JP2010159370A - Composition containing inorganic particle, method for forming inorganic layer using the same, and plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition containing inorganic particles which is capable of forming a desired inorganic material or inorganic layer at an energy lower than the conventional one as well as which is capable of decreasing the adverse effect resulting from an organic compound and does not greatly change the viscosity of the composition due to an added solvent amount and thus is profitable for workability and cost; a method for forming an inorganic layer using the same; and a plasma display panel. <P>SOLUTION: This composition containing inorganic particles includes (A) an organic compound expressed by general formula (1) (wherein R is a 1-10C alkylene group; (n+m) is an integer of 1-3; and when two or more Rs are present in the same molecule, Rs are each the same or different), (B) an organic solvent and (C) inorganic particles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an inorganic particle-containing composition, a method for forming an inorganic layer using the composition, and a plasma display panel.

As one of flat panel displays, there is known a plasma display panel (hereinafter referred to as PDP) that enables multicolor display by providing a phosphor layer that emits light by plasma discharge. In a PDP, a flat plate-like front plate and a back plate made of glass are arranged in parallel and opposite to each other, and both are held at a constant interval by a barrier rib provided between the front plate, the back plate, It is structured to discharge in a space surrounded by barrier ribs. In such a space, electrodes for display, a dielectric layer, a phosphor layer, and the like are attached, and the phosphor is caused to emit light by ultraviolet rays generated from the sealed gas by discharge, so that the observer can visually recognize this light. It has become.
By the way, the above-mentioned electrodes, dielectric layers, and phosphor layers are conventionally produced as follows. First, as a material for electrodes, dielectrics or phosphors, a slurry liquid in which metal or metal oxide particles, glass particles such as glass frit for dielectrics or phosphor particles are dispersed in a mixture of an organic polymer binder and a solvent. Alternatively, each paste is prepared and applied onto a glass substrate by an application method such as screen printing or die coating, and then the organic material such as a resin component is removed by firing the coating film to remove the electrode, dielectric layer or fluorescent material. A body layer is formed (see, for example, Patent Document 1).
In addition, binder compositions suitable for the production of electrodes, dielectric layers or phosphor layers of plasma display panels, which have an appropriate viscosity for application and can disappear organic substances at a relatively low temperature, have been studied. (For example, refer to Patent Document 2).

JP 11-349349 A JP 2007-217603 A

However, the organic polymer binder used in the method of Patent Document 1 is effective for forming a good coating film, but has the following problems. That is, in order to decompose the organic polymer binder, it is necessary to increase the temperature in an electric furnace or the like, and a great deal of energy is required. In addition, when an organic polymer binder is used, there is a problem that decomposition products accumulate on the walls in the electric furnace. Furthermore, if the organic polymer binder remains as it carbonizes during decomposition, bubbles and blisters may occur, or it may gradually evaporate during discharge and adversely affect discharge characteristics. .
In addition, in the inorganic fine particle-containing composition described in Patent Document 2, it is necessary to strictly adjust the ratio of the organic compound and the organic solvent when preparing the inorganic fine particle-containing composition in order to obtain a desired viscosity. The reason why it is necessary to strictly adjust the ratio of the raw materials at the time of preparing the composition is the organic compound selected in the above-mentioned Patent Document 1, wherein the heating residue at 300 ° C. is 0 to 1% and can achieve the desired viscosity However, it is presumed that it is sensitive to the addition ratio of the diluting solvent, and the difference in the solvent addition amount greatly affects the viscosity of the finally obtained composition. Thus, strictly controlling the addition ratio of the diluent solvent tends to complicate operations such as weighing in the production of the composition, and is likely to lead to an increase in production cost.
The present invention has been made in view of the above circumstances, and it is possible to form a desired inorganic body or inorganic layer with lower energy than before, and to reduce adverse effects caused by organic compounds. An object of the present invention is to provide an inorganic particle-containing composition that is advantageous in workability and cost without greatly changing the viscosity of the composition. Another object of the present invention is to provide a method for forming an inorganic layer using such an inorganic particle-containing composition, and a plasma display including the inorganic layer formed by the method for forming an inorganic layer.

  The first inorganic particle-containing composition of the present invention that solves the above problems includes: [1] (A) an organic compound represented by the following general formula (1), (B) an organic solvent, (C) inorganic particles, And an inorganic particle-containing composition.

