of the binder polymer (A) is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, particularly preferably 10 ° C. or lower, and 0 ° C. or lower. It is very preferable that Glass transition temperature of binder polymer is 30 ℃
If the temperature exceeds the above range, the embedding property of the resin composition layer for forming a barrier rib into the relief pattern substrate in the case of a resin composition element for forming a barrier rib described later tends to decrease. Further, from the viewpoint of handleability when used as a resin composition element for forming a barrier rib, Tg is -1.
It is preferably at least 00 ° C.

As the organosilicon compound (B) constituting the resin composition for forming a barrier rib in the present invention, for example, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5- N-tris (triethoxysilylpropyl) isocyanurate, 1,
3,5-N-tris (trimethoxyethoxysilylpropyl) isocyanurate, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-methacryloxypropyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-
silane coupling agents such as γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane No. These can be used alone or in combination of two or more.

The compound having a carboxyl group (C) constituting the resin composition for forming a barrier rib in the present invention includes, for example, saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, and aliphatic tribasic acids. Basic acids, aromatic tribasic acids and the like can be mentioned.

Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid,
Capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, palmitooleic acid, oleic acid, elaidic acid, linolenic acid, linoleic acid, Oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, monomethyl malonate,
Monoethyl malonate, succinic acid, methylsuccinic acid, adipic acid, methyladipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, maleic acid, itaconic acid,
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like. Among them, oxalic acid, malonic acid,
Succinic acid and the like are preferred. These are used alone or in combination of two or more.

As the inorganic material (D) constituting the resin composition for forming a barrier rib of the present invention, a known inorganic material for a barrier rib may be used. For example, a glass frit material such as low-melting glass, titanium oxide, alumina , Magnesia, calcium oxide, zinc oxide, iron oxide, chromium oxide,
Copper oxide and the like can be mentioned, and these can be used alone or in combination of two or more.

Specific components constituting the glass frit material include PbO, Bi ₂ O ₃ , B ₂ O ₃ , SiO ₂ , P ₂
O ₅ , Al ₂ O ₃ , TiO ₂ , Li ₂ O, Na ₂ O, K ₂ O,
SnO, CaO, ZnO and the like are mentioned, and these are used alone or in combination of two or more kinds. The softening point of these glass powders is 300-1,000 ° C., and the particle size is 0.1.
The thickness is preferably 1 to 20 μm from the viewpoint of workability, strength of the barrier ribs, and the like.

In the resin composition for forming a barrier rib of the present invention, a plasticizer may be used, if necessary, for the purpose of, for example, exhibiting the flexibility of the resin composition for forming a barrier rib. . Known plasticizers can be used, and examples thereof include polyethylene glycol diacetate and polypropylene glycol diacetate.

It is preferable to add a dispersant to the barrier rib forming resin composition of the present invention in order to improve the dispersion of the barrier rib inorganic material. Dispersants include inorganic dispersants (silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite, beidellite, etc.), and organic dispersants (aliphatic amide, aliphatic ester). , Polyethylene oxide-based, sulfate-based anion activator, polycarboxylic acid amine salt-based, polycarboxylic acid-based, polyamide-based,
Polymer polyether type, acrylic copolymer type, special silicon type, etc.). These can be used alone or in combination of two or more.

The compounding amount of the binder polymer (A) constituting the barrier rib-forming resin composition of the present invention is 1 to 20 with respect to 100 parts by weight of the total amount of the (D) barrier rib inorganic material.
0 parts by weight, preferably 2 to 150 parts by weight, more preferably 3 to 130 parts by weight, more preferably 4 to 100 parts by weight, and 5 to 90 parts by weight. It is particularly preferred that
It is extremely preferred to be 80 parts by weight. When the compounding amount is less than 1 part by weight, the strength of the barrier rib before firing composed of the barrier rib forming resin composition described below tends to decrease, and when it exceeds 200 parts by weight, the volume shrinkage of the barrier rib after firing increases. There is a tendency for the barrier ribs formed on the substrate to peel off.

