JP2009263448A - Inorganic particle-containing resin composition and inorganic layer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic particle-containing resin composition maintaining advantages of containing a binder polymer (suppressing sedimentation, preventing alteration and adjusting a viscosity) while reducing a generation amount of amorphous carbon during pyrolysis of the binder polymer, and to provide an inorganic layer using the composition. <P>SOLUTION: The inorganic particle-containing resin composition comprises at least: (A) an organic compound having a viscosity of 10,000 to 1,000,000 mPa s at 25°C and a heating residue of 0 to 1 wt.% at 300°C; (B) a binder polymer; and (C) inorganic fine particles. The inorganic layer is obtained by applying and calcining the above inorganic particle-containing resin composition on a substrate to form a layer containing the inorganic fine particles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition containing inorganic fine particles and an inorganic layer using the same.

  In the resin composition containing inorganic fine particles, it is easy to control the thickness of the layer to be formed in the step of forming the applied inorganic fine particle layer or inorganic layer (hereinafter sometimes referred to as inorganic layer). In addition, due to the high degree of freedom of transportation that can be handled like a liquid depending on the viscosity, and the ability to suppress scattering of fine particles by mixing inorganic fine particles with resin, the cleanliness of the work space is improved, etc. Therefore, it is applied to many inorganic fine particle layer or inorganic layer forming processes.

  Conventionally, this inorganic fine particle-containing resin composition has been produced with a composition containing at least (A) a binder polymer, (B) a diluting solvent, and (C) inorganic fine particles. Such a resin composition is finally applied on the substrate in accordance with the desired thickness of the inorganic layer, the diluted solvent is evaporated by heating, and the binder polymer is further desorbed by thermal decomposition, whereby inorganic fine particles are removed. A process of forming an inorganic layer by forming a layer on a substrate and further binding inorganic fine particles by heating to form a layer is widely used (see, for example, Patent Document 1).

  In the inorganic layer forming process, the binder polymer is thermally decomposed, so that a large amount of amorphous carbon is generated. Since these amorphous carbons adhere to the inside of the heating device, heating efficiency is deteriorated and the atmosphere is easily contaminated. In addition, the treatment of the generated amorphous carbon generally requires heat treatment and complete combustion, but this causes problems such as an increase in environmental load and an increase in cost. Therefore, the present inventors have replaced the binder polymer with an organic compound that has a high viscosity and evaporates at a temperature lower than the thermal decomposition temperature of the binder polymer, and the present inventors have prepared an inorganic fine particle-containing composition that can omit the thermal decomposition step of the binder polymer. Proposed. In particular, isobornylcyclohexanol has a heating residue at 300 ° C. of 0 to 1% by weight, and celluloses used as ordinary binder polymers achieve the same heating residue as that of isobornylcyclohexanol. Is a useful compound that needs to be heated to a temperature of about 300 to 500 ° C., which is higher than that, and can suppress the heating residue at a low temperature.

JP-A-9-102272

However, when the composition containing inorganic fine particles contains a binder polymer together, (1) it can impart thixotropy to the composition and suppress sedimentation of the inorganic fine particles during storage, (2) the binder polymer For example, the surface of the inorganic fine particles is protected to prevent alteration, and (3) by adjusting the molecular weight of the binder polymer, the paste viscosity can be easily guided to an arbitrary range. Therefore, in the composition consisting only of a compound such as isobornylcyclohexanol and inorganic fine particles, the advantages (1) to (3) cannot be obtained, and the physical properties of the inorganic fine particle-containing composition may be significantly deteriorated. There is. Ethyl cellulose is a polymer that is excellent in suppressing sedimentation of inorganic fine particles, but has a high thermal decomposition temperature, and is not preferable for forming electrodes, dielectric layers, and phosphor layers for plasma display panel glass substrates.
The binder polymer used in the above method is effective for forming a good coating film, but in order to decompose the binder polymer as described above, a high temperature is required, and a great deal of energy is required. There is a problem that decomposition products accumulate on the walls in the electric furnace. Furthermore, if the binder polymer remains by being carbonized during decomposition, problems such as bubbles and blisters may occur, or it may gradually evaporate during discharge and adversely affect discharge characteristics.
The present invention has been made in view of the above circumstances, and is an inorganic material that satisfies the conflicting purpose of reducing the amount of amorphous carbon generated during thermal decomposition of the binder polymer while maintaining the advantages of containing the binder polymer. An object is to provide a fine particle-containing resin composition and an inorganic layer using the same.