（一般式（１）中、Ｒは炭素数１〜１０アルキレン基を示し、ｎ＋ｍは１〜３の整数を示し、同一分子中にＲが２以上存在する場合、それぞれのＲは同一でも異なっていても良い。）
本発明の無機粒子含有組成物によれば、上記構成を有することにより、良好な塗膜を形成できるとともに、トリシクロデカン骨格を有する上記有機化合物（Ａ）が比較的低温で除去可能であることから、塗膜を焼成するに際して有機化合物の含有量を従来よりも小さくすることができる。よって、本発明の無機粒子含有組成物によれば、従来よりも低エネルギーで所望の無機体或いは無機物層を形成でき、且つ、有機化合物に起因する悪影響を低減することが可能となる。また、電気炉内の壁に堆積する分解生成物の量を低減することも可能となる。
また、本発明は、［２］前記一般式（１）で表わされる有機化合物の含有量が、前記無機粒子含有組成物中に含まれる有機化合物全量に対して５０〜９５質量％であることを特徴とする。
本発明の無機粒子含有組成物は、プラズマディスプレイパネルの電極、誘電体層又は蛍光体層を形成するために用いられることが好ましい。
また、本発明は、［３］基板上に上記［１］又は［２］に記載の無機粒子含有組成物を塗工して無機粒子含有組成物層を設ける工程と、前記無機粒子含有組成物層を加熱する工程と、を備える無機物層の形成方法を提供する。
本発明の無機物層の形成方法によれば、無機粒子含有組成物を用いることにより、基板上に所望の無機物層を低エネルギーで形成することができる。また、本発明の無機物層の形成方法によれば、有機化合物に起因する悪影響が十分低減された無機物層を形成することが可能となる。
また、本発明は、［４］本発明の無機物層の形成方法においては、上記［３］に記載の基板が、プラズマディスプレイ用基板であり、上記無機粒子がガラス粒子であり、上記無機物層としてプラズマディスプレイ用誘電体層を形成することができる。
また、本発明は、［５］本発明の無機物層の形成方法においては、上記［３］に記載の基板が、プラズマディスプレイ用基板であり、上記無機粒子が蛍光体粒子であり、上記無機物層としてプラズマディスプレイ用蛍光体層を形成することができる。
本発明は、また、［６］上記［４］に記載の本発明の無機物層の形成方法により形成されたプラズマディスプレイ用誘電体層、又は、上記［５］に記載の本発明の無機物層の形成方法により形成されたプラズマディスプレイ用蛍光体層を備えるプラズマディスプレイを提供する。
また、本発明は、基板上に、無機粒子としてガラス粒子を含有する無機粒子含有組成物から形成される無機粒子含有組成物層を設ける工程と、無機粒子含有組成物層を焼成する工程とを備える無機層の形成方法により形成された誘電体層を提供できる。
また、本発明は、基板上に、無機粒子として金属粒子又は金属酸化物粒子を含有する無機粒子含有組成物から形成される無機粒子含有組成物層を設ける工程と、無機粒子含有組成物層を焼成する工程とを備える無機層の形成方法により形成された電極を提供できる。
また、本発明は、プラズマディスプレイパネル用背面基板上に、無機粒子として蛍光体粒子を含有する無機粒子含有組成物から形成される無機粒子含有組成物層を設ける工程と、無機粒子含有組成物層を焼成する工程とを備える無機層の形成方法により形成された蛍光体層を提供できる。
また、本発明は、本発明を用いた電極、誘電体層又は蛍光体層を備えるプラズマディスプレイパネルを提供する。

(In the general formula (1), R represents an alkylene group having 1 to 10 carbon atoms, n + m represents an integer of 1 to 3, and when two or more R exist in the same molecule, each R is the same or different. May be.)
According to the inorganic particle-containing composition of the present invention, by having the above-described configuration, a good coating film can be formed, and the organic compound (A) having a tricyclodecane skeleton can be removed at a relatively low temperature. Therefore, the content of the organic compound can be made smaller than before when the coating film is baked. Therefore, according to the inorganic particle-containing composition of the present invention, a desired inorganic body or inorganic layer can be formed with lower energy than before, and adverse effects caused by organic compounds can be reduced. It is also possible to reduce the amount of decomposition products deposited on the walls in the electric furnace.
Moreover, this invention is [2] Content of the organic compound represented by the said General formula (1) is 50-95 mass% with respect to the organic compound whole quantity contained in the said inorganic particle containing composition. Features.
The inorganic particle-containing composition of the present invention is preferably used for forming an electrode, a dielectric layer or a phosphor layer of a plasma display panel.
The present invention also provides [3] a step of coating the inorganic particle-containing composition according to [1] or [2] on a substrate to provide an inorganic particle-containing composition layer, and the inorganic particle-containing composition. And a step of heating the layer.
According to the method for forming an inorganic layer of the present invention, a desired inorganic layer can be formed on a substrate with low energy by using an inorganic particle-containing composition. In addition, according to the method for forming an inorganic layer of the present invention, it is possible to form an inorganic layer in which adverse effects caused by organic compounds are sufficiently reduced.
Moreover, this invention is [4] In the formation method of the inorganic substance layer of this invention, the board | substrate of said [3] is a board | substrate for plasma displays, The said inorganic particle is glass particle, As said inorganic substance layer A dielectric layer for a plasma display can be formed.
The present invention also provides [5] In the method for forming an inorganic layer according to the present invention, the substrate according to the above [3] is a substrate for plasma display, the inorganic particles are phosphor particles, and the inorganic layer. A phosphor layer for plasma display can be formed.
The present invention also provides [6] the dielectric layer for plasma display formed by the method for forming an inorganic layer of the present invention described in [4], or the inorganic layer of the present invention described in [5]. Provided is a plasma display including a phosphor layer for plasma display formed by the forming method.
The present invention also includes a step of providing an inorganic particle-containing composition layer formed from an inorganic particle-containing composition containing glass particles as inorganic particles on a substrate, and a step of firing the inorganic particle-containing composition layer. The dielectric layer formed by the formation method of the inorganic layer provided can be provided.
The present invention also includes a step of providing an inorganic particle-containing composition layer formed from an inorganic particle-containing composition containing metal particles or metal oxide particles as inorganic particles on a substrate, and an inorganic particle-containing composition layer. The electrode formed by the formation method of an inorganic layer provided with the process to bake can be provided.
The present invention also provides a step of providing an inorganic particle-containing composition layer formed from an inorganic particle-containing composition containing phosphor particles as inorganic particles on a back substrate for a plasma display panel, and an inorganic particle-containing composition layer The phosphor layer formed by the formation method of an inorganic layer provided with the process of baking can be provided.
The present invention also provides a plasma display panel comprising an electrode, dielectric layer or phosphor layer using the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the inorganic particle containing composition which can reduce the bad influence resulting from an organic compound while being able to form a desired inorganic body or an inorganic substance layer with lower energy than before can be provided. Moreover, according to this invention, the plasma display provided with the formation method of the inorganic substance layer using the inorganic particle containing composition of this invention, and the inorganic substance layer formed by the formation method of the inorganic substance layer of this invention can be provided. . In addition, according to the present invention, by using the inorganic particle-containing composition of the present invention, electrodes, dielectric layers and phosphors that can be formed with lower energy than before, and these electrodes, dielectric layers or phosphors can be formed. A plasma display comprising a body can be provided.