The compounding amount of the organosilicon compound (B) constituting the resin composition for forming a barrier rib of the present invention is 0.04 parts by weight based on 100 parts by weight of the total amount of the inorganic material (D) for a barrier rib.
The amount is preferably 1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight, and very preferably 1 to 10 parts by weight. . If the amount is less than 0.01 parts by weight, the adhesion between the barrier ribs (before firing) and the substrate (before firing), which is made of the resin composition for forming a barrier ribs described below, tends to decrease, and 30 parts by weight. If it exceeds, when the resin composition element for forming a barrier rib, the resin composition for forming a barrier rib exudes from an end portion,
There is a tendency that the handleability of the resin composition element for forming a barrier rib is reduced.

In the present invention, the compounding amount of (C) the compound having a carboxyl group is determined by (D) the inorganic material for barrier rib 1
The amount is preferably 0.01 to 30 parts by weight, more preferably 0.02 to 20 parts by weight, particularly preferably 0.05 to 15 parts by weight, relative to 00 parts by weight. It is extremely preferred that the amount be 07 to 10 parts by weight. When the amount is less than 0.01 part by weight, the effect of improving the storage stability of the barrier rib-forming resin composition tends to be low. When the amount exceeds 30 parts by weight, the barrier rib-forming resin composition element is used. In addition, the resin composition for forming a barrier rib exudes from the end portion, and the handleability of the resin composition element for forming a barrier rib tends to decrease.

In the barrier rib-forming resin composition of the present invention, the amount of the plasticizer is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the total amount of the inorganic material for barrier ribs. Is more preferable. When the amount is more than 20 parts by weight, when the resin composition element for forming a barrier rib is used, the resin composition for forming a barrier rib oozes from an end portion, and the handleability of the resin composition element for forming a barrier rib tends to decrease. There is.

In the resin composition for forming a barrier rib of the present invention, the amount of the dispersant to be compounded is 100 or less.
It is preferably 0.01 to 20 parts by weight based on parts by weight. If this amount is less than 0.01 part by weight, the effect of addition tends to not be exhibited, and if it exceeds 20 parts by weight,
In the case of a resin composition element for forming a barrier rib,
The resin composition for forming a barrier rib exudes from the end, and the handleability of the resin composition element for forming a barrier rib tends to decrease.

[0027] The barrier rib-forming resin composition element of the present invention is obtained by dissolving or mixing each of the components constituting the barrier rib-forming resin composition in a solvent capable of being dissolved or dispersed to form a uniformly dispersed solution. It is obtained by coating and drying on a support film to form a barrier rib-forming resin composition layer. Examples of the solvent capable of dissolving or dispersing the respective components constituting the barrier rib forming resin composition include, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, dimethyl Examples include formamide, tetramethyl sulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

As the support film in the present invention,
Chemically and thermally stable, and, furthermore, composed of a flexible substance, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and the like, among them, polyethylene terephthalate, polyethylene is preferred, polyethylene terephthalate is preferred More preferred. Since the support film must be removable from the barrier rib-forming resin composition layer described below, it may have been subjected to a surface treatment that makes removal impossible, or may be a material. No. The thickness of the support film is preferably 5 to 100 μm, more preferably 10 to 80 μm.

As the coating method, a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. The drying temperature is 6
The temperature is preferably from 0 to 130 ° C, and the drying time is preferably from 3 minutes to 1 hour.

The barrier rib forming resin composition element having the support film and the barrier rib forming resin composition layer is provided on the barrier rib forming resin composition layer.
Further, a peelable cover film may be laminated. Examples of such a cover film include polyethylene, polypropylene, polyethylene terephthalate, and polycarbonate, and more than the adhesive force between the support film and the barrier rib-forming resin composition layer, the cover film and the barrier rib-forming resin composition layer. Is preferably smaller in adhesive strength. The thickness of the cover film is not particularly limited, but is preferably 5 to 100 μm, and more preferably 10 to 90 μm.
The barrier rib forming resin composition element thus obtained can be stored in a roll shape.