The present invention provides [1] an organic compound having a viscosity at 25 ° C. of 10,000 to 1,000,000 mPa · s and a heating residue at 300 ° C. of 0 to 1% by weight, (B) a binder polymer, and (C) It relates to an inorganic fine particle-containing resin composition comprising at least inorganic fine particles.
The present invention also relates to [2] the inorganic particle-containing composition according to [1], wherein (A) the organic compound is isobornylcyclohexanol represented by the following structural formula (1).

また、本発明は、［３］前記（Ｂ）バインダポリマが、アクリル樹脂である、上記［１］又は上記［２］に記載の無機粒子含有組成物に関する。
また、本発明は、［４］（Ａ）２５℃における粘度が１０，０００〜１，０００，０００ｍＰａ・ｓで、３００℃における加熱残分が０〜１重量％である有機化合物が、テルペン系化合物である上記［１］に記載の無機微粒子含有樹脂組成物に関する。
また、本発明は、［５］上記［１］ないし上記［４］のいずれかに記載の無機微粒子含有樹脂組成物を基材上に形成し焼成して無機微粒子を含む層を形成して得られる無機物層に関する。

The present invention also relates to [3] the inorganic particle-containing composition according to [1] or [2] above, wherein the (B) binder polymer is an acrylic resin.
The present invention also provides: [4] (A) an organic compound having a viscosity at 25 ° C. of 10,000 to 1,000,000 mPa · s and a heating residue at 300 ° C. of 0 to 1% by weight is a terpene series. The inorganic fine particle-containing resin composition according to [1], which is a compound.
The present invention is also obtained by [5] forming the inorganic fine particle-containing resin composition according to any one of [1] to [4] above on a base material, and baking it to form a layer containing inorganic fine particles. It relates to an inorganic material layer.

  The inorganic fine particle-containing resin composition of the present invention can reduce the amount of amorphous carbon generated due to thermal decomposition of the binder polymer during heat treatment, and can also reduce the amount of amorphous carbon generated, thereby reducing its processing cost. It is possible to maintain the advantages of containing the binder polymer when forming the inorganic layer, and to provide an inorganic layer with little residual binder polymer decomposition product and free from bubbles and blisters. .

Details of the present invention will be described below.
As the organic compound (A) used in the inorganic fine particle-containing resin composition of the present invention, the viscosity at 25 ° C. is 10,000 to 1,000,000 mPa · s, and the heating residue at 300 ° C. is 0 to 1% by weight. Terpene compounds are preferred.
The terpene compound is particularly preferably isobornylcyclohexanol represented by the following structural formula (1).

  The viscosity of the organic compound in the present invention means a value measured at 25 ° C. by a method based on JIS Z 8803 and JIS K7117. Moreover, the heating residue when (A) the organic compound is heated at 300 ° C. for 10 minutes is 1% by weight or less. The heating environment is in the atmosphere. When such an organic compound is used, an adverse effect caused by the organic compound can be further reduced in the inorganic body obtained by firing.

The binder polymer (B) in the present invention is not particularly limited as long as it is a resin that can stably contain inorganic powder, but other solvents in the resin composition such as solvents and additives that are added as necessary. It is preferable that the compatibility with the component is excellent. Specifically, for example, (meth) acrylic resin, hydroxystyrene resin, novolak resin, polyester resin and the like can be suitably used. Among these, (meth) acrylic resins having a low thermal decomposition temperature are preferable. Here, in this specification, “(meth) acryl” means methacryl or acrylic, and “(meth) acrylic resin” means a monomer unit derived from a monomer having a methacryl group or an acrylic group. Means a polymer mainly composed of
Examples of the (meth) acrylic resin used as the resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) What polymerized (meth) acrylic acid ester, such as (2-ethyl) hexyl acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Can be mentioned. These monomers may be polymerized singly or in combination of two or more.