It is a schematic cross section for explaining one embodiment of a method for forming a dielectric layer according to the present invention. It is a schematic cross section for explaining one embodiment of a method for forming a phosphor layer according to the present invention. It is principal part sectional drawing which shows the plasma display panel of this invention. It is a figure which shows the relationship between the viscosity of the mixture which mixed bishydroxymethyl tricyclodecane (it abbreviated as DCPD below) and the organic solvent (B), and the addition amount of the organic solvent (B).

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

<Inorganic particle-containing composition>
The inorganic particle-containing composition according to the embodiment of the present invention includes (A) an organic compound represented by the following general formula (1), (B) an organic solvent, and (C) inorganic particles.

（一般式（１）中、Ｒは炭素数１〜１０アルキレン基を示し、ｎ＋ｍは１〜３の整数を示し、同一分子中にＲが２以上存在する場合、それぞれのＲは同一でも異なっていても良い。）
上記一般式（１）で表わされる化合物としては、ｍ＝１、及びｎ＝１のものがアルドリッチ社から商業的に入手可能である。
また、上記一般式（１）で表わされる有機化合物（Ａ）は、３００℃で１０分間加熱したときの加熱残分が１質量％以下であるものが好ましい。なお、加熱環境は、大気中である。このような有機化合物（Ａ）を用いた場合、焼成して得られる無機体において、有機化合物に起因する悪影響を更に低減することができる。
本実施形態の無機粒子含有組成物における有機化合物（Ａ）の含有量は、無機粒子含有組成物全量を基準として２０〜９５質量％が好ましく、３０〜９０質量％がより好ましく、４０〜９０質量％が更により好ましく、４０〜６０質量％が最も好ましい。有機化合物（Ａ）の含有量を上記範囲内とすることにより、範囲外の場合に比べて均一な塗膜を形成しやすくなるという効果が得られやすくなる。
また、本実施形態の無機粒子含有組成物における有機化合物（Ａ）の含有量は、無機粒子含有組成物中に含まれる有機化合物全量を基準として５０〜９５質量であるが、５５〜９５質量％が好ましく、６０〜９０質量％がより好ましく、７０〜９０質量％が特に好ましい。有機化合物（Ａ）の含有量を上記範囲内とすることにより、範囲外の場合に比べて均一な塗膜を形成しやすくなるという効果が得られやすくなる。

(In the general formula (1), R represents an alkylene group having 1 to 10 carbon atoms, n + m represents an integer of 1 to 3, and when two or more R exist in the same molecule, each R is the same or different. May be.)
As the compound represented by the general formula (1), those having m = 1 and n = 1 are commercially available from Aldrich.
The organic compound (A) represented by the general formula (1) preferably has a heating residue of 1% by mass or less when heated at 300 ° C. for 10 minutes. The heating environment is in the atmosphere. When such an organic compound (A) is used, an adverse effect caused by the organic compound can be further reduced in the inorganic body obtained by firing.
The content of the organic compound (A) in the inorganic particle-containing composition of the present embodiment is preferably 20 to 95 mass%, more preferably 30 to 90 mass%, and more preferably 40 to 90 mass% based on the total amount of the inorganic particle-containing composition. % Is even more preferred, with 40-60% by weight being most preferred. By making content of an organic compound (A) into the said range, it becomes easy to acquire the effect that it becomes easy to form a uniform coating film compared with the case outside a range.
In addition, the content of the organic compound (A) in the inorganic particle-containing composition of the present embodiment is 50 to 95 mass% based on the total amount of the organic compound contained in the inorganic particle-containing composition, but is 55 to 95 mass%. Is preferable, 60 to 90 mass% is more preferable, and 70 to 90 mass% is particularly preferable. By making content of an organic compound (A) into the said range, it becomes easy to acquire the effect that it becomes easy to form a uniform coating film compared with the case outside a range.

The inorganic particles may be appropriately selected according to the use of the inorganic body or inorganic layer to be formed, and examples thereof include metal particles, metal oxide particles, glass particles, and phosphor particles. Examples of the metal particles include gold powder and silver powder. Moreover, you may add the glass particle mentioned later as a binder to these particle | grains. Examples of the metal oxide particles include ruthenium oxide, copper oxide, tin oxide, ITO, and the like, and glass particles described later as a binder may be added to these particles.
0.01-20 micrometers is preferable and, as for the average particle diameter of a metal particle and a metal oxide particle, 0.1-10 micrometers is more preferable.

  The glass particles preferably have a low melting point, and preferably have a softening point in the range of 300 to 600 ° C. When the softening point of the glass particles is less than 300 ° C., the glass particles are melted at a stage where the organic compound (A) is not completely removed, and the organic matter remains, thereby causing problems such as coloring. On the other hand, when the softening point exceeds 600 ° C., the glass substrate tends to be distorted.

As the glass particles, for example, lead oxide, boron oxide, silicon oxide _{(PbO-B 2 O 3 -SiO} 2 system), lead oxide, boron oxide, silicon oxide, aluminum oxide-based _(PbO-B 2 O 3 -SiO _2- Al ₂ O ₃ system), zinc oxide, boron oxide, silicon oxide system (ZnO—B ₂ O ₃ —SiO ₂ system), zinc oxide, boron oxide, silicon oxide, aluminum oxide system (ZnO—B ₂ O ₃₎ -SiO ₂ -Al ₂ O ₃ system), lead oxide, zinc oxide, boron oxide, silicon oxide _{(PbO-ZnO-B 2 O} 3 -SiO 2 system), lead oxide, zinc oxide, boron oxide, silicon oxide, based on aluminum oxide _{(PbO-ZnO-B 2 O} 3 -SiO 2 -Al 2 O 3 system), bismuth oxide, boron oxide, silicon oxide _{(Bi 2 O 3 -B 2 O} 3 -SiO 2 system), acid Bismuth, boron oxide, silicon oxide, aluminum oxide-based _{(Bi 2 O 3 -B 2 O} 3 -SiO 2 -Al 2 O 3 system), bismuth oxide, zinc oxide, boron oxide, silicon oxide _(Bi 2 _{O 3} - ZnO—B ₂ O ₃ —SiO ₂ system), bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide system (Bi ₂ O ₃ —ZnO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system), etc. Glass particles. These may be used alone or in combination of two or more.
The average particle size of the glass particles is preferably from 0.01 to 20 μm, more preferably from 0.1 to 10 μm.

