JP2010157419A - Composition for flat panel display member formation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for FPD member formation of which an insulation film having a high heat resistance, high transparency, high surface smoothness and large thickness, can be obtained without causing cracks with fewer number of times of coating. <P>SOLUTION: This composition includes: inorganic particles; and at least one kind of silane compound selected from a group consisting of organosilane represented by formula (1) of R<SP>1</SP><SB>n</SB>Si(OR<SP>2</SP>)<SB>4-n</SB>, its hydrolysate, its condensation product and polysiloxane having structural units represented by formula (2) of R<SP>3</SP><SB>a1</SB>R<SP>4</SP><SB>a2</SB>SiO<SB>b</SB>(OH)<SB>c</SB>(OR<SP>5</SP>)<SB>d</SB>(Y)<SB>e</SB>. In these formulae, R<SP>1</SP>and R<SP>3</SP>are each an aromatic hydrocarbon group in which the number of carbons is 6 to 20, R<SP>2</SP>is an alkyl group in which the number of carbons is 1 to 5 or an acyl group in which the number of carbons is 1 to 6, R<SP>4</SP>is an organic group in which the number of carbons is 1 to 8, R<SP>5</SP>is an alkyl group in which the number of carbons is 1 to 6 or an acyl group or a phenyl group in which the number of carbons is 1 to 6, n is an integer of 0 to 2, Y is halogen or hydrogen, a1 is more than 0 and 4 or less, and a2, b, c, d and e are each independently 0 or more and 4 or less and satisfy a relation of a1+a2+b/2+c+d+e=4. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for forming a flat panel display member used for forming a flat panel display member such as a dielectric layer or a partition wall.

In recent years, flat panel displays (hereinafter also referred to as “FPD”) such as a plasma display and a field emission display (hereinafter also referred to as “FED”) have attracted attention as flat fluorescent displays.
In the plasma display, each transparent electrode is fixed, and an inert gas such as argon or neon is sealed between two glass plates arranged in close proximity to each other. It is a display that displays information by emitting light. On the other hand, the FED is a display that displays information by causing a phosphor to emit light by emitting electrons from a cathode into a vacuum by applying an electric field and irradiating the electrons on the anode.
FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In the figure, 101 and 102 are glass substrates arranged opposite to each other, 103 is a partition, and cells are partitioned by the glass substrate 101, glass substrate 102 and partition 103. 104 is a transparent electrode fixed on the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, 106 is an address electrode fixed on the glass substrate 102, 107 is The fluorescent material held in the cell, 108 and 109 are dielectric layers formed on the surface of the glass substrate 101 so as to cover the bus electrode 104, 110 is a protective film made of, for example, magnesium oxide, and 111 is a partition.
FIG. 2 is a schematic diagram showing the cross-sectional shape of the FED. In the figure, 201 and 202 are glass substrates, 203 is an insulating layer, 204 is a transparent electrode, 205 is an emitter, 206 is a cathode electrode, 207 is a phosphor, 208 is a gate, and 209 is a spacer.

As a method for producing such members as dielectrics, partition walls, electrodes, phosphors, color filters, and black stripes (matrix) used in such FPDs, for example, after forming an inorganic powder-containing resin layer on a substrate A method of firing this (see Patent Document 1) is known.
Further, as a material for forming the FPD member, a low dielectric material using a Si compound has been studied (see Patent Document 2 and Patent Document 3).

JP-A-9-102273 JP 2001-135222 A JP 2007-299624 A

However, when the FPD member is formed of the above materials, there is a problem that a crack is generated in the obtained member. In particular, when a film is formed on a substrate on which a concavo-convex pattern is previously formed by another member, such a problem of cracks becomes significant.
In particular, when used for an FPD front plate, it is important to have high smoothness. Furthermore, from the viewpoint of FPD productivity, it is also important that the desired film thickness can be obtained with a small number of coatings.

The present invention has been made based on the circumstances as described above, and an object thereof is to obtain an insulating film suitable as an FPD member having high heat resistance and high transparency without causing cracks. An object of the present invention is to provide a composition for forming a flat panel display member.
Another object of the present invention is to provide a composition for forming a flat panel display member, which can obtain an insulating film suitable for an FPD member with high smoothness and thickness, with a small number of coatings. .

The composition for forming a flat panel display member of the present invention comprises inorganic particles (A),
Selected from the group consisting of at least one organosilane represented by the following formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, and a polysiloxane having an average composition represented by the following formula (2) And at least one silane compound (B).
Formula (1) R ¹ _n Si (OR ² ) _4-n
[Wherein, R ¹ represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and when two R ¹ are present, they may be the same as or different from each other. R < ² > shows a C1-C5 alkyl group or a C1-C6 acyl group each independently. n is an integer of 1 to 3. ]
Formula (2) R ³ _a1 R ⁴ _a2 SiO _b (OH) _c (OR ⁵ ) _d (Y) _e
[Wherein R ³ represents a monovalent organic group having an aromatic ring having 1 to 3 carbon atoms, and when a plurality of R ³ are present, they may be the same or different from each other. . R ⁴ represents an organic group having 1 to 8 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other. R ⁵ represents an organic group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and a phenyl group, and when a plurality of R ⁵ are present, they are They may be the same or different. R ⁴ and R ⁵ may be the same or different. Y represents a halogen atom or a hydrogen atom. a1 is greater than 0 and 4 or less, and a2, b, c, d, and e are each independently 0 or more and 4 or less, and satisfy a1 + a2 + b / 2 + c + d + e = 4. ]

In the composition for forming a flat panel display member of the present invention, the polymer (C) [however, excluding those corresponding to the silane compound (B). ] Is further preferably contained. Moreover, it is preferable that the weight average molecular weight of polystyrene conversion of a polymer (C) is 10,000-500,000.
Moreover, it is preferable that mass ratio of the polymer (C) with respect to the sum total of an inorganic particle (A) and a silane compound (B) is 1-30.
Moreover, it is preferable to use a silica particle as an inorganic particle (A), The said silica particle contains the particle | grains of the range whose particle diameter measured by the laser diffraction method is 0.03-0.3 micrometer 50% or more on a volume basis. It is preferable.
Further, the inorganic particles (A) are 65 parts by mass or more and less than 100 parts by mass, and the silane compound (B) is more than 0 parts by mass in terms of SiO ₂ and 35 parts by mass or less (however, the inorganic particles (A) and the silane compound (B the sum of the SiO ₂ equivalent amount of) preferably contains a to.) and 100 parts by weight.
Moreover, the composition for flat panel display member formation of this invention can be used suitably as a material for forming the dielectric material layer in a flat panel display.