  In addition to monomers such as the above (meth) acrylic acid esters, aromatic vinyl monomers such as styrene and α-methylstyrene, conjugated dienes such as butadiene and isoprene, polystyrene, poly (meth) acrylate methyl , Macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as poly (meth) ethyl acrylate and poly (meth) acrylate benzyl, o-hydroxystyrene, m- Examples thereof include polymers obtained by polymerizing monomers such as monohydroxy phenol-containing monomers such as hydroxystyrene and p-hydroxystyrene, alone or in combination.

(B) The binder polymer preferably has a weight molecular weight of 40,000 to 2,000,000, more preferably 50,000 to 300,000, and 100,000 to 200,000. Is particularly preferred. If it is less than 40,000, the blending amount necessary for obtaining the desired viscosity increases, so that the tendency to increase the amount of amorphous carbon generated becomes strong, and if it exceeds 2,000,000, the solubility of the binder polymer deteriorates. However, the solvent that can be used for the dissolution is excessively limited, and the time required for the dissolution process tends to be long.
Furthermore, the molecular weight of the binder polymer should be appropriately selected according to the viscosity of the target paste. For example, when the target paste viscosity is 10,000 to 100,000 mPa · s, 50,000 to 300,000 is more preferable, and 100,000 to 200,000 is particularly preferable.
The molecular weight of the binder polymer in the present invention is a weight average molecular weight (Mw) estimated by a GPC (gel permeation chromatography) method based on a calibration curve created using a polystyrene standard substance.

  The (C) inorganic fine particles used in the present invention are not particularly limited, 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, the glass particle mentioned later may be added to these particles as a binder. Examples of the metal oxide particles include ruthenium oxide, copper oxide, tin oxide, ITO and the like, and glass particles which will be described later may be added to these particles as a binder. The glass particles preferably have a low melting point and preferably have a softening point in the range of 400 to 600 ° C. If the softening point exceeds 600 ° C., the glass substrate tends to be distorted. 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 average particle size of the glass particles is preferably from 0.01 to 20 μm, more preferably from 0.1 to 10 μm. The average particle diameter of the phosphor particles is preferably 0.01 to 20 μm, and more preferably 0.1 to 10 μm.

Examples of the glass particles include lead oxide, boron oxide, silicon oxide (PbO—B ₂ O ₃ —SiO ₂ ), lead oxide, boron oxide, silicon oxide, and aluminum oxide (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 system (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 , Bismuth oxide, 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) ) And the like. These may be used alone or in combination of two or more.

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 the blue color phosphor 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 the green color fluorescent material 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.

  As described above, (A) an organic compound having a viscosity of 10,000 to 1,000,000 mPa · s (25 ° C.) and a heating residue at 300 ° C. of 0 to 1% by weight, (B) a binder polymer, and (C) The inorganic fine particle-containing resin composition comprising at least inorganic fine particles can be mixed into a slurry liquid or paste by using a known mixing method.

The (A) organic compound and the (B) binder polymer in the inorganic fine particle-containing resin composition of the present invention are preferably (A) / (B) = 98/2 to 50/50 (weight ratio), and (A) / ( B) = 96/4 to 75/25 is more preferable. (A) If the organic compound is less than 50% by weight, the binder polymer ratio is high, and the effect of reducing the amount of amorphous carbon generated during thermal decomposition of the binder polymer is low. If the organic compound exceeds 98% by weight, the binder polymer is effective. When applying the surface protection of the inorganic fine particles to be exhibited, the suppression of the precipitation of the inorganic fine particles, and the resin composition containing the inorganic fine particles, it tends to be difficult to ensure the surface smoothness of the coating film.
Further, (C) inorganic fine particles are preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and more preferably 50 to 70% by weight based on the total of (A) organic compound and (B) binder polymer. . (C) If the inorganic fine particles are less than 5% by weight, the amount of the inorganic fine particles is dilute, so the thickness of the resulting inorganic layer may be non-uniform. If it exceeds 80% by weight, the inorganic fine particle-containing resin The thixotropy of the composition increases, and it tends to be difficult to form a smooth layer at the time of coating, or to coat itself.