Examples of the phosphor particles include phosphors mainly composed of metal oxides. Examples of red-colored phosphors include Y ₂ O ₂ S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ O. ₃ : Eu, YVO ₄ : Eu, (Y, Gd) BO ₃ : Eu, and the like. Examples of blue-colored phosphors include ZnS: Ag, ZnS: Ag, Al, ZnS: Ag, Ga, Al, ZnS: Ag, Cu, Ga, Cl, ZnS: Ag ⁺ In ₂ O ₃ , and Ca ₂ B. ₅ O ₉ Cl: Eu ²⁺ , (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgAl ₁₆ O ₂₆ : Eu ^{2+ and the} like. Examples of green phosphors include ZnS: Cu, Zn ₂ SiO ₄ : Mn, ZnS: Cu ⁺ Zn ₂ SiO ₄ : Mn, Gd ₂ O ₂ S: Tb, Y ₃ Al ₅ O ₁₂ : Ce, ZnS. ^{_{: Cu, Al, Y 2 O}} 2 S: Tb, ZnO: Zn, ZnS: Cu, Al + In 2 O 3, LaPO 4: Ce, Tb, BaO · 6Al 2 O 3: Mn , and the like.

The average particle diameter of the phosphor particles is preferably 0.01 to 20 μm, and more preferably 0.1 to 10 μm.
When the inorganic particle-containing composition of the present embodiment contains metal particles or metal oxide particles as inorganic particles, the inorganic particle-containing composition is suitable for forming an electrode. In addition, when glass particles are included, such an inorganic particle-containing composition is suitable for forming a dielectric layer. When the phosphor particles are included, the inorganic particle-containing composition is suitable for forming a phosphor layer.

The content of the inorganic particles in the inorganic particle-containing composition of the present embodiment is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total amount of the composition, from the viewpoint of improving the coatability to the substrate. 10-60 mass% is still more preferable, and 30-50 mass% is the most preferable.
The organic solvent (B) used in the inorganic particle-containing composition of the present embodiment preferably contains an organic solvent having a boiling point in the range of 150 to 250 ° C. in terms of the flatness of the coating film. In the present specification, the boiling point of the solvent indicates a value under atmospheric pressure.
Examples of the solvent having a boiling point in the range of 150 to 250 ° C. include ketone solvents such as holon (boiling point: 198 ° C.), cyclohexanone (boiling point: 155 ° C.), methylcyclohexanone (boiling point: 170 ° C.), methyl phenyl ether ( Boiling point: 153 ° C), ethyl phenyl ether (172 ° C), methoxytoluene (boiling point: 172 ° C), benzyl ethyl ether (boiling point: 189 ° C), diethylene glycol dimethyl ether (boiling point: 160 ° C), diethylene glycol diethyl ether (boiling point: 188 ° C) ), Diethylene glycol monomethyl ether (boiling point: 194 ° C.), diethylene glycol monobutyl ether (boiling point: 231 ° C.), diethylene glycol monobutyl ether acetate (boiling point: 247 ° C.), ethylene glycol monobutyl ether ( Point: 171 ° C), ether solvents such as ethylene glycol monoisoamyl ether (boiling point: 181 ° C), butyl carbitol (boiling point: 231 ° C), 1-hexanol (boiling point: 157 ° C), 1-heptanol (boiling point: 176) ° C), 2-heptanol (boiling point: 160 ° C), 3-heptanol (boiling point: 156 ° C), 1-octanol (boiling point: 195 ° C), 2-octanol (boiling point: 179 ° C), 2-ethyl-1-hexanol (Boiling point: 184 ° C), cyclohexanol (boiling point: 161 ° C), 1-methylcyclohexanol (boiling point: 155 ° C), 2-methylcyclohexanol (boiling point: 165 ° C), 3-methylcyclohexanol (boiling point: 173 ° C) ), 4-methylcyclohexanol (boiling point: 174 ° C.), furfuryl alcohol (boiling point: 170 ° C.) Benzyl alcohol ((boiling point: 205 ° C), ethylene glycol (boiling point: 198 ° C), propylene glycol (boiling point: 187 ° C), 1,2-butylene glycol (boiling point: 191 ° C), hexylene glycol (boiling point: 197 ° C) Alcohol solvents such as 3-methyl-3-methoxybutanol (boiling point: 174 ° C.), butylpropylene diglycol (boiling point: 231 ° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point: 188 ° C.) , Acetate solvents such as ethylene glycol monoacetate (boiling point: 182 ° C.), diethylene glycol monobutyl ether acetate (boiling point: 247 ° C.), cyclic carbonate solvents such as propylene carbonate (boiling point: 241 ° C.), γ-butyrolactone (boiling point: 204) Lactone) solvent, N-methyl Pyrrolidone solvents such as 2-pyrrolidone (boiling point: 202 ° C), α-pinene (boiling point: 156 ° C), β-pinene (boiling point: 161 ° C), limonene (boiling point: 177 ° C), terpineol (boiling point: 217 ° C) Terpene solvents such as dihydroterpineol (boiling point: 207 ° C.) and dihydroterpinyl acetate (boiling point: 220 ° C.), dimethylformamide (boiling point: 153 ° C.), dimethyl sulfoxide (boiling point: 189 ° C.) and the like. These can be used alone or in combination of two or more.
Among these, a compound having an alicyclic group and a hydroxyl group or an ester group such as cyclohexanol, terpineol, dihydroterpineol, dihydroterpinel acetate is preferable, terpene alcohol such as terpineol, dihydroterpineol, dihydroterpinel acetate or the like It is more preferable to contain a tenlpenic solvent such as a terpene ester. Thereby, when the inorganic particle-containing composition of the present invention applied on the substrate is dried, unevenness such as film thickness variations caused by the temperature distribution on the substrate surface can be more reliably reduced. .