  According to the composition for forming a flat panel display member of the present invention, by containing inorganic particles and a specific silane compound, an insulating film excellent in balance between transparency and heat resistance can be formed. Since a thick insulating film having smoothness can be obtained with a small number of coatings, a cured body having excellent transparency and heat resistance and having high smoothness does not cause cracks even during thick film formation. It can be obtained with a small number of coatings.

Hereinafter, embodiments of the composition for forming a flat panel display member of the present invention will be described in detail.
The composition for forming a flat panel display member of the present invention (hereinafter referred to as “FPD member forming composition”) contains inorganic particles (A) and a specific silane compound (B) as essential components, and is an optional component. As a polymer (C).

[Inorganic particles (A)]
The inorganic particles (A) used in the composition for forming an FPD member of the present invention vary depending on the type of an object to be formed, such as an FPD member, and can be appropriately selected according to the type of the FPD member.
Specific examples of the inorganic particles (A) in the composition for forming an FPD member of the present invention will be described below for each type of FPD member.

Examples of the inorganic particles (A) used for the dielectric layer forming material for forming the dielectric layer include glass powder.
Preferable specific examples of the glass powder include a mixture of lead oxide, boron oxide, silicon oxide and calcium oxide (PbO—B ₂ O ₃ —Si ₂ —CaO system);
A mixture of zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₂ —SiO ₂ system); lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system) A mixture of
A mixture of lead oxide, zinc oxide, boron oxide and silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ system);
A mixture of lead oxide, zinc oxide, boron oxide, silicon oxide and titanium oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ —TiO ₂ system);
Examples thereof include a mixture of bismuth oxide, boron oxide and silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system).

  As an inorganic particle (A) used for the electrode forming material for forming an electrode, what consists of Ag, Au, Al, Ni, an Ag-Pd alloy, Cu, Cr, Co etc. is mentioned, for example.

The inorganic particles used in the resistor forming material for forming a resistor (A), include those made of, for example, such as RuO _2.

Examples of the inorganic particles (A) used for the phosphor-forming material for forming the phosphor include, for example, Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu. ³⁺ , YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : red phosphor such as Mn;
Green phosphors such as Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y _3. (Al, Ga) ₅ O ₁₂ : Tb;
Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ C ₁₂ : Eu ²⁺ , (Zn, Cd) Examples thereof include those made of a blue phosphor such as S: Ag.

Examples of inorganic particles (A) used as a color filter forming material for forming a color filter include Fe ₂ O ₃ , Pb ₃ O ₄ , CdS, CdSe, PbCrO ₄ , PbSO ₄ , and Fe (NO ₃ ) _3. Red pigments such as
Green pigments such as Cr ₂ O ₃ , TiO ₂ —CoO—NiO—ZnO, CoO—CrO—TiO ₂ —Al ₂ O ₃ , Co ₃ (PO ₄ ) ₂ , CoO—ZnO;
_{2 (Al 2 Na 2 Si 3} O 10) · Na 2 S 4, other blue pigments such as CoO-Al ₂ O _3, as an inorganic pigment for color correction,
Yellow pigments such as PbCrO ₄ —PbSO ₄ , PbCrO ₄ , PbCrO ₄ —PbO, CdS, TiO ₂ —NiO—Sb ₂ O ₃ ;
Orange pigments such as Pb (Cr—Mo—S) O ₄ ;
Examples thereof include violet pigments such as Co ₃ (PO ₄ ) ₂ .

  Examples of the inorganic particles (A) used for the black matrix forming material for forming the black matrix include those composed of Mn, Fe, Cr, Ni, Co and oxides and composite oxides thereof.

Examples of other inorganic particles which can be used for the flat display panel member forming material _{(A), SiO 2, Al} 2 O 3, ZrO 2, TiO 2, ZnO, AlGaAs, Al (OH) 3, Si 3 N 4, Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co—FeO _x , CrO ₂ , Fe ₄ N, BaTiO ₃ , BaO—Al ₂ O ₃ —SiO ₂ , Ba ferrite, SmCO ₅ , YCO ₅ , CeCO ₅ , PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂ Fe ₁₄ B, Al ₄ O ₃ , α-Si, _{SiN 4, CoO, Sb-SnO} 2, Sb 2 O 5, MnO 2, MnB, Co 3 O 4, Co 3 B, LiTaO 3, MgO, MgAl 2 O 4, BeAl 2 O 4, ZrSiO 4, ZnSb, _{bTe, GeSi, FeSi 2, CrSi} 2, CoSi 2, MnSi 1.73, Mg 2 Si, β-B, BaC, BP, Ti 2, ZrB 2, HfB 2, Ru 2 Si 3, TiO 3, PbTiO 3, Al 2 _{TiO 5, Zn 2 SiO 4,} Zr 2 SiO 4, 2MgO 2 -Al 2 O 3 -5SiO 2, Nb 2 O 5, Li 2 O-Al 2 O 3 -4SiO 2, Mg ferrite, Ni ferrite, Ni-Zn Examples thereof include ferrite, Li ferrite, and Sr ferrite.

As the inorganic particles (A), inorganic single particles or inorganic compound particles exemplified for each type of FPD member to be formed, and other inorganic compound particles exemplified as those that can be used alone, or two or more kinds thereof are used. They can be used in combination, and particles composed of a composite of inorganic compounds can also be used.
The electrode forming material, the resistor forming material, the phosphor forming material, the color filter forming material, and the black matrix forming material are each composed of the inorganic compound particles exemplified as the inorganic particles (A) and the dielectric layer forming material. Further, the glass powder exemplified as the inorganic particles (A) related to the partition wall forming material may be contained (combined).

As described above, the inorganic particles (A) used in the composition for forming an FPD member of the present invention can be appropriately selected and used according to the type of FPD member to be formed. In order to form a low dielectric layer, it is particularly preferable to use silica (SiO ₂ ) particles.
The silica particles are preferably used in an amount of 40% by mass or more when the total amount of (A) inorganic particles is 100% by mass.