The thickness of the resin composition layer for forming a barrier rib in the present invention is not particularly limited, but is preferably 10 to 150 μm, more preferably 20 to 120 μm, and more preferably 30 to 100 μm. Particularly preferred. If the thickness is less than 10 μm, the amount of embedding the barrier rib forming resin composition into the relief pattern gap tends to be insufficient. If the thickness exceeds 150 μm, the unnecessary resin composition for forming the barrier rib on the relief pattern is unnecessary. Tend to remain, and the removal process time tends to be long.

Hereinafter, an example of a method for producing a barrier rib of the present invention will be described. The substrate used in the present invention is not particularly limited, and examples thereof include a ceramic plate, a plastic plate, and a glass plate. On this substrate, an insulating layer, an electrode, a protective layer, and the like may be provided.

In the present invention, the relief pattern provided on the substrate can be obtained by using various materials without any particular limitation as long as it can be removed later. From the viewpoint that a relief pattern having a desired fine structure can be easily obtained, it is preferable to form the relief pattern by a photolithographic method using a photosensitive resin composition. As the photosensitive resin composition, known ones can be used without particular limitation, for example,
Photosensitive films generally used as etching resists, plating resists, solder masks and the like in the manufacture of printed wiring boards (for example, JP-A-5-249658, JP-A-4-157467, JP-B-4-598)
No. 1, Japanese Unexamined Patent Publication No. Hei.
No. 10183, Photek H-N350, Photek HF240, Photek HS-950, Photek SR-2300G-
75 (all manufactured by Hitachi Chemical Co., Ltd.) and the like.

When the photosensitive film comprising the photosensitive resin composition is used, the photosensitive film is laminated on the substrate to form a photosensitive resin layer having a thickness of 50 to 250 μm. On the laminated photosensitive resin layer, there is a support film after imagewise irradiation using a material that effectively emits ultraviolet rays such as a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. as an actinic ray. In this case, the relief film can be formed by removing the support film and selectively removing the photosensitive resin layer by development. The developing method is not particularly limited, and examples thereof include wet development and dry development. In the case of wet development, a developer corresponding to the photosensitive resin composition is used. As a developer,
For example, a weak alkaline dilute aqueous solution of sodium carbonate, potassium carbonate or the like can be mentioned, and the developing system can be a dip system, a spray system or the like.

The thickness (height) of the thus obtained relief pattern is usually 50 to 250 μm, and if it is a stripe type or rectangular type relief pattern,
Its width is 50-500 μm.

In the method of manufacturing the barrier rib according to the present invention, for example, on the substrate provided with the relief pattern, the barrier rib-forming resin composition element is arranged such that the barrier rib-forming resin composition layer is in contact with the element. A method in which pressure is applied to the barrier rib-forming resin composition layer to laminate the barrier rib-forming resin composition layer on the substrate provided with the relief pattern, and then the relief pattern is removed. When laminating using the barrier rib-forming resin composition element, when the cover film is present in the barrier rib-forming resin composition element, after removing the cover film, on the surface provided with the relief pattern, It can be carried out by, for example, pressing with a pressure roll so that the resin composition layer for barrier rib contact is in contact.

The pressure roll may be provided with a heating means so as to be capable of thermocompression, and the heating temperature for thermocompression is preferably 10 to 200 ° C.
The temperature is more preferably 0 to 180 ° C, and 30 to 160 ° C.
C. is particularly preferred, and 40 to 140 C. is particularly preferred. When the heating temperature is lower than 10 ° C., the embedding property of the relief pattern of the barrier rib-forming resin composition layer into the gap tends to decrease.
If it exceeds 300, the organic material constituting the barrier rib forming resin composition tends to thermally decompose. Further, the pressing pressure at the time of heating and pressing is preferably 50 to 1 × 10 ⁵ N / m, more preferably 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m as a linear pressure. It is particularly preferable that the density be from × 10 ² to 4 × 10 ⁴ N / m. If the pressure is less than 50 N / m, the embedding property of the barrier rib-forming resin composition layer into the gap of the relief pattern tends to decrease. If the pressure exceeds 1 × 10 ⁵ N / m, the relief pattern is broken. Tend to