  Turpineol is an isomer mixture of α-, β-, and γ-terpineol derived from gum turpentine oil represented by the following formula, and “Terpineol C” (trade name, manufactured by Nippon Terpene Chemical Co., Ltd.) is commercially available. It is available.

ジヒドロターピネオールは、下記式で示される、ガムテレビン油から誘導されるターピネオールに水素添加した化合物であり、日本テルペン化学株式会社より商業的に入手可能である。

Dihydroterpineol is a compound obtained by hydrogenation of terpineol derived from gum turpentine oil represented by the following formula, and is commercially available from Nippon Terpene Chemical Co., Ltd.

ジヒドロターピニルアセテートは、下記式で示される、ガムテレビン油から誘導されるターピネオールに水素添加及びエステル化した化合物であり、日本テルペン化学株式会社より商業的に入手可能である。

Dihydroterpinyl acetate is a compound obtained by hydrogenation and esterification of terpineol derived from gum turpentine oil represented by the following formula, and is commercially available from Nippon Terpene Chemical Co., Ltd.

  From the viewpoint of preventing unevenness in the coating film after drying, the content of the organic solvent having a boiling point in the range of 150 to 250 ° C. in the inorganic particle-containing composition of the present invention is an organic compound contained in the composition. It is preferable that it is 3-48 mass% with respect to whole quantity (an organic compound (A) is included), it is more preferable that it is 3-43 mass%, it is especially preferable that it is 3-38 mass%, 8- Most preferably, it is 28 mass%.

Moreover, in the inorganic particle containing composition of this embodiment, you may contain the organic solvent whose boiling point is 50 degreeC or more and less than 150 degreeC in order to control the drying property of a coating film.
Examples of organic solvents having a boiling point of 50 ° C. or higher and lower than 150 ° C. include alcohol organic solvents (methanol (boiling point: 64.7 ° C.), ethanol (boiling point: 78 ° C.), isopropyl alcohol (boiling point: 82.4 ° C.)). N-butyl alcohol (boiling point: 117 ° C), aromatic organic solvents (benzene (boiling point: 80.1 ° C), toluene (boiling point: 110.6 ° C), xylene (boiling point: 144 ° C), etc.), Ketone solvents (acetone (boiling point: 56.5 ° C.), methyl ethyl ketone (boiling point: 79.5 ° C.), methyl isobutyl ketone (boiling point: 116.2 ° C.)), ether solvents (tetrahydrofuran (boiling point: 66 ° C.)), Dioxane (boiling point: 101.1 ° C), ethylene glycol monomethyl ether (boiling point: 124.5 ° C), ethylene glycol monoethyl ether (boiling point: 1 5 ° C.)), ethyl acetate (boiling point: 77.1 ° C.), cyclohexane (boiling point: 81 ° C.), and the like.

The content of the organic solvent in the inorganic particle-containing composition of the present embodiment is not particularly limited, but is set so that the viscosity at 25 ° C. of the mixture when mixed with the organic compound (A) is 500 to 50000 mPa · s. Is preferably set to 1000 to 25000 mPa · s, more preferably set to 1000 to 10000 mPa · s, and the viscosity of the inorganic particle-containing composition is within a range described below. It is preferable to set so that
For example, in an inorganic particle-containing composition comprising an organic compound having a tricyclodecane skeleton represented by the general formula (1) as an organic compound (A) and inorganic particles, it is difficult to adjust the viscosity to be coatable. is there. Therefore, it is preferable to adjust the viscosity using the organic solvent (B). However, the organic solvent (B) having a large decrease in viscosity and a large decrease in viscosity has a large change in viscosity due to a slight difference in addition amount. It is not preferable because it must be strictly controlled. From the viewpoint of ease of viscosity control, when adjusting the viscosity of the inorganic particle-containing composition by blending the organic solvent (B), select the one that decreases the viscosity decrease and the viscosity decrease rate even if the addition amount is increased. It is preferable to do.

FIG. 4 shows the viscosity at 25 ° C. of the mixture of bishydroxymethyltricyclodecane (DCPD) as the organic compound (A) and the organic solvent (B), and the amount of the organic solvent (B) added. It is a figure which shows a relationship. Here, the addition amount of the organic solvent (B) on the X axis indicates mass% of the organic solvent (B) in the mixture of DCPD and the organic solvent (B). In FIG. 4, TPO is terpineol (boiling point: 217 ° C.), BC is an organic solvent (B) of butyl carbitol (boiling point: 231 ° C.), and MTPH is isobornylcyclohexanol (Nippon Terpene Chemical). This is an organic compound for comparison with DCPD.
In a mixed system of MTPH and an organic solvent (B) that is TPO or BC, the rate of decrease in viscosity accompanying the increase in the amount of organic solvent (B) added (the slope of the graph in FIG. 4) is large. On the other hand, in the mixed system of DCPD and the organic solvent (B) which is TPO or BC, the rate of decrease in viscosity due to the increase in the amount of organic solvent (B) added is small.
From such a tendency, it is preferable to use an organic compound (A) having a tricyclodecane skeleton such as DCPD from the viewpoint of easy viscosity control. In addition, in this embodiment, it is also possible to aim at coexistence with the ease of viscosity control and the drying property control of a coating film by combining multiple types of organic solvent (B).
When the inorganic particle-containing composition of the present embodiment contains one or more organic solvents selected from the group consisting of the organic solvent (B), the content of the organic solvent is the total amount of organic compounds contained in the composition. It is preferable that it is 3-30 mass% with respect to.
In the inorganic particle-containing composition of the present embodiment, the viscosity at 25 ° C. is preferably 1000 to 100,000 mPa · s, more preferably 2000 to 60000 mPa · s, and particularly preferably 2500 to 50000 mPa · s. . When the viscosity of the inorganic particle-containing composition is less than 1000 mPa · s, the inorganic particles tend to settle during storage of the inorganic particle-containing composition, while when the viscosity is greater than 100,000 mPa · s, the flatness of the coating film Tends to decrease.