<Silica particles>
As silica particles, in addition to those in powder form, water-based sols or colloids dispersed in water, or solvent-based sols or colloids dispersed in polar solvents such as isopropyl alcohol or nonpolar solvents such as toluene, etc. Can be used.
Here, when using a solvent-based sol or colloid form, the dispersion state of the silica particles can be adjusted by further adding water and a solvent to the dispersion to dilute, For the purpose of improving the dispersibility of the silica particles, silica particles that have been subjected to a surface treatment can be used. In the solvent-type sol or colloid form, the solid content concentration is usually more than 0% by mass and 50% by mass or less, preferably 0.01% by mass to 40% by mass. is there.
In addition, when the colloidal silica in which the silica particles are dispersed in the organic solvent is used as the inorganic particles (A), the obtained cured body (FPD member) has further excellent transparency and heat resistance.

As a specific example of such silica particles, surface treatment is performed on the surface thereof such as “# 150”, “# 200” and “# 300” manufactured by Nippon Aerosil Co., Ltd. "R972", "R974", "R976", "RX200", "RX300", "RY200S", "RY300" and "R106" manufactured by Nippon Aerosil Co., Ltd., "SS50A" manufactured by Tosoh Corporation, Fuji Examples thereof include those obtained by subjecting the surface thereof to a hydrophobization treatment such as “Silo Hovic 100” manufactured by Siricia. Examples of the solvent-dispersed colloidal silica include alcohol-based solvent-dispersed colloidal silica such as isopropyl alcohol manufactured by Nissan Chemical Industries, ketone-based solvent-dispersed colloidal silica such as methylisobutyl, and nonpolar solvent-dispersed colloidal silica such as toluene. It is done.
Further, when colloidal silica is used as the silica particles constituting the inorganic particles (A), other components (specifically, specific silane compounds are used when preparing the FPD member forming composition of the present invention. (B) and the polymer (C), etc.) may also be mixed, and they can also be added to the reaction system for hydrolysis and condensation reactions to obtain the specific silane compound (B) described below.

Further, the silica particles preferably contain particles having a particle diameter in the range of 0.03 to 0.3 μm on a volume basis, usually 50% or more, preferably 60% or more, more preferably 70% or more. .
In the present specification, the particle size distribution of silica particles is measured using a particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device “UPA-150” manufactured by Nikkiso Co., Ltd.) in a state where silica particles are dispersed in an organic solvent. It is measured by a laser diffraction method.

When the silica particles contain particles having a particle size of 0.03 μm or less, and accordingly the content ratio of particles having a particle size in the range of 0.03 to 0.3 μm is 50% or less on a volume basis. May cause cracks during film formation for forming the FPD member and when the formed FPD member is placed at a high temperature. On the other hand, when the particle size contains particles having a particle size of 0.3 μm or more, and accordingly, the content ratio of particles in the range of 0.03 to 0.3 μm is 50% or less on a volume basis, There is a possibility that sufficient transparency cannot be obtained in the cured body (FPD member).
The silica particles may have a content ratio of particles having a particle diameter in the range of 0.03 to 0.3 μm of 50% or more on a volume basis, and various (plural) particles within a range satisfying this condition. It may contain particles having a diameter.

[Specific silane compound (B)]
The specific silane compound (B) used in the composition for forming an FPD member of the present invention is an organosilane represented by the above formula (1) (hereinafter also referred to as “compound (b1)”), the compound (b1). And a condensate of the compound (b1) and a compound selected from the group consisting of polysiloxanes having a structural unit represented by the above formula (2) (hereinafter these are also referred to as “compound (b2)”) Say.)
The specific silane compound (B) may be any compound that contains at least the compound (b1) or the compound (b2), and two or more types even if the organosilane constituting the compound (b1) is one type. Each of the hydrolyzate and condensate constituting the compound (b2) and the polysiloxane having the structural unit represented by the formula (2) may be one type or two or more types. Also good.

<Compound (b1)>
In the formula (1) showing the compound (b1), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, anthonyl, tetranyl, Examples include a pentanyl group.
Furthermore, examples of the group R ¹ include substituted derivatives of these organic groups.
Examples of substituents of such substituted derivatives include halogen atoms, unsubstituted or substituted amino groups, hydroxyl groups, mercapto groups, isocyanate groups, glycidoxy groups, 3,4-epoxycyclohexyl groups, (meth) acryloxy groups, and ureidos. Groups, ammonium bases and the like. However, when the group R ¹ is composed of a substituted derivative having these substituents, the number of carbon atoms of the substituted derivative is preferably 20 or less including the carbon atoms constituting the substituent.
In Formula (1), when there are a plurality of R ¹ (specifically, two) R ¹ , these may be the same or different from each other.

In Formula (1), R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. Can be mentioned.
Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
In formula (1), there are a plurality of R ² (specifically, 2 to 4) R ^{2 s} , which may all be the same or different.

As a specific example of the organosilane which is such a compound (b1),
Trialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane (n = 1 in formula (1));
Dialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane (n = 2 in formula (1));
Monoalkoxysilanes such as triphenylmethoxysilane and triphenylethoxysilane (n = 3 in formula (1));
Etc.
These can be used alone or in combination of two or more.
The compound (b1) is preferably contained in the total silane in an amount of 0.1% by mass or more.

<Compound (b2)>
Compound (b2) is a hydrolyzate of compound (b1) (hereinafter referred to as “specific hydrolyzate”), a condensate of compound (b1) (hereinafter referred to as “specific condensate”), or the above. It is a polysiloxane having a structural unit represented by the formula (2) (hereinafter referred to as “specific polysiloxane”).
<Specific hydrolyzate and specific condensate>
The specific hydrolyzate constituting the compound (b2) is a hydrolyzate produced by hydrolyzing the organosilane represented by the formula (1) which is the aforementioned compound (b1), and the compound (b2). The specific condensate constituting is a hydrolyzate produced by hydrolyzing the organosilane represented by the formula (1) which is the aforementioned compound (b1), and the formula (1) which is a raw material of the hydrolyzate. The silanol group formed by hydrolyzing the OR ² group constituting the organosilane represented by (3) is condensed to form a Si—O—Si bond.
The specific hydrolyzate may be any compound as long as at least one of 1 to 4 OR ² groups is hydrolyzed in the formula (1) indicating the compound (b1) as a raw material. For example, one obtained by hydrolyzing one OR ² group, one obtained by hydrolyzing two or more OR ² groups, or a mixture thereof may be used.
In addition, the specific condensate does not have to be condensed with all of the silanol groups generated by hydrolysis of the compound (b1), and a small part of the silanol groups are condensed, most (including all). ) In which silanol groups are condensed, or a mixture thereof.