Furthermore, the inorganic fine particle-containing resin composition in the present invention includes, for example, an organic solvent, a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, a stabilizer, and an adhesion imparting agent as necessary. Etc. can be added as needed.
Among them, the organic solvent is the most frequently used additive because it is almost completely desorbed from the resin composition by drying at about 250 ° C. or less and has a very high degree of freedom in adjusting the viscosity.
In the present invention, an organic solvent having a boiling point in the range of 150 to 250 ° C. is preferable from the viewpoint of the flatness of the coating film. In the present specification, the boiling point of the solvent refers to 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.), ethylene glycol monobutyl ether (boiling point: 171 ° C.), ethylene glycol monoisoamyl ether (boiling point: 1 Ether solvents such as 1 ° 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), 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), 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), and γ-butyrolactone Lactone solvents such as (boiling point: 204 ° C), pyrrolidone solvents such as N-methyl-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: 209 ° C), dihydroterpineo And terpene solvents such as 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, terpene solvents such as terpineol (boiling point: 209 ° C), dihydroterpineol (boiling point: 207 ° C), dihydroterpinyl acetate (boiling point: 220 ° C) are preferable.
The content in the case of using a solvent having a boiling point in the range of 150 to 250 ° C. in the inorganic fine particle-containing resin composition of the present invention is 20 with respect to the total amount of the solvent (excluding the organic compound (A)) contained in the composition. It is preferably -90% by weight, more preferably 30-85% by weight, and particularly preferably 40-80% by weight.

  In addition, in the inorganic fine particle-containing resin composition of the present invention, the boiling point is 150 ° C. in addition to the above solvent from the viewpoint of further shortening the drying time of the coating film while preventing unevenness in the coating film after drying. Less than the solvent can be used in combination.

  Examples of the solvent having a boiling point of less than 150 ° C. include alcohol organic solvents (methanol, ethanol, isopropyl alcohol, n-butyl alcohol, etc.), aromatic organic solvents (benzene, toluene, xylene, etc.), ketone solvents (acetone). , Methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), ethyl acetate, methylpropyl diglycol, hexyl carbitol, butylpropylene diglycol, benzyl alcohol, butyl Examples include carbitol, DBE thinner (DuPont Co., Ltd .: trade name), cyclohexane, cyclohexanone, and the like.

  The content of the solvent in the inorganic fine particle-containing resin composition of the present invention is not particularly limited, but it is set so that the viscosity at 25 ° C. of the mixture when mixed with (A) the organic compound is 500 to 50000 mPa · s. Furthermore, it is preferable to set the viscosity of the inorganic-containing composition so as to be in a range described later.

  The inorganic fine particle-containing resin composition of the present invention preferably has a viscosity at 25 ° C. of 1000 to 100,000 mPa · s. When the viscosity is less than 1000 mPa · s, the inorganic fine particle particles are likely to settle during storage of the composition containing no fine particles, whereas when the viscosity is greater than 100,000 mPa · s, the flatness of the coating film is lowered. Tend.

  A desired inorganic powder layer or inorganic material layer can be obtained by applying the inorganic fine particle-containing resin composition of the present invention onto a substrate by a known method, drying, and firing. For example, after being applied to a glass substrate for a plasma display panel, it can be dried and fired to form an electrode, a dielectric layer, a phosphor layer, and the like.

  Examples of the coating method include knife coating, roll coating, spray coating, gravure coating, bar coating, die coating, and curtain coating. The drying temperature is not particularly limited, but is preferably about 100 to 150 ° C., and the drying time is preferably about 1 minute to 1 hour.

Next, the inorganic powder-containing resin composition layer thus formed can be fired to obtain an inorganic powder layer or an inorganic layer.
An example of the firing method is a method of heating in an electric furnace. For example, the firing temperature of the inorganic powder-containing resin composition layer formed on the glass substrate for plasma display panel is the highest temperature, preferably 300 to 700 ° C, and more preferably 400 to 600 ° C. This step is preferably performed in the atmosphere. The firing time is preferably about 5 minutes to 2 hours.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Binder polymer)
It is preferable that the binder polymer can disperse the inorganic fine particles well and has a low thermal decomposition temperature. As a result of various investigations on the binder polymer that can disperse the inorganic fine particles satisfactorily, acrylic resins and cellulose derivatives were satisfactory. The thermal decomposability of the acrylic resin and the cellulose derivative was compared. A polymer of ethyl methacrylate was employed as the acrylic resin, and ethoxycellulose was employed as the cellulose derivative, and the thermal decomposition characteristics were measured. Pyrolysis characteristics were measured by thermogravimetric analysis (TG), each sample was heated to 600 ° C., and the end temperatures of pyrolysis were compared based on weight loss. The measurement conditions for thermogravimetric analysis are shown below.
・ Measuring equipment: TG / DTA-6200 (manufactured by SII Nanotechnology)
・ Raising rate: 5 ° C / min
・ Measurement temperature: 20-600 ° C
・ Atmosphere In air 200ml / min
・ Sampling amount 10mg
The thermal decomposition characteristics of the acrylic resin are shown in FIG. 1, and the thermal decomposition characteristics of the cellulose derivative are shown in FIG. While the acrylic resin almost completes decomposition at about 400 ° C., the cellulose derivative needs to be heated to about 500 ° C.
It is not preferable that the decomposition end temperature is higher because the decomposition product of the resin component is likely to remain in the inorganic fine particle layer to be fired when the firing peak temperature is relatively low.
From the above results, an acrylic resin that is approximately 100 ° C. lower than the cellulose derivative having a decomposition end temperature of 400 ° C. is effective as the binder polymer.