Moreover, it is preferable that the heating residue when the organic compound contained in the inorganic particle containing composition of this embodiment is heated at 300 degreeC for 10 minutes is 1 mass% or less.
The inorganic particle-containing composition of the present embodiment is necessary if the heating residue of the organic compound contained in the inorganic particle-containing composition when heated at 300 ° C. for 10 minutes is within a range of 1% by mass or less. Depending on the conditions, for example, organic binder resins, dyes, color formers, plasticizers, pigments, polymerization inhibitors, surface modifiers, stabilizers, adhesion promoters, thermosetting agents, and the like can be added.
However, when an organic binder resin having a weight average molecular weight of 5000 to 1000000 is added, the heating residue when heated at 300 ° C. for 10 minutes of the organic compound contained in the inorganic particle-containing composition is 1% by mass or less. It is difficult. Therefore, when an organic binder resin having a weight average molecular weight of 5,000 to 1,000,000 is added, the content is preferably 0 to 1% by mass based on the total amount of organic compounds contained in the inorganic particle-containing composition, The content is more preferably 0 to 0.5% by mass, and particularly preferably 0% by mass (that is, not added).

  The inorganic particle-containing composition of the present embodiment is prepared, for example, by mixing the organic compound (A) with the organic solvent (B), then adding the inorganic particles, and mixing them by a known mixing means. can do.

<Method for forming dielectric layer and phosphor layer, dielectric layer and phosphor layer, and plasma display panel (PDP)>
Next, as a specific example of the method for forming an inorganic layer of the present invention, a preferred embodiment of a method for forming a dielectric layer and a phosphor layer will be described. The method for forming a dielectric layer according to the present embodiment includes a step of providing an inorganic particle-containing composition layer formed from the above-described inorganic particle-containing composition of the present invention containing glass particles as inorganic particles on a substrate, And a step of heating the composition layer. Hereinafter, an embodiment in which a dielectric layer is formed on a front glass substrate constituting a front substrate for PDP will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view for explaining a dielectric layer forming method of the present embodiment.
As shown in FIG. 1A, a front glass substrate 40 provided with display electrodes 52 is prepared.
Next, as shown in FIG.1 (b), the inorganic particle containing composition of this invention is apply | coated and dried on the side in which the display electrode 52 of the front glass substrate 40 is provided, and the inorganic particle containing composition layer 1 is dried. Form. In this embodiment, it is preferable to use the inorganic particle-containing composition containing the low melting point glass particles described above as the inorganic particles. In this case, the inorganic particle-containing composition layer 1 is a glass-containing composition layer.

Examples of the coating method include screen printing, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, die coating method, and curtain coating method.
Although there is no restriction | limiting in particular as drying temperature, 60 to 350 degreeC is preferable, 100 to 350 degreeC is more preferable, and 150 to 300 degreeC is especially preferable. The drying time is preferably about 1 minute to 2 hours, and preferably about 1 minute to 1 hour. In this heat drying step, the organic compound is preferably removed by 90% by mass or more, more preferably by 95% by mass or more, and particularly preferably by 99% by mass or more. In the drying step, the oxygen concentration in the heating atmosphere is preferably 10% by volume or less, more preferably 0 to 5% by volume, from the viewpoint of suppressing the reduction of organic compound residues and the discoloration of the inorganic particles. It is especially preferable to set it as -3 volume%. The oxygen concentration in the heating device is about 20% by volume equivalent to the oxygen concentration in the air in the natural state. Examples of means for reducing the oxygen concentration to 10% by volume or less include replacing the inside of the heating device with an inert gas such as nitrogen or argon, helium, or neon, using a vacuum pump, and the like. A value as low as possible is preferred. The measurement of the oxygen concentration can be easily performed with an oxygen concentration meter, and examples of a commercially available oxygen concentration meter include an oxygen concentration meter LC-750L (manufactured by Toray Engineering Co., Ltd.).

Next, the inorganic particle-containing composition layer 1 provided on the front glass substrate 40 is fired to obtain a dielectric layer 70 that is a sintered body (see FIG. 1C). Examples of the firing method include a method in which a laminate of the substrate and the inorganic particle-containing composition layer is accommodated in an electric furnace and heated, a method in which the laminate is placed on a hot plate and heated. Can be mentioned.
The firing temperature is not particularly limited as long as the inorganic particle-containing composition layer is sufficiently sintered, but the maximum temperature is preferably 300 to 700 ° C, more preferably 300 to 600 ° C, It is especially preferable that it is 400 to 600 degreeC. The firing time is preferably about 5 minutes to 2 hours. Moreover, it is preferable that baking is implemented in air | atmosphere.
It is considered that the organic component in the inorganic particle-containing composition layer is volatilized through the above firing step, and a dielectric layer containing only the inorganic component is formed.
According to the method for forming a dielectric layer of the present embodiment, the inorganic particle-containing composition layer 1 is formed from the inorganic particle-containing composition of the present invention, and dried, whereby the inorganic particle-containing composition layer 1 is fired. Since the organic component contained in can be reduced as compared with the conventional case, the firing process can be completed with lower energy to form a good dielectric layer, and the deposition of decomposition products in an electric furnace or the like is sufficiently reduced. It becomes possible.
A laminate including a dielectric layer on a substrate obtained by the dielectric layer forming method of the present embodiment can be suitably used as a PDP front substrate (PDP substrate).