≪Hydrolysis condensation catalyst≫
Catalyst used for hydrolysis reaction and condensation reaction to obtain specific hydrolyzate and specific condensate (hereinafter collectively referred to as “specific hydrolyzate / condensate”) (hydrolysis condensation catalyst) ) As basic compounds, acidic compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter, these “organometallic compounds and / or partial hydrolysates thereof” are collectively referred to as “organometallic compounds”. .).

≪Basic compounds≫
Specific examples of the basic compound include ammonia (including aqueous ammonia); organic amine compounds; alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium methoxide and sodium ethoxide. Alkali metal alkoxides such as Of these, ammonia and organic amine compounds are preferred.

  Specific examples of the organic amine compound include alkylamine, alkoxyamine, alkanolamine, arylamine and the like.

  Specific examples of the alkylamine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-di Examples thereof include alkylamines having an alkyl group having 1 to 4 carbon atoms such as butylamine, trimethylamine, triethylamine, tripropylamine, and tributylamine.

  Specific examples of the alkoxyamine include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, Examples thereof include alkoxyamines having an alkoxy group having 1 to 4 carbon atoms such as butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine.

  Specific examples of the alkanolamine include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N- Ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethano Ruamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanol Nolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N -Propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N -(Aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl) Ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- Examples include alkanolamines having an alkyl group having 1 to 4 carbon atoms such as (aminobutyl) butanolamine.

  Specific examples of the arylamine include aniline and N-methylaniline.

  Furthermore, as the organic amine compound, in addition to the above-mentioned alkylamine, alkoxyamine, alkanolamine and arylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide Tetraalkylammonium hydroxide such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, etc .; methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethyl Amine, ethylaminoethylamine, ethylaminopro Alkylaminoalkylamines such as ruamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine; pyridine, Pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene and the like can also be used.

As the basic compound, ammonia, organic amine compounds, alkali metal and alkaline earth metal hydroxides, and alkali metal alkoxides may be used alone or in combination of two or more.
As the basic compound, ammonia and an organic amine compound are preferably used as described above. Of these, triethylamine, tetramethylammonium hydroxide and pyridine exemplified as the organic amine compound are used. Particularly preferred.

≪Acid compound≫
Organic acids and inorganic acids can be used as the acidic compound.
Specific examples of the organic acid include, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipine Acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p- Examples include toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Specific examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Of these, maleic acid, maleic anhydride, methanesulfonic acid and acetic acid are particularly preferred.
Moreover, these can be used individually by 1 type or in combination of 2 or more types.

≪Organic metal compounds≫
Examples of the organometallic compounds include, for example, a compound represented by the following formula (3) (hereinafter also referred to as “organometallic compound (3)”), one tin atom having 1 to 10 carbon atoms. Single or two bonded tetravalent tin organometallic compounds (hereinafter referred to as “organotin compounds”) and partial hydrolysates thereof (specifically, partial hydrolysates of organometallic compounds (3) and A partial hydrolyzate of an organotin compound).

[Wherein, M represents one type of metal atom selected from the group consisting of a zirconium atom, a titanium atom, an aluminum atom and a sodium atom, and R ¹⁰ and R ¹¹ are each independently of 1 to 6 carbon atoms. R ¹² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 16 carbon atoms. r and s are each independently an integer of 0 to 4, and satisfy the relationship of (r + s) = (M valence). ]

In the formula (3), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by R ¹⁰ and R ¹¹ and R ¹² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group and the like.
Examples of the alkoxyl group having 1 to 16 carbon atoms represented by the group R ¹² include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, A lauryloxy group, a stearyloxy group, etc. are mentioned.

Specific examples of the organometallic compound (3) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxy Organic zirconium compounds such as tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
Tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (acetyl acetate) titanium, di -Organotitanium compounds such as i-propoxy bis (acetylacetone) titanium;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) ) Organic aluminum compounds such as aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum; sodium alkoxides such as sodium methoxide.

  Specific examples of the organotin compounds include carboxylic acid type organotin compounds such as compounds represented by the following formulas (a-1) to (a-14); and the following formulas (b-1) to (b-9). Mercaptide-type organotins such as compounds represented by the following: Sulfide-type organotin compounds such as the compounds represented by the following (c-1) to (c-3); represented by the following (d-1) to (d-4) Chloride-type organotin compounds such as compounds; organotin oxides such as compounds represented by the following (e-1) and (e-2) and these organotin oxides, silicates, dimethyl maleate, diethyl maleate, phthalic acid Reaction products with ester compounds such as dioctyl and the like can be mentioned.

  Other organometallic compounds include methyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, i-propyltriethoxysilane, n-hexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, etc. Trialkoxysilanes: dimethyldiethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-pentyldimethoxy Run, it can be used di -n- octyl diethoxy silane, di -n- cyclohexyl dimethoxysilane, titanium alcoholates and condensates thereof such as dialkoxysilane such as diphenyl dimethoxysilane.

≪Amount of hydrolysis condensation catalyst used≫
The usage-amount of the said hydrolysis-condensation catalyst is 0.001-20 mass parts normally with respect to 100 mass parts of sum total (complete hydrolysis-condensation product conversion) of a compound (B1), Preferably 0.01-10 mass parts More preferably, it is 0.1 to 5 parts by mass.
Here, “in terms of complete hydrolysis condensate” is a theoretical value calculated on the assumption that the silicon compound has been completely hydrolyzed and condensed, and is the OR ² of the silane compound of formula (1) and the formula (2). This corresponds to the mass when OH, OR ⁵ and Y of the silane compound are substituted with ½ mol of oxygen atoms.

<Hydrolysis reaction / condensation reaction>
In order to obtain a specific hydrolyzate / condensate, the compound (b1) is hydrolyzed / condensed by adding water to the starting compound (b1) to cause a hydrolysis reaction and a condensation reaction.

The amount (addition amount) of water used for the hydrolysis reaction and condensation reaction of this compound (b1) is usually 10 with respect to 100 parts by mass of the total of the compound (b1) (in terms of complete hydrolysis condensate). -500 mass parts, Preferably it is 20-200 mass parts, More preferably, it is 30-100 mass parts.
It is preferable that the amount of water used be in the above range since the hydrolysis reaction and the condensation reaction proceed sufficiently and the amount of water to be removed after the reaction is completed is reduced.

≪Solvent≫
Moreover, it is preferable that the hydrolysis reaction and condensation reaction of the compound (b1) are performed in an organic solvent.
As an organic solvent for performing the hydrolysis reaction and condensation reaction of this compound (b1), for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be used.

