JP2010192377A - Flat panel display member-forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flat panel display member-forming composition that can obtain a cured body having large thickness with the fewer number of coating processes, can restrain generation of cracks in the obtained cured body, and can use it as a forming material of the flat panel display member. <P>SOLUTION: The flat panel display member-forming composition includes (A) silica particles, (B) at least one silane compound selected from a specific organosilane, hydrolyzate of the organosilane, condensate of the organosilane and polysiloxane having an average composition expressed in a specific formula, and (C) a polymer having a specific structure unit. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for forming a flat panel display member used as a material for forming a panel member of a flat panel display, and more particularly to a composition for forming a flat panel display member comprising a composition containing silica particles. .

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.
FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”), and FIG. 2 is an explanatory view showing a cross-sectional shape of a panel member of the FED.
In FIG. 1, 1 and 2 are glass substrates, 3 and 11 are partition walls, 4 is a transparent electrode, 5 is a bus electrode, 6 is an address electrode, 7 is a phosphor, 8 and 9 are dielectric layers, and 10 is a protective film. is there. 2, 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 a dielectric, barrier rib, electrode, phosphor, color filter, and black stripe (matrix) as a panel member (FPD member) of such a flat panel display, for example, a composition containing inorganic powder and a binder resin A method is known in which an inorganic powder-containing resin layer is formed on a substrate by using an object as a material, and this is fired (see Patent Document 1).

  On the other hand, as a material for forming the FPD member, a situation in which the FPD member is placed at a high temperature in the FPD panel manufacturing process occurs. Therefore, the FPD member requires high heat resistance. Particularly, in the FPD member used for forming the front plate of the FPD, since it is also important to have high transparency and smoothness, various compositions have been proposed to meet these demands. ing.

Further, from the viewpoint of forming a member having a low dielectric constant, a composition containing a silica compound has been studied (see, for example, Patent Document 2 and Patent Document 3).
However, when an FPD member is formed with such a composition, there is a problem that cracks occur.

JP-A-9-102273 JP 2001-135222 A JP 2007-299642 A

  Based on the above circumstances, the present invention solves the above-mentioned problems, and in the material for forming the FPD member, the target film can be formed with a small number of coatings from the viewpoint of panel productivity. As a result of diligent research focusing on the fact that it is important to obtain a thickness, it was found that the object is to obtain a cured product having a large thickness with a small number of coatings. An object of the present invention is to provide a composition for forming a flat panel display member that can suppress the occurrence of cracks in the cured product and can be used as a material for forming a flat panel display member.

The composition for forming a flat panel display member of the present invention is
(A) silica particles,
(B) It comprises 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). At least one silane compound selected from the group,
(C) A polymer having a structural unit represented by the following formula (3) is contained.

[Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more 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 0-3. ]

[In formula, R < ³ > shows a C1-C8 organic group, and when two or more exist, they may mutually be same or different. 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. It may be. R ³ and R ⁴ may be the same or different. Y represents a halogen atom or a hydrogen atom. a, b, c, d, and e are each independently 0 or more and 4 or less, and satisfy a + 2b + c + d + e = 4. ]

[Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Indicates. ]

  In the composition for flat panel display member formation of this invention, it is preferable that the polymerization average molecular weight of polystyrene conversion of (C) polymer is 10,000-500,000.

  In the composition for flat panel display member formation of this invention, it is preferable that the mass ratio of (C) polymer with respect to a total of 100 mass parts of (A) silica particle and (B) silane compound is 1-30.

  In the composition for forming a flat panel display member of the present invention, (A) 65 parts by mass or less of silica particles in terms of solid matter and (B) 0 part by mass of silane compound in terms of complete hydrolysis condensate. More than 35 parts by mass (however, (A) the total amount of silica particles in terms of solids and (B) the total amount of silane compounds in terms of complete hydrolysis condensate is 100 parts by mass). Is preferred.

  The composition for forming a flat panel display member of the present invention is preferably used as a dielectric forming material for a flat panel display.

  According to the composition for forming a flat panel display member of the present invention, since it contains a specific polymer together with silica particles and a specific silane compound, excellent film formability is obtained by the action of this polymer. Therefore, it is possible to obtain a cured body having a large thickness with a small number of coatings, and it is possible to suppress the occurrence of cracks in the formed cured body. Therefore, it is suitable as a material for forming a flat panel display member. Can be used.

It is a typical sectional view showing a general PDP. It is sectional drawing for description which shows a general FED.

Hereinafter, 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 is a composition comprising an A component composed of silica particles, a B component composed of a specific silane compound, and a C component composed of a specific polymer, It is used as a material for forming a flat panel display member (FPD member).

[(A) Silica particles]
In the composition for forming a flat panel display member of the present invention, the silica particles are contained as the component A. In particular, when the composition for forming a flat panel display member is used as a dielectric forming material, it is obtained. The dielectric can have a low dielectric constant.