  Next, a preferred embodiment of the method for forming a phosphor layer according to the present invention will be described. The method for forming a phosphor layer according to this embodiment includes a step of providing an inorganic particle-containing composition layer formed from the above-described inorganic particle-containing composition of the present invention containing phosphor particles as inorganic particles on a substrate; And heating the composition layer. Hereinafter, an embodiment in which a phosphor layer is formed on a PDP rear glass substrate will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view for explaining the method for forming the phosphor layer of the present embodiment.

A rear glass substrate 41 provided with address electrodes 54 is prepared. Next, the rear dielectric layer 72 is formed on the side of the rear glass substrate 41 where the address electrodes 54 are provided. Barrier ribs 80 are formed on the formed dielectric layer 72 (see FIG. 2A).
The inorganic particle-containing composition according to the present invention containing phosphor particles as inorganic particles is applied to the gaps between adjacent barrier ribs 80 to form an inorganic particle-containing composition layer 1 ′ (see FIG. 2B).
Examples of the coating method include screen printing, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, die coating method, curtain coating method, dispenser coating method, and the like.
Next, the phosphor layer 90 as an inorganic layer is formed by drying and baking the inorganic particle-containing composition layer 1 ′ (see FIG. 2C).
The drying temperature is not particularly limited, but is preferably about 60 to 200 ° C., and the drying time is preferably about 1 minute to 1 hour.
Examples of the firing method include a method in which a laminated body of the back substrate and the inorganic particle-containing composition layer is accommodated in an electric furnace and heated, a method in which the laminated body is placed on a hot plate and heated, etc. Is mentioned.
The firing temperature is not particularly limited as long as the organic component in the inorganic particle-containing composition layer is completely removed, but the maximum temperature is preferably 300 to 700 ° C, and preferably 300 to 600 ° C. Is more preferable. The firing time is preferably about 5 minutes to 2 hours. Moreover, it is preferable that baking is implemented in air | atmosphere.

Moreover, in the formation method of the fluorescent substance layer of this embodiment, oxygen concentration is 10 volume% or less, Preferably it is 0-5 volume%, More preferably, it is 0-3 as drying conditions of inorganic particle content composition layer 1 '. By heating at 150 to 350 ° C., preferably 170 to 300 ° C., more preferably 200 to 280 ° C. in an atmosphere of volume%, almost all organic compounds can be removed. In this case, the firing step can be omitted, and a phosphor layer forming method with a simplified process can be realized.
In this embodiment, it is preferable to heat in an inert gas atmosphere. The heating temperature is preferably about 150 to 300 ° C., and the heating time is preferably about 1 minute to 1 hour. Specific conditions include, for example, a condition of heating at 250 ° C. for 30 minutes.
According to the method for forming the phosphor layer of the present embodiment, since the impurities derived from the organic compound contained in the inorganic particle-containing composition layer can be reduced when firing, the phosphor layer 90 due to the residual impurities derived from the organic compound. The performance degradation can be suppressed. In addition, according to the method for forming a phosphor layer of the present embodiment, the firing step can be omitted, and a method for forming a phosphor layer with a simplified process can be realized.
The laminate including the phosphor layer obtained by the phosphor layer forming method of the present embodiment can be suitably used as the PDP rear substrate (PDP substrate) 200.

Next, an embodiment of a PDP having a dielectric layer and a phosphor layer formed by the method of this embodiment will be described with reference to FIG.
FIG. 3 is a partial perspective view showing an embodiment of a PDP according to the present invention. A PDP 300 shown in FIG. 3 is mainly composed of a PDP front substrate 100 and a PDP rear substrate 200. The front substrate 100 for PDP is composed of the laminate 3 and a protective layer 71 provided so as to cover the surface of the front dielectric layer 70 in the laminate 3. The laminate 3 is configured by laminating a front glass substrate 40, a strip-shaped display electrode 52, and a front dielectric layer 70 in order. The front dielectric layer 70 is obtained by heating an inorganic particle-containing composition layer formed from the inorganic particle-containing composition of the present invention. The PDP rear substrate 200 includes a rear glass substrate 41, a strip-shaped address electrode 54 provided on the rear glass substrate 41, a rear dielectric layer 72 provided on the rear glass substrate 41 and the address electrode 54, and a rear surface. The barrier rib 80 provided on the dielectric layer 72 and a phosphor layer 90 formed so as to cover the wall surface of the barrier rib 80 and the surface of the back dielectric layer 72 are mainly configured. The phosphor layer 90 is obtained by heating an inorganic particle-containing composition layer formed from the inorganic particle-containing composition of the present invention. The PDP front substrate 100 and the PDP rear substrate 200 are bonded together so that the protective layer 71 and the barrier rib 80 are in close contact with each other, thereby forming a discharge space 76 surrounded by the phosphor layer 90 and the protective layer 71. Has been. In the PDP 300, the constituent members such as the glass substrates 40 and 41, the protective layer 71, the back dielectric layer 72, the barrier rib 80, and the electrodes 52 and 54 can be formed by a conventionally known material and method. The back dielectric layer 72 may be formed by the method for forming an inorganic layer of the present invention.