Specific examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n- Examples include octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.
Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like.
Specific examples of the ethers include tetrahydrofuran and dioxane.
Specific examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like.
Specific examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like. Is mentioned.
These can be used alone or in combination of two or more.
Of these, from the viewpoint of promoting the reaction, it is preferable to use organic solvents other than alcohols, specifically, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like.
Furthermore, these are preferably used in a state where moisture has been removed by performing a dehydration treatment in advance.

  Such an organic solvent can be appropriately used for the purpose of controlling the hydrolysis reaction and condensation reaction of the compound (b1), and the amount used can be appropriately set according to desired conditions. .

≪Reaction conditions≫
In such hydrolysis reaction and condensation reaction of the compound (b1), the reaction conditions are such that the reaction temperature is preferably 10 to 100 ° C, more preferably 15 to 80 ° C, and particularly preferably 20 to 70 ° C. . The reaction time is preferably 0.3 to 48 hours, more preferably 0.5 to 24 hours, and particularly preferably 1 to 12 hours.

  The reaction system for the hydrolysis reaction and condensation reaction of compound (b1) may contain inorganic particles (A) such as silica particles. In particular, when colloidal silica is contained as inorganic particles (A) in the reaction system of the hydrolysis reaction and condensation reaction of compound (b1), the acid used during the production remains in the colloidal silica. If so, this acid also acts as a hydrolysis catalyst, so that the amount of catalyst added can be reduced as necessary.

≪Neutralization≫
Moreover, the silane compound as a reaction product obtained by the hydrolysis reaction and the condensation reaction of the compound (b1) is used as a decatalytic treatment for the reaction product of the hydrolysis reaction and the condensation reaction from the viewpoint of storage stability. It is preferable to perform washing with water. In particular, when a basic compound is used as the hydrolysis-condensation catalyst, it is more preferable to wash with water after neutralizing the reaction product of the hydrolysis reaction and condensation reaction with an acidic compound.

Examples of the acidic compound for neutralizing the reaction product of the hydrolysis reaction and the condensation reaction include the above acidic compounds exemplified as the hydrolysis-condensation catalyst for obtaining a specific hydrolyzate / condensate.
The amount of the acidic compound used is usually 0.5 to 2 N, preferably 0.8 to 1.5 N, more preferably 0 with respect to 1 N of the basic compound used as a catalyst in the hydrolysis reaction and condensation reaction. .9 to 1.3.
Moreover, as an acidic compound, it is preferable to use a water-soluble thing from a viewpoint that it is easy to extract to an aqueous layer at the time of the water washing performed after neutralization.
In addition, when a water-soluble acidic compound is used by dissolving in water, the amount of the acidic compound added to water is usually 0.5 to 100 parts by mass, preferably 1 to 100 parts by mass of water. 50 parts by mass, more preferably 2 to 10 parts by mass.

Washing with water as a decatalyst treatment is performed after adding water to the object to be washed and stirring sufficiently, and confirming that the aqueous phase and the organic solvent phase have been phase-separated. This is done by removing The number of such washings is preferably 1 or more, more preferably 2 or more. Then, the target specific hydrolyzate / condensate is obtained by distilling off the solvent.
Here, the target of washing with water, when neutralization with an acidic compound is performed on the reaction product of the hydrolysis reaction and condensation reaction, the system after neutralization is sufficiently agitated and allowed to stand, It is a reaction product after neutralization obtained by confirming that the aqueous phase and the organic solvent phase have been phase-separated, and then removing the lower layer moisture. On the other hand, when neutralization is not performed It is the reaction product itself of the hydrolysis and condensation reactions.

  The amount of water used for washing is usually 10 to 500 parts by mass, preferably 20 to 100 parts by mass of the total compound (b1) used, that is, the compound (b1) subjected to hydrolysis reaction and condensation reaction. -300 parts, more preferably 30-200 parts.

<Weight average molecular weight>
The weight average molecular weight (Mw) of the specific hydrolyzate / condensate obtained by the hydrolysis reaction and condensation reaction of the compound (b1) is usually from 500 to 100 in terms of polystyrene measured by gel permeation chromatography. 000, preferably 1,000 to 40,000.
When Mw of a specific hydrolyzate / condensate is within the above range, it is possible to suppress the occurrence of cracks during film formation for forming an FPD member and when the formed FPD member is placed at a high temperature. Can do.

<Specific polysiloxane>
The specific polysiloxane constituting the compound (b2) has a structural unit represented by the above formula (2) as an average composition, and is obtained from a halogenated silane. Certain polysiloxanes do not need to have all the halogen groups derived from the halogenated silane as the raw material eliminated and condensed, but only a small part of the halogen groups are eliminated and condensed. In which all halogen groups are eliminated and condensed, in which the halogen group is modified to an alkoxy group with an alcohol, or in which the halogen group is partially hydrolyzed into a silanol group with water, Furthermore, these may be mixed.
The specific polysiloxane includes several types of the specific condensate described above.

In the formula (2) showing a specific polysiloxane, R ³ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, anthonyl, tetranyl, Examples include a pentanyl group.
Furthermore, examples of the group R ³ include substituted derivatives of these organic groups.
Examples of substituents of such substituted derivatives include halogen atoms, unsubstituted or substituted amino groups, hydroxyl groups, mercapto groups, isocyanate groups, glycidoxy groups, 3,4-epoxycyclohexyl groups, (meth) acryloxy groups, and ureidos. Groups, ammonium bases and the like. However, when the group R ³ is composed of a substituted derivative having these substituents, the number of carbon atoms of the substituted derivative is preferably 20 or less including the carbon atoms constituting the substituent.
In the formula (2), when a plurality of R ³ are present, these may be the same as or different from each other.

In Formula (2), R ⁴ represents an organic group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and a phenyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. be able to.
Examples of the acyl group having 1 to 6 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, trioyl group, caproyl group and the like.
In Formula (2), when there are a plurality of R ^{4 s} , these may be the same or different.

As specific polysiloxane, in the above formula (2), a is 0 or more and 4 or less, preferably 0 or more and 2 or less, more preferably 0 or more and 1.8 or less.
When a in Formula (2) is in the above range, the coating film formed in the manufacturing process of the FPD member can have excellent heat resistance.
In addition, the value of a in this Formula (2) can be set by adjusting suitably the kind of halogenated silane used as a raw material, and its mixture ratio.