As the raw material of the silica particles according to the present invention, in the form of powder, an aqueous sol or colloid dispersed in water, or a solvent dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene A system sol or colloid form 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. Further, in the solvent-based 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 or more and 40% by mass or less. is there.
In addition, when the colloidal silica in which the silica particles are dispersed in an organic solvent is used as the raw material for the silica particles as the component A, the obtained cured product (FPD member) has excellent transparency and heat resistance. It becomes.

The silica particles according to the present invention 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. Preferably there is.
Here, in the present specification, the particle size distribution of the silica particles is a particle size distribution measuring device in a state where the silica particles are dispersed in an organic solvent (for example, Nanotrack particle size distribution measuring device “UPA-150” manufactured by Nikkiso Co., Ltd.). 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 less than 50% on a volume basis. May cause cracks during film formation for forming a cured body (FPD member) and when the formed cured body (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).
In the silica particles according to the present invention, the content ratio of the particles having a particle diameter in the range of 0.03 to 0.3 μm may be 50% or more on a volume basis. It may be a mixture of particles having a particle size distribution.

As a specific example of the raw material of the silica particles according to the present invention, as a powder shape, for example, “# 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 ”,“ Silo Hovic 100 ”manufactured by Fuji Silysia, etc., and the like whose surface is hydrophobized. 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.
In addition, when using colloidal silica as a raw material of the silica particle which comprises A component, when preparing the flat panel display member formation composition of this invention, other components (specifically, at least B component) And a silane compound as a C component and a polymer as a C component), or can be added to a reaction system for hydrolysis and condensation reaction to obtain a silane compound as a B component described later.

  Here, in the composition for forming a flat panel display member of the present invention, inorganic particles other than silica particles can be used together with silica particles.

Examples of inorganic particles that can be used in combination with silica particles include ZrO ₂ , Al ₂ O ₃ , 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, PbTe, GeSi, FeSi 2, CrSi 2, CoSi 2, MnSi 1.73 _{Mg 2 Si, β-B,} BaC, BP, TiB 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 ferrite, Li ferrite, those including, for example, Sr ferrite.
These inorganic particles can be used alone or in combination of two or more, and particles composed of a composite of inorganic compounds can also be used.

The content ratio of the inorganic particles is preferably less than 40 parts by mass, more preferably less than 30 parts by mass with respect to 100 parts by mass of the total of the silica particles as the component A and the inorganic particles.
When the content ratio of the inorganic particles is within the above range, the possibility of adversely affecting the optical characteristics can be reduced.

[(B) Silane compound]
The silane compound as the B component constituting the composition for forming a flat panel display member of the present invention is an organosilane represented by the above formula (1) (hereinafter also referred to as “(b1) component”) or the formula ( 1) hydrolyzate of organosilane, condensate of organosilane, and polysiloxane having an average composition represented by the above formula (2) (hereinafter these hydrolyzate, condensate and polysiloxane are Collectively, it is a compound selected from the group consisting of “(b2) component”.
The silane compound as the component B only needs to contain at least the component (b1) or the component (b2). Moreover, even if the organosilane constituting the component (b1) is one type, it is at least two types. The hydrolyzate and condensate constituting the component (b2) and the polysiloxane having the average composition represented by the formula (2) may each be one type or two or more types. Good.

((B1) component)
(B1) In the formula (1) showing the organosilane constituting the component, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl Group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.
Furthermore, examples of the group R ¹ include substituted derivatives of these organic groups.
Examples of the substituent of the substituted derivative representing the group R ¹ include a halogen atom, an unsubstituted or substituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acrylic group. An oxy group, a ureido group, an ammonium base, etc. are mentioned. However, when the group R ¹ is composed of a substituted derivative having these substituents, the carbon number of the substituted derivative is preferably 8 or less including the carbon atoms constituting the substituent.
In the formula (1), when there are a plurality of R ¹ (specifically, 2 or 3), these may be the same as 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.
Here, 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.
Examples of the alkyl group having 1 to 5 carbon atoms representing the group R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- Examples include a pentyl group.
The acyl group having 1 to 6 carbon atoms a group R ^2, for example, acetyl group, propionyl group, butyryl group, valeryl group, etc. caproyl group.

Specific examples of such organosilane as the component (b1) include trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonoethoxysilane, tri-n-propylmonomethoxysilane, tri-n-propylmonoethoxysilane, Tri-i-propylmonomethoxysilane, tri-i-propylmonoethoxysilane, tri-n-butylmonomethoxysilane, tri-n-butylmonoethoxysilane, di-methyl-phenylmonomethoxysilane, di-ethyl-phenyl Monoalkoxysilanes such as monoethoxysilane (n = 3 in formula (1));
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane (n = 0 in formula (1));
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Cypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- Trialkoxysilanes (n = 1 in the formula (1)) such as (meth) acrylicoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl Diethoxysilane, diphenyl Silane, dialkoxy silanes such as diphenyl diethoxy silane (n = 2 in formula (1));
Examples thereof include methyltriacetyloxysilane (n = 1 in formula (1)) and dimethyldiacetyloxysilane (n = 2 in formula (1)).
These can be used alone or in combination of two or more.