If the barrier rib-forming resin composition element is heated as described above, it is not necessary to pre-heat the substrate provided with the relief pattern, but it is necessary to pre-heat the substrate to the gap between the relief patterns of the barrier rib-forming resin composition layer. In order to further improve the embedding property of the substrate, it is preferable that the substrate provided with the relief pattern is pre-heat treated. The preheating temperature at this time is preferably 30 to 180 ° C., and the preheating time is preferably 0.5 to 20 minutes. Further, in order to further improve the embedding property of the relief pattern of the barrier rib forming resin composition layer into the gap, the surface of the pressure roll may be made of a material having high flexibility such as rubber and plastic. it can.

Further, for the same purpose, the above-mentioned press bonding and heat pressing can be performed under reduced pressure of 5 × 10 ⁴ Pa or less. After the lamination is completed, 30 to 200 ° C.
Can be heated for 1 to 120 minutes. At this time, if a support film exists on the barrier rib forming resin composition layer, the support film may be removed as necessary. Thus, the barrier rib forming resin composition layer can be uniformly formed in the gaps between the relief patterns.

Further, the heating conditions, the pressure conditions, the preheating conditions of the substrate provided with the relief pattern and the film of the barrier rib forming resin composition of the barrier rib forming resin composition element of the present invention are also described. By changing the combination of the conditions such as the thickness, the unnecessary thickness of the resin composition layer for forming a barrier rib on the relief pattern can be extremely reduced.

With respect to the thickness of the barrier rib forming resin composition layer, specifically, the region of the barrier rib forming resin composition in a region equal to the region where the unevenness is formed on the substrate provided with the relief pattern (substrate having unevenness) In the material layer, the ratio ((V1) / (V2)) of the volume (V1) of the barrier rib-forming resin composition layer to the volume (V2) of the concave space of the substrate provided with the relief pattern is (V1). / (V2) =
It is preferable that the thickness be in the range of 1 to 1.2 in that the thickness of the unnecessary resin composition for forming a barrier rib on the relief pattern can be extremely reduced, and (V1) / (V2) is 1.02.
To 1.18, more preferably (V
It is particularly preferred that 1) / (V2) be in the range of 1.05 to 1.15. Here, when (V1) / (V2) is less than 1, there is a tendency that a portion on the inner surface of the concave portion where the resin composition for forming a barrier rib cannot be filled occurs.
When (V1) / (V2) exceeds 1.2,
A large amount of unnecessary resin composition for forming a barrier rib on the relief pattern tends to remain.

For the purpose of facilitating the removal of the relief pattern, the unnecessary resin composition for forming a barrier rib on the relief pattern can be removed by simple polishing or the like before the removal of the relief pattern. In the present invention, the relief pattern is finally removed by various methods. When the relief pattern is stripped using a stripper, the stripper used is, for example, 1 to 10 of sodium hydroxide or potassium hydroxide. % By weight aqueous solution.
When the concentration is less than 1% by weight, the peeling effect is so small that the peeling time tends to be too long.
When the ratio exceeds the above range, the laminated resin composition for forming a barrier rib tends to be attacked. The temperature of the stripping solution is not particularly limited, and it is desirable to set conditions for suitably performing the stripping of the relief pattern and to adjust the conditions as needed. As the peeling method, any of the immersion method and the spray method is suitable, and a method using both the immersion method and the spray method is also preferable.

The thickness (height) of the barrier rib obtained by removing the relief pattern in this manner is usually 5
The width is 20 to 120 μm in the case of a stripe type or lattice type barrier rib. Removing organic components from the barrier rib forming resin composition,
For the purpose of improving the strength, gas impermeability, and the like, the resin composition for forming a barrier rib can be fired. The firing temperature and time are usually from 350 to 580 ° C and from 1 to 20 hours.