In the PDP 300 configured in this manner, the front dielectric layer 70 and the phosphor layer 90 are formed with lower energy than before, and adverse effects caused by organic compounds are sufficiently reduced. It is excellent in terms of.
Moreover, in this embodiment, you may form the display electrode 52 using the inorganic particle containing composition of this invention. In this case, the inorganic particle-containing composition layer is formed on the substrate 40 by applying the inorganic particle-containing composition containing the metal particles or metal oxide particles described above as the inorganic particles, and is dried and fired. Thus, an electrode can be formed.
Examples of the coating method include screen printing, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, die coating method, and curtain coating method. The drying temperature is not particularly limited, but is preferably about 60 to 200 ° C., and the drying time is preferably about 1 minute to 1 hour.
Examples of the firing method include a method in which a laminate of the substrate and the inorganic particle-containing composition layer is accommodated in an electric furnace and heated, a method in which the laminate is placed on a hot plate and heated. Can be mentioned.
The firing temperature is not particularly limited as long as the inorganic particle-containing composition layer is sufficiently sintered, but the maximum temperature is preferably 300 to 700 ° C, and more preferably 300 to 600 ° C. The firing time is preferably about 5 minutes to 2 hours. Moreover, it is preferable that baking is implemented in air | atmosphere.
As described above, the plasma display using the PDP in which the electrode, the dielectric layer, or the phosphor layer is formed using the inorganic particle-containing composition of the present invention is excellent in terms of display characteristics, manufacturing cost, and environment. It becomes. In particular, when all of the electrode, the dielectric layer, and the phosphor layer are formed using the inorganic particle-containing composition of the present invention, the display characteristics, production cost, and environment are further improved.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
<Preparation of inorganic particle-containing composition>
Hereinafter, the present invention will be described by way of examples.
(Experimental example)
(A) Bishydroxymethyltricyclodecane (hereinafter abbreviated as DCPD) as the organic compound, (B) Terpineol (isomer mixture, trade name, manufactured by Nippon Terpene Chemical Co., Ltd.) (hereinafter abbreviated as TPO) as the organic solvent, or Phosphor fine particles were mixed as 2- (2-butoxyethoxy) ethanol (hereinafter abbreviated as BC from the conventional name (butyl carbitol)) and inorganic fine particles (C) to prepare a solution containing inorganic fine particles.

(Examples 1-6)
DCPD, BC or TPO and phosphor fine particles (Zn ₂ SiO ₄ : Mn) are mixed at the ratio of parts by mass shown in Table 2, mixed and dispersed for 15 minutes using a bead mill, and further an opening of 30 μm square. And filtered through a filter cloth having a phosphor fine particle-containing resin composition.

(Comparative Examples 1-6)
In place of DCPD of the examples, isobornylcyclohexanol represented by the following general formula (manufactured by Nippon Terpene Chemical Co., Ltd., trade name: Tersolve MTPH) was used, and in the ratio of parts by mass shown in Table 2, BC or TPO, And phosphor fine particles (Zn ₂ SiO ₄ : Mn) are mixed, mixed and dispersed for 15 minutes using a bead mill, and further filtered through a filter cloth having a 30 μm square opening, to obtain a phosphor fine particle-containing resin A composition was prepared.

Comparing the viscosities of the obtained phosphor fine particle-containing resin compositions, the compositions of Examples 1 to 3 increased in viscosity by 167% when the ratio of the added solvent decreased by 5 parts by mass. On the other hand, the viscosities of the compositions of Comparative Examples 1 to 3 increased by 360%. In the compositions of Examples 4 to 6, the viscosity increased by 210% when the ratio of the added solvent decreased by 10 parts by mass. On the other hand, the viscosities of the compositions of Comparative Examples 4 to 6 increased by 287%.
As described above, in the composition using DCPD represented by the general formula (1) as the organic compound (A), the ratio of the dilution solvent is higher than that in the composition using MTPH which is the other organic compound. The change in viscosity was moderate with respect to the change.

（蛍光体微粒子含有組成物の組成（質量部））

(Composition of phosphor fine particle-containing composition (parts by mass))

（蛍光体微粒子含有組成物の組成（質量部））

(Composition of phosphor fine particle-containing composition (parts by mass))

  As can be seen from the above results, the inorganic fine particle-containing resin composition of the present invention has a gentle change in viscosity with respect to the blending amount of the dilution solvent to obtain a desired viscosity, and an error in blending amount at the time of preparing the composition It turns out that the tolerance of the solution viscosity with respect to becomes wide. Thereby, it becomes easy to suppress coating unevenness and control the film thickness in the step of applying the inorganic fine particle-containing solution to the substrate. In addition, it is possible to form a desired inorganic body or inorganic layer with lower energy than before, and to reduce the adverse effects caused by organic compounds, and to form an inorganic layer that is advantageous in terms of workability and cost, and a method for forming such an inorganic layer A plasma display including an inorganic layer formed by the above can be provided.

DESCRIPTION OF SYMBOLS 1, 1 'Inorganic particle containing composition layer 3 Laminated body 40 Front glass substrate 41 Back glass substrate 52 Display electrode 54 Address electrode 70 Dielectric layer (front dielectric layer)
71 Protective layer 72 Rear dielectric layer 76 Discharge space 80 Barrier rib 90 Phosphor layer 100 PDP front substrate 200 PDP rear substrate (PDP substrate)
300 PDP

Claims (6)

(A) an organic compound represented by the following general formula (1);
(B) an organic solvent;
(C) Inorganic particle-containing composition containing inorganic particles.

(In the general formula (1), R represents an alkylene group having 1 to 10 carbon atoms, n + m represents an integer of 1 to 3, and when two or more R exist in the same molecule, each R is the same or different. May be.)   The inorganic particle containing composition whose content of the organic compound represented by the said General formula (1) is 50-95 mass% with respect to the organic compound whole quantity contained in the said inorganic particle containing composition. On the substrate, coating the inorganic particle-containing composition according to claim 1 or 2 to provide an inorganic particle-containing composition layer;
Heating the inorganic particle-containing composition layer;
A method for forming an inorganic layer.   The method for forming an inorganic layer according to claim 3, wherein the substrate is a plasma display substrate, the inorganic particles are glass particles, and a dielectric layer for plasma display is formed as the inorganic layer.   The method for forming an inorganic layer according to claim 3, wherein the substrate is a plasma display substrate, the inorganic particles are phosphor particles, and a phosphor layer for plasma display is formed as the inorganic layer.   A plasma display comprising the dielectric layer for plasma display formed by the method for forming an inorganic layer according to claim 4 or the phosphor layer for plasma display formed by the method for forming an inorganic layer according to claim 5. .

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