((B2) component)
The component (b2) includes a hydrolyzate of the organosilane represented by the formula (1) constituting the component (b1) and a polysiloxane (organosilane obtained from the organosilane represented by the formula (1). And polysiloxanes obtained from halogenated silanes.

(Organosilane hydrolyzate and condensate)
The hydrolyzate of the organosilane constituting the component (b2) is a hydrolyzate produced by hydrolyzing the organosilane represented by the formula (1) constituting the component (b1), and (b2 The condensate of the organosilane constituting the component is a hydrolyzate produced by hydrolyzing the organosilane represented by the formula (1) constituting the component (b1). A silanol group formed by hydrolysis of an OR ² group constituting an organosilane represented by a certain formula (1) is condensed to form a Si—O—Si bond.
In the hydrolyzate of organosilane constituting the component (b2), at least one of 1-4 OR ² groups constituting the organosilane represented by the formula (1) as a raw material is hydrolyzed. it is sufficient that, specifically, for example, those in which one oR ² group is hydrolyzed, those two or more oR ² group is hydrolyzed, or even what they will be mixed Good. In the organosilane condensate, the silanol groups produced by hydrolysis need not be all condensed, but some silanol groups are condensed, most (including all) silanol groups. It may be a condensed group or a mixture thereof.

(Hydrolysis condensation catalyst)
Catalyst used for hydrolysis reaction and condensation reaction to obtain the hydrolyzate of organosilane and the condensate of organosilane (hereinafter collectively referred to as “hydrolyzate / condensate of organosilane”) ( As the hydrolysis condensation catalyst, basic compounds, acidic compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as “organometallic compounds and / or partial hydrolysates thereof” are collectively referred to as “organometallics”. Compound ")).

(Basic compound)
Examples of the basic compound include ammonia (including aqueous ammonia solution); organic amine compound; alkali metal or alkaline earth metal hydroxide such as sodium hydroxide and potassium hydroxide; alkali such as sodium methoxide and sodium ethoxide Examples thereof include metal alkoxides. Of these, ammonia and organic amine compounds are preferred.

Examples of the organic amine compound include alkylamine, alkoxyamine, alkanolamine, arylamine, tetramethylammonium hydroxide and pyridine.
Of these, alkylamine, tetramethylammonium hydroxide and pyridine are preferred.

  Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine And alkylamines having an alkyl group having 1 to 8 carbon atoms such as triethylamine, tripropylamine, and tributylamine.

The said basic compound can be used individually by 1 type or in combination of 2 or more types.
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.

(Acidic compounds)
Examples of the acidic compound include organic acids and inorganic acids, and maleic acid, maleic anhydride, methanesulfonic acid and acetic acid are particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.

(Organometallic compounds)
Examples of the organometallic compounds include, for example, a compound represented by the following general formula (1) (hereinafter also referred to as “specific organometallic compound”), one tin atom having one alkyl group having 1 to 10 carbon atoms. Alternatively, two bonded tetravalent tin organometallic compounds (hereinafter referred to as “specific organotin compounds”) and partial hydrolysates thereof (specifically, partial hydrolysates and specific organics of specific organometallic compounds). A partial hydrolyzate of a tin compound).

[Wherein, M represents a 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 a monovalent monovalent group having 1 to 6 carbon atoms. It represents a hydrocarbon group, R ¹² is a monovalent hydrocarbon group or an alkoxyl group having 1 to 16 carbon atoms having 1 to 6 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 general formula (1), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms representing R ¹⁰ and R ¹¹ and R ¹² include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group and the like.
As the alkoxyl group having 1 to 16 carbon atoms a group R ^12, for example a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy group, sec- butoxy group, t-butoxy group, A lauryloxy group, a stearyloxy group, etc. are mentioned.

  Specific examples of the organotin compounds include carboxylic acid type organotin compounds, mercaptide type organotin compounds, sulfide type organotin compounds, chloride type organotin compounds, organotin oxides, and these organotin oxides, silicates, and maleates. Reaction products with ester compounds such as dimethyl acid, diethyl maleate, dioctyl phthalate and the like can be mentioned.

The amount of the hydrolysis condensation catalyst used is usually 0.001 to 100 parts by mass of the total of organosilane monomers (organosilane represented by the formula (1) as a raw material) (in terms of complete hydrolysis condensate). 20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
Here, the complete hydrolysis-condensation product relating to the organosilane monomer (organosilane represented by the formula (1)) means that all of the OR ² groups (100%) contained in the organosilane monomer are hydrolyzed to form OH groups. And a Si-OH group is formed, and the Si-OH group is completely condensed to form a siloxane structure.

(Hydrolysis reaction / condensation reaction)
In order to obtain the hydrolyzate / condensate of organosilane, water is added to the organosilane represented by the formula (1) (hereinafter also referred to as “organosilane monomer”) as a raw material, The organosilane monomer is hydrolyzed and condensed by a condensation reaction.