  Examples of the compound (b2) having such a structure include “MKC silicate” manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin manufactured by Toray Dow Corning Silicone, Inc., Momentive Performance・ Phenyl-modified silicone resin (for example, trade names “SF1555” and “Silshine 151”) manufactured by Materials Japan GK, and silicone alkoxy oligomers (for example, trade names “KR213”, “KR217”, “X”) manufactured by Shin-Etsu Silicone Co., Ltd. Commercial products such as “−40-9227” can be used.

  Preferable specific examples of the specific silane compound (B) used in the present invention include a hydrolysis / condensation product of phenyltrimethoxysilane, a hydrolysis / condensation product of diphenyldimethoxysilane, a combination of phenyltrimethoxysilane and diphenyldimethoxysilane. Hydrolyzed / condensed products are exemplified.

[Contents of inorganic particles (A) and specific silane compound (B)]
In the composition for forming an FPD member of the present invention, the content ratio of the inorganic particles (A) and the specific silane compound (B) is the mass of the inorganic particles (A) and the specific silane compound (B) in terms of SiO _2. When the total amount is 100 parts by mass, the content ratio of the inorganic particles (A) is preferably 65 parts by mass or more and less than 100 parts by mass, and particularly preferably 70 parts by mass or more and 98 parts by mass or less. On the other hand, the content ratio of the specific silane compound (B) is preferably more than 0 parts by mass and 35 parts by mass or less in terms of SiO ₂ .
In the relationship between the inorganic particles (A) and the specific silane compound (B), the content ratio of the inorganic particles (A) is 65 parts by mass or more, that is, the ratio of the specific silane compound (B) is 35 parts by mass or less. Thus, the insulating film formed in the manufacturing process of the FPD member can have excellent heat resistance.
On the other hand, when the content ratio of the specific silane compound (B) exceeds 35 parts by mass, that is, when the content ratio of the inorganic particles (A) is less than 65 parts by mass, the film formation for forming the FPD member is performed. And there exists a possibility that a crack may arise when the formed FPD member is put under high temperature.

[Polymer (C)]
In the composition for forming an FPD member of the present invention, in addition to the inorganic particles (A) and the specific silane compound (B), the polymer (C) [however, corresponding to the specific silane compound (B) except for. It is preferable to contain the above, and thereby, for example, by using a slit coater or the like, the viscosity of the coating liquid at the time of film formation can be increased and the film formability can be improved.

  As such a polymer (C), a homopolymer of a (meth) acrylate compound represented by the following formula (4) (hereinafter also referred to as “specific (meth) acrylate compound”), a specific (meth) acrylate It is preferable to use a copolymer of two or more kinds of compounds and a copolymer of a specific (meth) acrylate compound and another copolymerizable monomer.

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Specific examples of the specific (meth) acrylate compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy. Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate and 3-hydroxybutyl (meth) acrylate;
Alkoxyalkyls such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, etc. ) Acrylate;

The copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with a specific (meth) acrylate compound. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, un Sil (meth) acrylate, dodecyl (meth) acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene Polyalkylene glycol (meth) acrylates such as glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;
Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate;
Unsaturated carboxylic acids such as (meth) acrylic acid, vinyl benzoic acid, maleic acid and vinyl phthalic acid; vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene and isoprene Etc. can be used.

The polymer (C) is particularly preferably a substance that is completely oxidized and removed by the firing temperature at the time of forming the FPD member. For example, a (co) polymer that decomposes or volatilizes at a temperature of 700 ° C. or lower is preferable.
The weight average molecular weight of the polymer (C) is usually 10,000 to 500,000, preferably 100,000 to 300,000 in terms of polystyrene by gel permeation chromatography. When the weight average molecular weight of the polymer (C) is within this range, it is possible to form a thick insulating film without causing cracks.

In the composition for forming an FPD member of the present invention, the content ratio of the polymer (C) is 1 by a mass ratio calculated by the following mathematical formula with respect to the sum of the inorganic particles (A) and the specific silane compound (B). It is preferable that it is -30, More preferably, it is 1-20, More preferably, it is the range of 5-15.
When the content ratio of the polymer (C) is too small, there is a possibility that cracks are likely to occur when an insulating film having a large thickness is formed. On the other hand, when the content ratio of the polymer (C) is excessive, the polymer tends to remain in the film-forming material layer obtained by heat-treating the coating film. By baking the film-forming material layer, There is a possibility that the obtained insulating film is colored and cannot be suitably used as an FPD member.

Wherein, W _A represents the mass of the inorganic particles of FPD member forming composition (A), W _B represents the mass of the specific silane compounds of FPD member forming composition (B), W _C represents the mass of the polymer (C) in the composition for forming an FPD member. ]

[Organic solvent (D)]
In the composition for forming an FPD member of the present invention, for the purpose of adjusting the solid content concentration and viscosity of the composition for forming an FPD member, or adjusting the thickness of an insulating film obtained by firing, an organic solvent ( D) may be contained.
Moreover, by containing this organic solvent (D), the dispersion stability and the storage stability of the composition for forming an FPD member are further improved.

The amount of the organic solvent (D) used can be appropriately set according to desired conditions. For example, the solid content concentration of the obtained FPD member forming composition is preferably 5 to 99% by mass, more preferably The amount is 7 to 95% by mass, particularly preferably 10 to 90% by mass.
Here, the “solid content concentration” indicates the concentration of components other than the organic solvent (D) in the composition for forming an FPD member.

  As the organic solvent (D), alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like exemplified as the organic solvent used in the production of the specific silane compound (B) can be used. . These can be used alone or in combination of two or more.

The organic solvent (D) preferably has a boiling point at 1 atm of 100 ° C. or higher and 300 ° C. or lower, particularly preferably 150 ° C. or higher and 250 ° C. or lower.
When the boiling point at 1 atm is 100 ° C. or less, the FPD member forming composition applied in the application operation is rapidly dried, and the dried product adheres to the surface to be coated. There is a risk of uneven coating. On the other hand, when the boiling point at 1 atm exceeds 300 ° C., the organic solvent (D) tends to remain in the insulating film obtained through the baking treatment, resulting in a decrease in strength or surface of the insulating film. Roughness may occur.