[0044]

The present invention will be described below with reference to examples.

Production Example 1 [Preparation of Binder Polymer Solution (a-1)] In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer, (1) shown in Table 1 was charged, and nitrogen was added. 8 under gas atmosphere
Raise the temperature to 0 ° C and keep the reaction temperature at 80 ° C ± 2 ° C.
(2) shown in Table 1 was dropped uniformly over 4 hours.
After dropping (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content: 40.1% by weight) (a-1) having a weight average molecular weight of 30,000.

[0046]

[Table 1]

Production Example 2 [Preparation of Binder Polymer Solution (a-2)] (1) shown in Table 2 was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. 8 under gas atmosphere
Raise the temperature to 0 ° C and keep the reaction temperature at 80 ° C ± 2 ° C.
(2) shown in Table 2 was dropped uniformly over 4 hours.
After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and (3) shown in Table 2 was added. After the addition of (3), the temperature of the reaction system was raised to 100 ° C., and the results are shown in Table 2 over 0.5 hours (4).
Was added dropwise. After the dropwise addition of (4), stirring was continued at 100 ° C. for 20 hours, and then the mixture was cooled to room temperature, and the weight average molecular weight was 60,
000, a binder polymer (solid content: 41.4% by weight) (a-2) having an acid value of 0.2 KOH mg / g was obtained.

[0048]

[Table 2]

Example 1 [Production of Barrier Rib-Forming Resin Composition Element (i)] The materials shown in Table 3 were mixed for 3 hours using a ball mill, and a solution (A-1) for a barrier rib-forming resin composition layer was prepared. Was prepared.

[0050]

[Table 3]

The obtained solution (A-1) for forming a resin composition layer for forming a barrier rib is uniformly applied on a polyethylene terephthalate film having a thickness of 50 μm, and dried with a hot air convection dryer at 110 ° C. for 10 minutes. Then, the solvent was removed to form a resin composition layer for forming a barrier rib. The thickness of the obtained resin composition layer for forming a barrier rib was 50 μm. Next, on the barrier rib forming resin composition layer,
A polyethylene film having a thickness of 25 μm was laminated as a cover film to prepare a barrier rib-forming resin composition element (i).

Example 2 [Production of resin composition element (ii) for forming barrier ribs] The materials shown in Table 4 were mixed for 3 hours using a ball mill, and a solution (A-2) for a resin composition layer for forming barrier ribs was prepared. Was prepared.

[0053]

[Table 4]

The obtained solution (A-2) for forming a barrier rib-forming resin composition layer was uniformly applied on a 50 μm-thick polyethylene terephthalate film, and dried with a hot air convection dryer at 110 ° C. for 10 minutes. Then, the solvent was removed to form a resin composition layer for forming a barrier rib. The thickness of the obtained resin composition layer for forming a barrier rib was 50 μm. Next, on the barrier rib forming resin composition layer,
A polyethylene film having a thickness of 25 μm was laminated as a cover film to prepare a barrier rib-forming resin composition element (ii).

Example 3 [Production of Barrier Rib Forming Resin Composition Element (iii)] The materials shown in Table 5 were mixed for 3 hours using a ball mill, and a solution (A-3) for a barrier rib forming resin composition layer was prepared. Was prepared.

[0056]

[Table 5]

The obtained solution (A-3) for forming a resin composition layer for forming a barrier rib is uniformly applied on a polyethylene terephthalate film having a thickness of 50 μm and dried with a hot air convection dryer at 110 ° C. for 10 minutes. Then, the solvent was removed to form a resin composition layer for forming a barrier rib. The thickness of the obtained resin composition layer for forming a barrier rib was 50 μm. Next, on the barrier rib forming resin composition layer,
A polyethylene film having a thickness of 25 μm was laminated as a cover film to prepare a barrier rib-forming resin composition element (iii).

Comparative Example 1 [Production of Barrier Rib Forming Resin Composition Element (iv)] The materials shown in Table 6 were mixed for 3 hours using a ball mill, and a solution (A-4) for a barrier rib forming resin composition layer was prepared. Was prepared.