The amount of water used for the hydrolysis reaction and condensation reaction of the organosilane monomer (addition amount) is usually 10 to 500 with respect to 100 parts by mass of the total organosilane monomer (in terms of complete hydrolysis condensate). It is 20 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)
The hydrolysis reaction and condensation reaction of the organosilane monomer are preferably performed in an organic solvent.
Examples of the organic solvent used in the reaction system of the hydrolysis reaction and condensation reaction of the organosilane monomer include alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like.
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 organosilane monomer, and the amount used can be appropriately set according to desired conditions.

(Reaction conditions)
In such hydrolysis reaction and condensation reaction of the organosilane monomer, 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 organosilane monomer hydrolysis reaction and condensation reaction reaction system may contain silica particles as component A. In particular, when colloidal silica as a raw material for silica particles is contained in the reaction system of the hydrolysis reaction and condensation reaction of the organosilane monomer, the acid used during the production remains in the colloidal silica. In this case, since this acid also acts as a hydrolysis catalyst, the addition amount of the catalyst may be reduced as necessary.

(Neutralization)
In addition, the silane compound as a reaction product obtained by hydrolysis reaction and condensation reaction of the organosilane monomer is washed with water as a decatalytic treatment for the reaction product of hydrolysis reaction and condensation reaction from the viewpoint of storage stability. It is preferable to carry out. 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 and condensation catalyst for obtaining the hydrolyzate and condensate of organosilane.
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 by adding water to the object to be washed and stirring sufficiently, confirming that the water phase and the organic solvent phase have been separated, and then lower layer moisture. By removing the. The number of such washings is preferably 1 or more, more preferably 2 or more. Then, the hydrolyzate and condensate of the target organosilane are obtained by distilling a solvent off.
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 then left 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 weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of all organosilane monomers used, that is, organosilane monomers subjected to hydrolysis and condensation reactions. Parts, more preferably 30 to 200 parts by mass.

(Weight average molecular weight)
The weight average molecular weight (Mw) of hydrolyzate / condensate of organosilane as component (b2) obtained by hydrolysis reaction and condensation reaction of the above organosilane monomer is a polystyrene equivalent value measured by gel permeation chromatography. 800 to 50,000, preferably 1,000 to 40,000.
When the weight average molecular weight of the hydrolyzate / condensate of organosilane as the component (b2) is in the above range, the cured product (FPD member) formed during the film formation for forming the cured product (FPD member). ) Can be prevented from being cracked by being placed under high temperature.

  As such a silane compound related to the component B, polysiloxane obtained from a halogenated silane can also be used. This polysiloxane does not need to have all halogen groups derived from the halogenated silane as a raw material eliminated and condensed, but a part of halogen groups eliminated and condensed, most (including all) In which the halogen group is 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. May be mixed.

(Polysiloxane)
The polysiloxane having the average composition represented by the formula (2) constituting the component (b2) contains the same kind of some of the above-mentioned organosiloxane condensates represented by the formula (1). ing.

(B2) In the formula (2) showing the polysiloxane constituting the component, R ³ is a monovalent organic group having 1 to 8 carbon atoms, and specifically includes, for example, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.
Furthermore, examples of the group R ³ include substituted derivatives of these organic groups.
Examples of the substituent of the substituted derivative showing the group R ³ include a halogen atom, an unsubstituted or substituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acrylic group. An oxy group, a ureido group, an ammonium base, etc. are mentioned. 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 8 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.
Here, in the formula (2), when there are a plurality of R ^{4 s} , these may be the same as or different from each other.
Examples of the alkyl group having 1 to 6 carbon atoms representing the group R ⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- Examples thereof include a pentyl group.
The acyl group having 1 to 6 carbon atoms a group R ^4, such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, Torioiru group, such as caproyl group.

As the polysiloxane having an average composition represented by the formula (2), in the formula (2), a is usually 0 or more and 2 or less, 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 production process of the cured body (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 organosilane monomer used as a raw material or a halogenated silane, and its mixture ratio.

  The weight average molecular weight (Mw) of this polysiloxane is 800 to 50 in terms of polystyrene measured by gel permeation chromatography, as in the hydrosilane / condensate of organosilane represented by the above formula (1). 000, preferably 1,000 to 40,000.

  Examples of the component (b2) according to the present invention having such a structure include “MKC silicate” manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, and silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd. Commercially available products (polysiloxane) such as terminal hydroxypolysiloxane resin (for example, trade name “YR3370”) manufactured by Momentive Performance Materials Japan G.K. and silicone resin manufactured by Shin-Etsu Chemical Co., Ltd. can be used. .

  Preferred specific examples of the silane compound as the component B according to the present invention include hydrolysis / condensation product of dimethyldimethoxysilane, hydrolysis / condensation product of methyltrimethoxysilane, and co-hydrolysis of dimethyldimethoxysilane and methyltrimethoxysilane. Examples include decomposition / condensation products.