Specific examples of such an organic solvent (D) include alcohols such as 1-pentanol, 2-pentanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 2-ethylbutanol, n -Hexanol (n-hexyl alcohol), 2-ethylhexanol, 2-octanol, terpineol, i-butyl alcohol, n-butyl alcohol, n-octyl alcohol, 2-heptyl alcohol, ethylene glycol, ethylene glycol diacetate, ethylene glycol Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether (2-butoxyethanol), ethylene glycol monobutyl ether acetate, ethylene glycol Monohexyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Examples thereof include monobutyl ether, propylene monomethyl ether acetate, diacetone alcohol and the like.
Aromatic hydrocarbons include toluene, xylene, etc., ethers include diethyl acetal, dibutyl ether, dioxane, etc., and ketones include acetylacetone, ethyl-n-butylketone, diacetone. Examples include alcohol, methyl isobutyl ketone, methyl-n-butyl ketone, methyl-n-propyl ketone, diethyl ketone, diisobutyl ketone, diisopropyl ketone, and the like. Examples of esters include ethyl acetoacetate, methyl acetoacetate, ethyl benzoate, and benzoic acid. Examples include methyl acid, amyl acetate, isoamyl acetate, propyl acetate, butyl acetate, diethyl carbonate, methyl lactate, ethyl lactate, and dibutyl maleate.
These can be used alone or in combination of two or more.

[Method for preparing composition for forming FPD member]
The composition for forming an FPD member of the present invention includes an organic solvent (D), inorganic particles (A), a specific silane compound (B), and, if necessary, a polymer (C), a basic compound, It can be prepared by adding a hydrolysis-condensation catalyst comprising an acidic compound or an organometallic compound and dispersing the inorganic particles (A) in the organic solvent (D).
In such a method for preparing an FPD member forming composition, depending on the dispersibility of the inorganic particles (A) and the like, for example, ball mill, sand mill (bead mill, high shear bead mill), hogenizer, ultrasonic homogenizer, nanomizer, propeller mixer It is preferable to use a known disperser such as a high shear mixer or a paint shaker, and a fine particle dispersion ball mill and a sand mill (bead mill, high shear bead mill) having high dispersion performance are particularly preferably used.

[Flat Panel Display Manufacturing Method]
When the composition for forming an FPD member of the present invention is used as a material for forming a flat panel display member, the FPD member-forming composition is applied on a substrate, and then subjected to a drying process and a baking process to obtain an FPD member. Obtainable.
Moreover, according to the FPD member which should be formed, the patterned member can also be formed by patterning the coating film formed on the board | substrate to the predetermined shape.

  As a method for applying the composition for forming an FPD member of the present invention, for example, a method of applying using a brush, roll coater, bar coater, flow coater, centrifugal coater, ultrasonic coater, (micro) gravure coater, etc .; A spray coating method; a screen process method; an electrodeposition method; a vapor deposition method and the like can be used.

When the composition for forming an FPD member of the present invention has fluidity, for example, the FPD member-forming composition is applied to the surface of a glass substrate by a screen printing method or the like to form a coating film. The film-forming material layer is formed by drying the coating film, and then the obtained film-forming material layer is fired to decompose and remove organic substances (solvents, etc.) and sinter. Thus, an FPD member made of a target insulating film can be formed.
Here, the drying treatment condition of the coating film is, for example, 40 ° C. to 150 ° C. for 1 to 60 minutes. Moreover, the thickness of the film forming material layer is, for example, 5 to 250 μm.
Moreover, as for the baking process conditions of a film formation material layer, heating temperature (baking process temperature) is 400-650 degreeC, for example, and baking time is 1-360 minutes, for example.

In the composition for forming an FPD member of the present invention, a film having a thickness (dry film thickness) of about 0.05 to 20 μm can be formed by one coating, and a thickness (dry film thickness) can be formed by two coatings. Can form a film having a thickness of about 0.1 to 40 μm.
Here, “one-time coating” means that when the composition for forming an FPD member is applied onto a substrate, the application operation of the composition for forming an FPD member and the drying treatment of the coating film obtained thereby are defined as one cycle. Means that this cycle is carried out only once, and “twice coating” means that the application operation of the composition for forming an FPD member and the drying treatment of the coating film obtained thereby are regarded as one cycle. It means that it is repeated twice.

According to the composition for forming an FPD member of the present invention, an insulating film excellent in balance between transparency and heat resistance can be formed by containing inorganic particles (A) and a specific silane compound (B). In addition, since a thick insulating film having smoothness can be obtained with a small number of coatings, cracks do not occur at the time of thick film formation, excellent in transparency and heat resistance, and smoothness. A high insulating film can be obtained with a small number of coatings.
The composition for forming an FPD member of the present invention can be used as a dielectric layer forming material, a partition wall forming material, an electrode forming material, a resistor forming material, a phosphor forming material, a color filter forming material, a black matrix forming material, and the like. However, since the obtained insulating film has high smoothness, it can be suitably used as a dielectric layer forming material.

Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, “parts” are based on mass unless otherwise specified.
Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Optical property evaluation:
The composition for forming an FPD member was applied on quartz glass so that the dry film thickness was 15 μm, then dried at 100 ° C. for 20 minutes, and then baked at 500 ° C. for 1 hour to form an insulating film. About the obtained insulating film, the transmittance | permeability was measured using the haze tester (touch panel type haze computer HZ-2S) by Suga Test Instruments Co., Ltd., and the following reference | standard evaluated.
A: When the transmittance exceeds 80% B: When the transmittance is 70% or more and 80% or less C: When the transmittance is less than 70%

(2) Evaluation of crack occurrence:
A 100 μm applicator is used on a substrate on which a plurality of reverse-tapered silver electrodes having a top surface width of 100 μm, a bottom surface width of 80 μm, and a height of 12 μm are provided at an interval of 100 μm. A coating film was formed by coating, and after drying the coating film at 100 ° C. for 20 minutes, an insulating film was formed by baking at 500 ° C. for 1 hour using an oven. The obtained insulating film was cut into 2 cm squares to prepare test pieces, and the surface of the test pieces was observed with an electron microscope at a magnification of 600 times, so that the presence or absence of cracks on the surface of the test pieces was observed. Were evaluated according to the following criteria.
A: When the number of cracks generated in the vicinity of the electrode in the entire test piece is 0 to 4 ○: When the number of cracks generated in the vicinity of the electrode is 5-10 in the entire test piece ×: The electrode in the entire test piece When the number of cracks in the vicinity is 10 or more

[Preparation of specific silane compound (B)]
49 parts of phenyltrimethoxysilane and 142 parts of diphenyldimethoxysilane (trifunctional / 2 functional = 30/70 (mass ratio): completely hydrolyzed condensate), 763 parts of methyl isobutyl ketone as a solvent, 152 parts of water, As a catalyst, 19 parts of triethylamine was mixed, and a hydrolysis condensation reaction was performed at 60 ° C. for 3 hours. After cooling the obtained reaction product to room temperature, 156 parts of 6 mass% oxalic acid aqueous solution was added, and neutralization reaction was performed at room temperature for 1 hour. Thereafter, the aqueous layer was separated and the organic phase was washed with 150 parts of water. After performing this washing operation three times, the solvent was distilled off to obtain a specific silane compound having a weight average molecular weight (Mw) of 5,000 (hereinafter referred to as “silane compound (B-1)”).