(Manufacture of organic components)
(A) As an organic compound having a viscosity of 10,000 to 1,000,000 mPa · s (25 ° C.) and a heating residue at 300 ° C. of 0 to 1% by weight, isobornyl cyclohexanol (abbreviated as MTPH) ), A terpineol isomer mixture (Terpineol C, manufactured by Nippon Terpene Chemical Co., Ltd.) as a diluent solvent, and (B) polyethyl methacrylate having a weight average molecular weight of 150,000 as a binder polymer in the composition shown in Table 1, The flask was equipped with a reflux condenser and a thermometer, heated to 120 ° C. under a nitrogen gas atmosphere with stirring, and stirred for 3 hours while maintaining 120 ± 5 ° C. to uniformly disperse. Then, it cooled to room temperature (25 degreeC) and took out the resin composition solution. The viscosity at 25 ° C. of the isobornylcyclohexanol and terpineol isomer mixture was 678,000 mPa and 35 mPa, respectively, and the heating residue at 300 ° C. for 10 minutes was 0.028 wt% and 0.020 wt%, respectively. there were.

（有機成分組成（重量部）

(Organic component composition (parts by weight)

(Production of inorganic powder-containing resin composition)
The organic component prepared above and inorganic powder (ZnO—B ₂ O ₃ —Al ₂ O ₃ glass powder) were mixed in the composition shown in Table 2, and dispersed for 5 minutes using a homomixer, and further 25 μm square It filtered through the filter cloth which has an opening part, and prepared the inorganic powder containing resin composition.

（無機粉末含有樹脂組成物の組成（重量部））

(Composition of inorganic powder-containing resin composition (parts by weight))

(Test example)
Each prepared composition was applied onto a 2 mm thick glass substrate and dried. After drying, it was fired at a maximum temperature of 560 ° C. to obtain a glass layer having a thickness of 10 μm. The light transmittance (linear transmittance (400, 550, 700 nm) total transmittance) and surface roughness (Ra) of the obtained glass layer were measured using a commercially available apparatus.
Also, 10 mg of each composition was weighed and heated to 600 ° C. by thermogravimetric analysis (TG), especially comparing the weight loss at 250 ° C. or higher, which is the desorption temperature from the main thermal decomposition of the binder polymer. did.
Further, each sample was separated into a container having a diameter of 50 mm by a depth of 45 mm and left in an environment of 40 ° C. for 14 days, and then the range from the liquid surface to a depth of 5 mm was scanned with a metal spatula (width 8 mm). The sedimentation state of the glass powder at the top was observed. Further, a metal spatula (width 8 mm) was applied to the bottom of the container for scanning, and the sedimentation / deposition state of the glass powder was observed.
The above evaluation results are summarized in Table 3.

(*) Weight reduction is weight reduction per 10mg of each sample (measurement range 250-600 ° C)
Evaluation regarding glass powder sedimentation was as follows: ○: No sedimentation, Δ: Signs of sedimentation, ×: Clear sedimentation.
The glass powder sedimentation at the liquid surface is mainly evaluated for the transparency of a paste of 5 mm from the liquid surface, ○: no change, Δ: slight increase in transparency due to glass powder sedimentation, x: completely Judgment was made based on the standard that the glass powder settled and became only a transparent resin.
Glass powder settling at the bottom is the main evaluation object, especially the presence or absence of glass powder agglomerates at the tip, pulling up the metal spatula after scanning,
○: No aggregates, Δ: Signs of aggregate formation are observed, ×: Clear aggregates are judged.
In the above-mentioned glass powder sedimentation evaluation, there is no particular difficulty in practical use until Δ, but when clear sedimentation / aggregation, which is an evaluation of ×, occurs, the aggregate remains on the coated surface in the coating process. The desired flatness cannot be obtained.