(Contents of (A) silica particles and (B) silane compound)
The content ratio of the silica particles as the component A and the content ratio of the silane compound as the component B in the composition for forming a flat panel display member of the present invention are the mass of the silica particles in terms of solids and the complete hydrolysis of the silane compound. In the case where the total with the mass in terms of condensate is 100 parts by mass, the content ratio of the silica particles 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. is there. On the other hand, it is preferable that the content rate of a silane compound exceeds 0 mass part and is 35 mass parts or less in conversion of a complete hydrolysis-condensation product.
In the relationship between the silica particles as the component A and the silane compound as the component B, the ratio of the silica particles is 65 parts by mass or more, that is, the ratio of the silane compound is 35 parts by mass or less. The coating film formed in the manufacturing process can have excellent heat resistance.
On the other hand, when the ratio of the silane compound exceeds 35 parts by mass, that is, when the ratio of the silica particles is less than 65 parts by mass, the cured body formed during the film formation for forming the cured body (FPD member) ( If the FPD member is placed at a high temperature, cracks may occur.
Here, in this specification, the complete hydrolysis-condensation product related to the silane compound includes the OR ² group according to the formula (1), the OR ⁴ group according to the formula (2), and the Y group contained in the silane compound. All of (100%) of the above form a Si—OH group by hydrolysis, and the Si—OH group is completely condensed to form a siloxane structure.

[(C) Polymer]
The polymer as the component C used in the composition for forming a flat panel display member of the present invention is to increase the viscosity of the coating solution when forming a film by using, for example, a slit coater, and to improve the film formability. It is contained.
The polymer as the component C is a polymer having a structural unit represented by the above formula (3).

In the formula (3), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ represents a hydrogen atom or a carbon number 1 to 1 4 represents an alkyl group.
Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms a group R ^6, for example, methylene group, ethylene group, propylene group, and butylene group.
The alkyl group having 1 to 4 carbon atoms a group R ^7, a methyl group, an ethyl group, a propyl group and a butyl group.

  In the polymer as the component C, the content ratio of the structural unit represented by the formula (3) is 10 to 50% by mass, preferably 20 to 40% with respect to 100% by mass of the entire structural unit constituting the polymer. % By mass. By containing the structural unit represented by Formula (3) in the above range, an FPD member having excellent crack resistance and optical properties can be obtained.

As such a polymer, a homopolymer of a (meth) acrylate compound represented by the following formula (4), a copolymer of two or more of a (meth) acrylate compound represented by the formula (4), and The copolymer of the (meth) acrylate compound represented by Formula (4) and another copolymerizable monomer is included.
As a polymer which comprises the composition for flat panel display member formation of this invention, the copolymer of the (meth) acrylate compound represented by Formula (4) and another copolymerizable monomer is preferable.

[Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Indicates. ]

Specific examples of the (meth) acrylate compound represented by the formula (4) include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxybutyl (meth) acrylate, 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 and the like.

The other copolymerizable monomer used for copolymerization with the (meth) acrylate compound represented by formula (4) is not particularly limited as long as it is a compound copolymerizable with the (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, undecyl (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 Is mentioned.

  As such a polymer as the component C, a substance that is completely oxidized and removed by a firing temperature (400 to 600 ° C.) at the time of forming a cured body (FPD member) is particularly preferable. Volatile (co) polymers are preferred.

  Here, as a specific example of a preferable (co) polymer as the polymer as the component C, for example, a copolymer of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and Examples thereof include a copolymer with isobutyl (meth) acrylate and a copolymer of 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate and isobutyl (meth) acrylate.

Moreover, the weight average molecular weight of the polymer which comprises C component is 10,000-500,000 normally in polystyrene conversion, Preferably it is 100,000-400,000.
By setting the molecular weight of the polymer within this range, a thick cured body (FPD member) can be formed without causing cracks.

The content ratio of the polymer as the C component in the composition for forming a flat panel display member of the present invention is a mass ratio with respect to a total of 100 parts by mass of the silica particles as the A component and the silane compound as the B component, specifically The mass ratio calculated by the following mathematical formula (1) is in the range of 1 to 30, preferably 1 to 20.
When the content ratio of the polymer is too small, that is, when the mass ratio to the total of the silica particles and the silane compound is 1 or less, there is a possibility that cracks are likely to occur after film formation. On the other hand, when the content ratio of the polymer is excessive, that is, when the mass ratio with respect to the total of the silica particles and the silane compound is 30 or more, the C-component is added to the film-forming material layer obtained by thermally decomposing the coating film. The polymer is likely to remain, and the fired layer (cured layer) obtained by firing the film-forming material layer becomes colored and cannot be suitably used as an FPD member.

[Wherein W _A represents the mass of silica particles as the A component in the composition for forming a flat panel display member, and W _B represents the silane compound as the B component in the composition for forming a flat panel display member. The mass indicates the mass, and W _C indicates the mass of the polymer as the C component in the composition for forming a flat panel display member. ]

[(D) Organic solvent]
In the composition for forming a flat panel display member of the present invention, an organic solvent is used as the D component for the purpose of adjusting the total solid content concentration and viscosity of the composition, or adjusting the thickness of the cured body (FPD member). May be contained.
Moreover, by containing this organic solvent, the dispersion stability and storage stability of the composition for forming a flat panel display member are further improved.