[0059]

[Table 6]

The obtained solution (A-4) for forming a barrier rib-forming resin composition layer is uniformly applied on a polyethylene terephthalate film having a thickness of 50 μm, and dried with a hot air convection dryer at 110 ° C. for 10 minutes. Then, the solvent was removed to form a resin composition layer for forming a barrier rib. The thickness of the obtained resin composition layer for forming a barrier rib was 50 μm. Next, on the barrier rib forming resin composition layer,
A polyethylene film having a thickness of 25 μm was laminated as a cover film to prepare a resin composition element (iv) for forming a barrier rib.

Comparative Example 2 [Production of Barrier Rib-Forming Resin Composition Element (v)] The materials shown in Table 7 were mixed for 3 hours using a ball mill, and a solution (A-5) for a barrier rib-forming resin composition layer was prepared. Was prepared.

[0062]

[Table 7]

The obtained solution (A-5) for forming a resin composition layer for forming a barrier rib is uniformly coated on a polyethylene terephthalate film having a thickness of 50 μm, and dried with a hot air convection dryer at 110 ° C. for 10 minutes. Then, the solvent was removed to form a resin composition layer for forming a barrier rib. The thickness of the obtained resin composition layer for forming a barrier rib was 50 μm. Next, on the barrier rib forming resin composition layer,
A polyethylene film having a thickness of 25 μm was laminated as a cover film to prepare a resin composition element (v) for forming a barrier rib.

Example 4 [Formation of Relief Pattern] Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer (weight ratio 53/3)
137 g of a 41% by weight methylcellosolve / toluene (weight ratio 8: 2) solution of 0/17, weight average molecular weight 100,000)
(Solid content 55 g), 34 g of bisphenol A polyoxyethylene dimethacrylate, 11 g of γ-chloro-β-hydroxypropyl-β-methacryloyloxyethyl-O-phthalate, stabilizer (AW-500, manufactured by Kawaguchi Chemical Co., Ltd.) 0 0.1 g, tribromomethylphenylsulfone 1.2 g, silicone leveling agent (SH-193, manufactured by Toray Silicon Co., Ltd.) 0.04 g, 1,7 bis-
0.2 g of (9-acridinyl) heptane, 3 g of benzyldimethyl ketal, leuco crystal violet
0 g, malachite green 0.05 g, toluene 7 g,
13 g of methyl ethyl ketone and 3 g of methanol were blended to obtain a solution of the photosensitive resin composition.

The solution of the photosensitive resin composition was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm and dried with a hot air convection dryer at 110 ° C. for about 10 minutes to obtain a photosensitive film. The film thickness of the photosensitive resin layer after drying was 50 μm. Next, the obtained photosensitive film was laminated on a substrate in three layers to form a photosensitive resin layer having a thickness of 150 μm. As a substrate, a glass plate (3.0 mm
Thickness). Lamination is performed at a laminating roll temperature of 13
0 ° C., roll pressure 0.4 MPa (4.0 kgf / cm ² ), speed 1.
The test was performed under the condition of 0 m / min. Next, a negative mask was placed on the polyethylene terephthalate film, and exposure was performed at 80 mJ / cm ² using a 3 kW high-pressure mercury lamp (HMW-590, manufactured by Oak Manufacturing Co., Ltd.). Heating was performed at 80 ° C. for 10 minutes within 5 minutes after exposure.

Next, after peeling off the polyethylene terephthalate film, spray development was carried out with a 1% by weight aqueous sodium carbonate solution at 30 ° C. Next, immersion treatment is performed at 20 ° C. in a 0.5% by weight aqueous solution of hydrogen chloride, washed with water, drained,
After drying for 5 minutes with a 7kW metal halide lamp (HMW-6
80, manufactured by Oak Manufacturing Co., Ltd.) at ² J / cm ² . Then
Heated at 150 ° C. for 10 minutes. Thus, a substrate having a rectangular cross-sectional shape and provided with a thick film relief pattern (sheet glass 3 mm thick, 10 cm long × 10 cm wide, L / S = 150/70)
μm, and a relief thickness of 150 μm).