As a result of the test, the optical characteristics (linear transmittance, total (light) transmittance) of the obtained glass layer were the same for all samples. From this, as a high-viscosity organic compound that replaces the binder polymer, an organic material having a viscosity of 10,000 to 1,000,000 mPa · s (25 ° C.) and a heating residue at 300 ° C. of 0 to 1% by weight. It has been found that the use of the compound does not affect the optical properties of the glass layer.
Regarding the surface roughness, a tendency was found that the surface becomes smoother due to the weight loss of the binder polymer. Therefore, a layer having a smooth surface can be obtained by adding an organic compound having a viscosity of 10,000 to 1,000,000 mPa · s (25 ° C.) and a heating residue at 300 ° C. of 0 to 1% by weight. It has been found that it can be formed.
The weight loss when heated to 250 ° C. to 600 ° C. was proportional to the blending amount of the binder polymer, and the lower the polymer amount, the smaller the weight loss.
The above results indicate that an organic compound having a viscosity of 10,000 to 1,000,000 mPa · s (25 ° C.) and a heating residue at 300 ° C. of 0 to 1% by weight can be used as an alternative to the binder polymer. It further indicates that the surface smoothness of the obtained inorganic layer is improved.

  However, from the observation results of glass powder sedimentation, it was found that it is inappropriate to omit the binder polymer completely. That is, the binder polymer is completely omitted, the viscosity is 10,000 to 1,000,000 mPa · s (25 ° C.) and the heating residue at 300 ° C. is 0 to 1% by weight in order to increase the viscosity. Only the comparative example 2 which mix | blended only the organic compound showed sedimentation / deposition of clear glass powder. This indicates that the binder polymer is important not only for increasing the viscosity but also for preventing sedimentation of the inorganic powder and improving the long-term stability of the composition.

  As can be seen from this test example, the inorganic fine particle-containing resin composition of the present invention is a conventional composition described in Comparative Example 1, that is, a composition prepared using only a binder polymer, an organic solvent, and an inorganic powder. It is possible to form an inorganic layer exhibiting performance equal to or higher than that of the inorganic layer provided by the material, and to reduce the amount of amorphous carbon generated by thermal decomposition of the binder polymer during heat treatment. Since the generation amount of amorphous carbon can be reduced, the processing cost can be reduced. Further, the composition described in Comparative Example 2, that is, the binder polymer was omitted completely, the viscosity was 10,000 to 1,000,000 mPa · s (25 ° C.), and the heating residue at 300 ° C. was 0 to 1 Compared to a composition prepared using only an organic compound in weight% as a material for increasing the viscosity, it is superior in the ability to prevent sedimentation of inorganic powder, which is characteristic of the binder polymer, and the composition has long-term stability. is there.

The thermal decomposition characteristic view of the acrylic resin used in the Example. The thermal decomposition characteristic view of the cellulose derivative used in the Example.

Claims (5)

  (A) an organic compound having a viscosity at 25 ° C. of 10,000 to 1,000,000 mPa · s and a heating residue at 300 ° C. of 0 to 1% by weight, (B) a binder polymer, and (C) inorganic An inorganic fine particle-containing resin composition comprising at least fine particles. The inorganic particle-containing composition according to claim 1, wherein the organic compound (A) is isobornylcyclohexanol represented by the following structural formula (1).

  The inorganic particle-containing composition according to claim 1 or 2, wherein the (B) binder polymer is an acrylic resin.   (A) The organic compound whose viscosity in 25 degreeC is 10,000-1,000,000 mPa * s and whose heating residue in 300 degreeC is 0 to 1 weight% is a terpene type compound. Inorganic fine particle-containing resin composition.   An inorganic material layer obtained by forming the inorganic fine particle-containing resin composition according to any one of claims 1 to 4 on a base material and firing to form a layer containing inorganic fine particles.

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