Although the usage-amount of the organic solvent as D component can be suitably set according to desired conditions, For example, the total solid content concentration of the obtained flat panel display member formation composition becomes like this. Preferably it is 5-99 mass%. The amount is more preferably 7 to 95% by mass, and particularly preferably 10 to 90% by mass.
Here, "solid content concentration" shows the density | concentration of structural components other than the organic solvent which occupies in the composition for flat panel display member formation.

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

In the organic solvent, the boiling point at 1 atm is preferably 100 ° C. or more and 300 ° C. or less, particularly preferably 150 ° C. or more and 250 ° C. or less.
When the boiling point at 1 atm is less than 100 ° C., the dried product is coated due to the rapid drying of the composition applied in the coating operation (the composition for forming a flat panel display member). There is a risk of adhesion to the work surface or uneven coating. On the other hand, when the boiling point at 1 atm exceeds 300 ° C., the organic solvent tends to remain in the cured body (FPD member) obtained through the baking treatment, resulting in a decrease in strength of the cured body. There is a risk of surface roughness.

Examples of the alcohols include 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, ethyl 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 monobutyl ether, propylene Examples thereof include monomethyl ether acetate and diacetone alcohol.
Examples of the aromatic hydrocarbons include toluene and xylene. Examples of the ethers include diethyl acetal, dibutyl ether and dioxane. Examples of the ketones include acetylacetone and ethyl-n-butylketone. , Diacetone alcohol, methyl isobutyl ketone, methyl-n-butyl ketone, methyl-n-propyl ketone, diethyl ketone, diisobutyl ketone, diisopropyl ketone and the like. Examples of the esters include ethyl acetoacetate, methyl acetoacetate, benzoic acid. Examples thereof include ethyl acid, methyl benzoate, 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.

  Specific examples of such an organic solvent include propylene glycol monomethyl ether, n-hexanol, 2-ethyl-1-hexanol, and 2-butoxyethanol.

[Method for producing composition for forming flat panel display member]
The composition for forming a flat panel display member of the present invention includes an organic solvent as the D component, silica particles as the A component, a silane compound as the B component, a polymer as the C component, and, if necessary, It can be prepared by adding a hydrolytic condensation catalyst comprising a basic compound, an acidic compound or an organometallic compound, and dispersing silica particles in an organic solvent.
In such a method for producing a composition for forming a flat panel display member, depending on the dispersibility of silica particles or the like, for example, a ball mill, a sand mill (bead mill, a high shear bead mill), a homogenizer, an ultrasonic homogenizer, a nanomizer, a propeller mixer, A known disperser such as a high shear mixer or paint shaker is preferably used, 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]
An FPD member can be obtained by coating the composition for forming a flat panel display member of the present invention on a substrate and forming a film.
Moreover, the member which has a pattern can also be formed by patterning the coating film formed on the board | substrate according to the FPD member which should be formed in a predetermined shape.

  As a method for applying the composition for forming a flat panel display member of the present invention, for example, a brush, a slit coater, a roll coater, a bar coater, a flow coater, a centrifugal coater, an ultrasonic coater, a (micro) gravure coater or the like is used. Dip coating method; flow coating method; spray method; screen process method; electrodeposition method; vapor deposition method.

Specifically, for example, by using a slit coater or the like, the composition for forming a flat panel display member is applied to the surface of a glass substrate to form a coating film, and the film forming material layer is formed by drying the coating film. Then, the obtained film-forming material layer is baked to decompose and remove the organic substance (solvent or the like) and sinter, thereby forming an FPD member made of a cured body.
Here, the drying conditions of the coating film are, for example, 40 to 150 ° C. for 1 to 60 minutes. The thickness of the film forming material layer is, for example, 5 to 250 μm.
Moreover, as for the baking conditions of the film forming material layer, the heating temperature (baking temperature) is, for example, 400 to 650 ° C., and the baking time is, for example, 1 to 360 minutes.

According to the composition for forming a flat panel display member of the present invention, a cured body (FPD member) having a thickness (fired film thickness) of 40 μm or more can be formed by a single coating.
Here, “one-time coating” means that, when a composition for forming a flat panel display member is applied onto a substrate, only one cycle of the coating operation and the drying operation of the coating film obtained by the coating operation are performed. Means that.

As described above, according to the composition for forming a flat panel display member of the present invention, it contains a specific polymer together with silica particles and a specific silane compound, and an excellent film is formed by the action of this polymer. Therefore, it is possible to obtain a cured body having a large thickness with a small number of coatings and to suppress the occurrence of cracks in the formed cured body. Can be suitably used.
Specifically, according to the composition for forming a flat panel display member of the present invention, for example, the occurrence of cracks is suppressed even during the formation of a thick film, and the surface is reversely tapered. A cured layer (firing layer) can also be formed on a substrate on which an electrode having a shape is formed in a state where the occurrence of cracks is suppressed to a level that does not cause any practical problems.
Here, the reason why the composition for forming a flat panel display member of the present invention can suppress the occurrence of cracks is that the polymer constituting the C component has a polar group such as a hydroxyl group or an alkoxy group in its structure. Therefore, it is presumed that the strength of the dry film (film forming material layer) and the fired film (fired layer) is increased due to the interaction with the silica particles. Specifically, for example, in the case where a dielectric made of the composition for forming a flat panel display member of the present invention is formed on an electrode made of silver / glass, a film formed by the composition for forming a flat panel display member Since the strength (film strength) that can sufficiently withstand the stress caused by the thermal expansion of the silver constituting the electrode is obtained (specifically, the film forming material layer or the fired layer), cracks It is thought that the occurrence of this will be suppressed.