Moreover, as the specific silane compound (B), the following commercially available products were prepared in addition to the silane compound (B-1).
Silane compound (B-2):
Silicone alkoxy oligomer “KR217” manufactured by Shin-Etsu Silicone
Structure: R ³ is a phenyl group and R ⁵ is a methyl group.
Silane compound (B-3):
Silicone alkoxy oligomer “KR213” manufactured by Shin-Etsu Silicone
Structure: R ³ is a phenyl group and R ⁴ and R ⁵ are methyl groups.
Silane compound (B-4):
Silicone alkoxy oligomer “X-40-9227” manufactured by Shin-Etsu Silicone
Structure: R ³ is a phenyl group and R ⁴ and R ⁵ are methyl groups.
Silane compound (B-5):
Phenyl-modified silicone oil “SF1555” manufactured by Momentive Performance Materials Japan GK
Silane compound (B-6):
Momentive Performance Materials Japan GK Phenyl-modified silicone resin “Silshine 151”

[Example 1]
95 parts of silica particles (hereinafter referred to as “silica particles (A-1)”) having a particle diameter in the range of 70 to 100 nm in a mixed solvent composed of 227 parts of 2-ethylhexanol and 6 parts of 2-butoxyethanol. And 5 parts of a silane compound (B-1) and iso-butyl methacrylate (hereinafter “i-BMA”). ) And hydroxypropyl methacrylate (hereinafter referred to as “HPMA”) (with a monomer mass ratio of i-BMA / HPMA = 80/20 and a weight average molecular weight of 400,000). i-BMA) ₈₀ (HPMA) ₂₀ ")) 9 parts were stirred and mixed to prepare a composition for forming an FPD member. The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

[Example 2]
In a mixed solvent composed of 227 parts of 2-ethylhexanol and 6 parts of 2-butoxyethanol, 97.5 parts of silica particles (A-1), 2.5 parts of silane compound (B-1), and poly (i -BMA) A composition for forming an FPD member was prepared by stirring and mixing 9 parts of ₈₀ (HPMA) ₂₀ . The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 3
A composition for forming an FPD member was prepared in the same manner as in Example 1 except that the silane compound (B-2) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 4
A composition for forming an FPD member was prepared in the same manner as in Example 2 except that the silane compound (B-2) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 5
A composition for forming an FPD member was prepared in the same manner as in Example 1 except that the silane compound (B-3) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 6
A composition for forming an FPD member was prepared in the same manner as in Example 1 except that the silane compound (B-4) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 7
A composition for forming an FPD member was prepared in the same manner as in Example 1 except that the silane compound (B-5) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

Example 8
A composition for forming an FPD member was prepared in the same manner as in Example 1 except that the silane compound (B-6) was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

[Comparative Example 1]
An FPD member-forming composition was prepared in the same manner as in Example 1 except that tetraethoxysilane was used instead of the silane compound (B-1). The results of optical property evaluation and crack generation evaluation of the obtained FPD member forming composition are shown in Table 1 below.

It is a schematic diagram which shows the cross-sectional shape of alternating current type PDP. It is a schematic diagram which shows the cross-sectional shape of FED.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Glass substrate 102 Glass substrate 103 Partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent substance 108 Dielectric layer 109 Dielectric layer 110 Protective film 111 Partition 201 Glass substrate 202 Glass substrate 203 Insulating layer 204 Transparent electrode 205 Emitter 206 Cathode electrode 207 Phosphor 208 Gate 209 Spacer

Claims (8)

Inorganic particles (A);
Selected from the group consisting of at least one organosilane represented by the following formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, and a polysiloxane having an average composition represented by the following formula (2) The composition for flat panel display member formation containing the at least 1 sort (s) of silane compound (B).
Formula (1) R ¹ _n Si (OR ² ) _4-n
[Wherein, R ¹ represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and when two R ¹ are present, they may be the same as or different from each other. R < ² > shows a C1-C5 alkyl group or a C1-C6 acyl group each independently. n is an integer of 1 to 3. ]
Formula (2) R ³ _a1 R ⁴ _a2 SiO _b (OH) _c (OR ⁵ ) _d (Y) _e
[Wherein R ³ represents a monovalent organic group having an aromatic ring having 1 to 3 carbon atoms, and when a plurality of R ³ are present, they may be the same or different from each other. . R ⁴ represents an organic group having 1 to 8 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other. R ⁵ represents an organic group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and a phenyl group, and when a plurality of R ⁵ are present, they are They may be the same or different. R ⁴ and R ⁵ may be the same or different. Y represents a halogen atom or a hydrogen atom. a1 is greater than 0 and 4 or less, and a2, b, c, d, and e are each independently 0 or more and 4 or less, and satisfy a1 + a2 + b / 2 + c + d + e = 4. ]   Polymer (C) [However, those corresponding to the silane compound (B) are excluded. ] The composition for flat panel display member formation of Claim 1 characterized by the above-mentioned.   The composition for forming a flat panel display member according to claim 2, wherein the polymer (C) has a polystyrene equivalent weight average molecular weight of 10,000 to 500,000.   The composition for forming a flat panel display member according to claim 2 or 3, wherein the mass ratio of the polymer (C) to the sum of the inorganic particles (A) and the silane compound (B) is 1 to 30. object.   The composition for forming a flat panel display member according to any one of claims 1 to 4, wherein silica particles are used as the inorganic particles (A).   6. The flat panel display according to claim 5, wherein the silica particles contain particles having a particle diameter in the range of 0.03 to 0.3 [mu] m measured by a laser diffraction method in a volume basis of 50% or more. A composition for forming a member. 65 parts by weight or more and less than 100 parts by weight of inorganic particles (A), and silane compound (B) in excess of 0 parts by weight in terms of SiO ₂ to 35 parts by weight or less (provided that inorganic particles (A) and silane compound (B) The composition for forming a flat panel display member according to any one of claims 1 to 6, wherein the total amount with respect to the SiO ₂ equivalent is 100 parts by weight.   The composition for forming a flat panel display member according to any one of claims 1 to 7, wherein the composition is used for forming a dielectric layer of a flat display panel.

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