[Formation of Barrier Rib] The polyethylene film of the resin composition element (i) for forming a barrier rib obtained in Example 1 was peeled off on the side of the substrate provided with such a relief pattern on which the relief pattern was formed. , Laminator (HLM, manufactured by Hitachi Chemical Co., Ltd.)
-1500 type), the lamination temperature is 130 ° C.,
The laminating speed is 0.5 m / min and the pressing pressure (cylinder pressure) is 4 × 10 ⁵ Pa (thickness 3 mm, length 10 cm × width 10 cm)
The linear pressure at this time was 9.8 × 10 ³ N /
In m), the barrier rib-forming resin composition layer was pressed and laminated via a polyethylene terephthalate film, and the barrier rib-forming resin composition layer was embedded in the gaps of the relief pattern.

The cross section of the obtained sample was visually observed with a stereoscopic microscope and an SEM, and the embedding state of the resin composition for forming a barrier rib in the gap of the relief pattern was evaluated. The results are shown in Table 8. The evaluation criteria are as follows. ：: The barrier rib forming resin composition is embedded in the gaps of the relief pattern without gaps. ×: The resin composition for forming a barrier rib was not embedded without a gap in the gap of the relief pattern.

Next, the obtained sample was immersed in a 5% by weight aqueous solution of sodium hydroxide at 40 ° C. for 7 minutes, and then immersed in hot water of 60 ° C. to peel off and remove the relief pattern. Was formed.
The cross section of the pattern formed of the obtained resin composition for forming a barrier rib was visually observed with a stereoscopic microscope and an SEM, and the formation state was evaluated. The results are shown in Table 8. Further, after the barrier rib-forming resin composition element (i) obtained in Example 1 was stored at 5 ° C. for 7 days, the same operation as the above-mentioned “barrier rib formation” was performed to obtain the barrier rib-forming resin composition. The layers were embedded in the gaps of the relief pattern. The cross section of the obtained sample was examined by a stereoscopic microscope and SEM.
The results were shown in Table 8 by observing the resin composition for barrier rib formation in the gaps between the relief patterns.

Example 5 In Example 4, the barrier rib-forming resin composition element (i) obtained in Example 1 was replaced with the barrier rib-forming resin composition element (ii) obtained in Example 2. Except for the above, a pattern composed of the barrier rib-forming resin composition was formed in the same manner as in Example 4, the embedding state of the barrier rib-forming resin composition in the gaps of the relief patterns was evaluated, and from the barrier rib-forming resin composition, The cross section of the pattern is visually observed with a stereoscopic microscope and a SEM to evaluate the state of formation, and further, the barrier rib-forming resin composition after storing the barrier rib-forming resin composition element (ii) at 5 ° C. for 7 days. The state of embedding the relief pattern of the composition in the gap was evaluated, and the results are shown in Table 8.

Example 6 In Example 4, the resin composition element (i) for forming a barrier rib obtained in Example 1 was replaced with the resin composition element (iii) for forming a barrier rib obtained in Example 3. Except for the above, a pattern composed of the barrier rib-forming resin composition was formed in the same manner as in Example 4, the embedding state of the barrier rib-forming resin composition in the gaps of the relief patterns was evaluated, and from the barrier rib-forming resin composition, The cross section of the pattern is visually observed with a stereoscopic microscope and a SEM to evaluate the formation thereof, and further, the barrier rib-forming resin composition (iii) is stored at 5 ° C. for 7 days. The state of embedding the relief pattern of the composition in the gap was evaluated, and the results are shown in Table 8.