Furthermore, in the composition for forming a flat panel display member of the present invention, the cured product of the composition for forming a flat panel display member of the present invention has an excellent balance between transparency and heat resistance by the action of a specific silane compound. Since it has high heat resistance with transparency, the occurrence of cracks is suppressed even when the cured body of the formed composition for forming a flat panel display member is placed at a high temperature. Become.
Specifically, the composition for forming a flat panel display member of the present invention includes a dielectric material, a partition material, an electrode material, a resistor material, a phosphor material, a color filter material, a black matrix material, and the like. Although it can be used as a material for forming a flat panel display member, it can be suitably used as a material for forming a dielectric material because a high smoothness can be obtained in the obtained cured body.
In addition, the composition for forming a flat panel display member of the present invention, particularly when used as a dielectric forming material, contains silica particles so that the formed dielectric has a low dielectric constant. Can do.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples.
However, the present invention is not limited to these examples.
In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

  Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) GPC measurement The weight average molecular weight of a silane compound is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL

(2) Critical film thickness evaluation The obtained composition was applied onto a glass substrate using an applicator having a gap of 100 to 300 μm to form a coating film, and this coating film was dried at 100 ° C. for 20 minutes. Then, a cured film having a film thickness of 2 to 40 μm was produced by further baking at 500 ° C. for 1 hour. By visually observing these cured films, the presence or absence of peeling and cracks was confirmed, and in the range of 2 to 40 μm thickness, the maximum film thickness that does not cause peeling and cracking was defined as the limit film thickness, The critical film thickness was measured.

(3) Evaluation of crack resistance on electrode An obtained applicator was applied to a 100 μm applicator on a substrate provided with a reverse-tapered silver electrode having a top surface width of 100 μm, a bottom surface width of 80 μm, and a height of 12 μm. A coating film is formed by applying the coating film, and the coating film is dried at 100 ° C. for 20 minutes, and then baked at 500 ° C. for one hour using an oven to form a cured film (baked film). Produced. A cut piece of 2 cm square size of this cured film was used as a test piece, and the surface was observed with an electron microscope at a magnification of 600 times to confirm the presence or absence of cracks on the surface. The case where the number of generated cracks is less than 5 is good as “◎”, and the case where the number of cracks generated on the side of the electrode in the whole test piece is more than 5 and less than 10 is considered as “no problem in practice”. The case where the number of cracks generated on the side of the electrode in the entire test piece was 10 or more was evaluated as “x” as a failure.

[Silane Compound Preparation Example 1]
142 parts of methyltrimethoxysilane and 49 parts of dimethyldimethoxysilane (trifunctional / 2 functional = 70/30 (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% oxalic acid aqueous solution was added, and neutralization reaction was performed at room temperature over 1 hour. Thereafter, the aqueous layer was separated, and the organic layer was washed with 150 parts of water. After performing this water washing operation 3 times, the solvent was distilled off to obtain a silane compound (B-1) having a weight average molecular weight (Mw) of 5,000.

[Example 1]
In a mixed solvent consisting of 227 parts of 2-ethyl-1-hexanol and 6 parts of 2-butoxyethanol, 95 parts of silica particles having an average particle diameter of 75 nm (hereinafter also referred to as “silica particles (A-1)”). And 5 parts of a silane compound (B-1) and a random copolymer of hydroxyethyl (meth) acrylate (HEMA) and isobutyl (meth) acrylate (i-BMA) (mass ratio (i-BMA / HEMA)) = 80/20, molecular weight 400,000, in Table 1, _{"poly (i-BMA) 80 -} (HEMA) 20 ". by mixing and stirring the indicated as) 9 parts of composition (hereinafter "composition (1) ". In this composition (1), hydroxyethyl (meth) acrylate and isobutyl (meth) as component C relative to the sum of silica particles (A-1) as component A and silane compound (B-1) as component B The mass ratio of the random copolymer with acrylate (the mass ratio calculated by the mathematical formula (1)) is 9.
About the obtained composition (1), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.
Moreover, about this composition (1), when a coating film was formed and this coating film was dried and hardened on the conditions of 500 degreeC, the cured film which has a film thickness of 30 micrometers or more by one application | coating is the formation process. It was confirmed that the film had good film formability because it could be formed without generating cracks.

[Example 2]
In Example 1, instead of a random copolymer of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate (HPMA) and isobutyl (meth) acrylate (i-BMA) Other than the copolymer (mass ratio (i-BMA / HPMA) = 80/20, molecular weight 400,000, indicated as “poly (i-BMA) ₈₀ − (HPMA) ₂₀ ” in Table 1). Obtained a composition (hereinafter, also referred to as “composition (2)”) in the same manner as in Example 1.
About the obtained composition (2), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

Example 3
In Example 1, instead of a random copolymer of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate (ETMA) and 2-methoxyethyl (meth) acrylate (MTMA) a copolymer of butyl (meth) acrylate (BMA) (mass ratio (BMA / ETMA / MTMA) = 60/2020, molecular weight 300,000, in Table 1, _{"poly (BMA) 60 - (ETMA} ) 20 - ( MTMA) ₂₀ -1 indicates a ".) in the same manner as the example 1 except for using in the composition (hereinafter, also referred to as" composition (3) ".) was obtained.
About the obtained composition (3), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

Example 4
In Example 1, instead of a random copolymer of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate (ETMA) and 2-methoxyethyl (meth) acrylate (MTMA) a copolymer of butyl (meth) acrylate (BMA) (mass ratio (BMA / ETMA / MTMA) = 60/2020, molecular weight of 100,000, in Table 1, _{"poly (BMA) 60 - (ETMA} ) 20 - ( MTMA) ₂₀ -2 shown as ".) in the same manner as the example 1 except for using in the composition (hereinafter, also referred to as" composition (4) ".) was obtained.
About the obtained composition (4), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

Example 5
In Example 2, a copolymer of 3-hydroxypropyl (meth) acrylate (HPMA) and isobutyl (meth) acrylate (i-BMA) (mass ratio (i-BMA / HPMA) = 80/20, molecular weight 400,000 In Table 1, a composition (hereinafter referred to as “composition”) was used in the same manner as in Example 1, except that the amount of “poly (i-BMA) _80- (HPMA) ₂₀ ” used was 3 parts. (5) ".
About the obtained composition (5), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

Example 6
In Example 2, a copolymer of 3-hydroxypropyl (meth) acrylate (HPMA) and isobutyl (meth) acrylate (i-BMA) (mass ratio (i-BMA / HPMA) = 80/20, molecular weight 400,000 In Table 1, a composition (hereinafter referred to as “composition”) was used in the same manner as in Example 1 except that the amount of “poly (i-BMA) _80- (HPMA) ₂₀ ”) was 15 parts. (6) ".
About the obtained composition (6), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, silica particles (A-1) were not used, the amount of the silane compound (B-1) used was 100 parts, and random copolymerization of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate. Example 1 except that 9 parts of a polymer of isobutyl (meth) acrylate (i-BMA) (molecular weight 400,000, indicated as “poly (i-BMA)” in Table 1) was used instead of the coalescence. In the same manner, a composition (hereinafter, also referred to as “comparative composition (1)”) was obtained.
About the obtained comparative composition (1), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, instead of a random copolymer of hydroxyethyl (meth) acrylate and isobutyl (meth) acrylate, a polymer of isobutyl (meth) acrylate (i-BMA) (molecular weight 400,000, in Table 1, “poly” (Indicated as (i-BMA).) A composition (hereinafter also referred to as “comparative composition (2)”) was obtained in the same manner as in Example 1 except that 9 parts were used.
About the obtained comparative composition (2), the critical film thickness evaluation and the crack resistance evaluation on an electrode were performed. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Phosphor 8 Dielectric layer 9 Dielectric layer 10 Protective film 11 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 (5)

(A) silica particles,
(B) It comprises 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). At least one silane compound selected from the group,
(C) A composition for forming a flat panel display member, comprising a polymer having a structural unit represented by the following formula (3).

[Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more 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 0-3. ]

[In formula, R < ³ > shows a C1-C8 organic group, and when two or more exist, they may mutually be same or different. 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. It may be. R ³ and R ⁴ may be the same or different. Y represents a halogen atom or a hydrogen atom. a, b, c, d, and e are each independently 0 or more and 4 or less, and satisfy a + 2b + c + d + e = 4. ]

[Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Indicates. ]   (C) Polymerization average molecular weight of polystyrene conversion of a polymer is 10,000-500,000, The composition for flat panel display member formation of Claim 1 characterized by the above-mentioned.   3. The flat panel display according to claim 1, wherein the mass ratio of the (C) polymer to the total of 100 parts by mass of the (A) silica particles and the (B) silane compound is 1 to 30. A composition for forming a member.   (A) Silica particles are 65 parts by mass or more and less than 100 parts by mass in terms of solid matter, and (B) Silane compounds are in excess of 0 part by mass in terms of complete hydrolysis condensate and 35 parts by mass or less (however, (A) silica 4. The composition according to claim 1, wherein the total amount of the solid equivalent of the particles and the equivalent of (B) the complete hydrolysis condensate of the silane compound is 100 parts by mass). A composition for forming a flat panel display member according to claim 1.   The composition for forming a flat panel display member according to any one of claims 1 to 4, wherein the composition is used as a dielectric forming material for a flat panel display.

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