Comparative Example 3 In Example 4, the resin composition element for barrier rib formation (i) obtained in Example 1 was replaced with the resin composition element for barrier rib formation (iv) obtained in Comparative Example 1. Except for the above, a pattern composed of the barrier rib-forming resin composition was formed in the same manner as in Example 4, the embedding state of the barrier rib-forming resin composition in the gaps of the relief patterns was evaluated, and from the barrier rib-forming resin composition, The cross section of the resulting pattern was visually observed with a stereoscopic microscope and SEM to evaluate the formation thereof, and the results are shown in Table 8.

Comparative Example 4 In Example 4, the barrier rib-forming resin composition element (i) obtained in Example 1 was replaced with the barrier rib-forming resin composition element (v) obtained in Comparative Example 1. Except for the above, a pattern composed of the barrier rib-forming resin composition was formed in the same manner as in Example 4, the embedding state of the barrier rib-forming resin composition in the gaps of the relief patterns was evaluated, and from the barrier rib-forming resin composition, The cross-section of the pattern is visually observed with a stereoscopic microscope and a SEM to evaluate the formation thereof, and further, the barrier rib-forming resin composition (v) is stored at 5 ° C. for 7 days. The state of embedding the relief pattern of the composition in the gap was evaluated, and the results are shown in Table 8.

[0074]

[Table 8]

From Table 8, it can be seen that (A) the binder polymer and (B)
Examples 4 to 6 using a barrier rib-forming resin composition element composed of an organic silicon compound, (C) an organic material containing a compound having a carboxyl group, and (D) an inorganic material for a barrier rib, The embedding property of the object into the relief pattern gap is good, and
The relief pattern can be removed and removed satisfactorily, a pattern composed of the resin composition for forming a barrier rib can be satisfactorily formed.
, The embedding property of the resin composition for forming a barrier rib into the relief pattern gap was good, and the storage stability was excellent. Examples 4 to
When the pattern made of the resin composition for forming a barrier rib obtained in 6 was fired, a high-quality barrier rib having excellent pattern accuracy corresponding to the pattern shape before firing was obtained.

On the other hand, in Comparative Example 3 using the barrier rib-forming resin composition element containing no organosilicon compound and no compound having a carboxyl group, a pattern comprising the barrier rib-forming resin composition could not be formed favorably. Comparative Example 4 using a resin composition element for forming a barrier rib containing no compound having a carboxyl group,
The barrier rib-forming resin composition element is heated at 5 ° C.
The embedding property of the barrier rib forming resin composition into the relief pattern gap after storage for one day was poor, and it was found that this barrier rib forming resin composition element had poor storage stability.

[0077]

According to the first aspect of the present invention, the resin composition for forming a barrier rib is excellent in barrier rib forming property and storage stability of a plasma display panel. The barrier rib-forming resin composition element according to the second aspect is excellent in workability in addition to the effect of the first aspect. According to the third aspect of the present invention, a barrier rib manufacturing process of a plasma display panel can be shortened, and a barrier rib having an excellent shape can be formed.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroyuki Kawakami 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. (72) Inventor Mariko Shimamura 4-13 Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. Research Laboratory (72) Inventor Seiji Tai 1-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Research Laboratory (72) Inventor Yoshiyuki Horibe Higashicho, Hitachi City, Ibaraki Prefecture 4-13-1, Hitachi Chemical Co., Ltd., Yamazaki Office

Claims (3)

[Claims] 1. A barrier rib forming resin composition comprising (A) a binder polymer, (B) an organic material containing an organosilicon compound and (C) a compound having a carboxyl group, and (D) an inorganic material. 2. A barrier rib-forming resin composition element comprising the barrier rib-forming resin composition layer according to claim 1 on a support film. 3. The barrier rib-forming resin composition element according to claim 2 is disposed on a substrate provided with a removable relief pattern such that the barrier rib-forming resin composition layer faces the substrate side. After applying pressure to the barrier rib forming resin composition layer, on the substrate provided with the relief pattern, after laminating the barrier rib forming resin composition layer and embedding the barrier rib forming resin composition in the gaps of the relief pattern, A method for producing a barrier rib, comprising removing a relief pattern to form a pattern comprising a resin composition for forming a barrier rib, and firing the pattern.