JP2009140805A - Composition for forming flat panel display member, transfer film for forming flat panel display member, and method for manufacturing flat panel display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming an FPD member which forms an FPD panel member having a high transmissivity, a high reflectivity, a high surface smoothness, and a high film thickness uniformity after calcination, and provide a transfer film which is excellent in a flexibility and a transfer property and a handling property and moreover which includes an FPD member forming composition layer composed of the above composition, and provide a method for manufacturing the FPD panel member which forms the FPD panel member which has a high transmissivity and reflectivity and is excellent in a surface smoothness and a film thickness uniformity. <P>SOLUTION: The FPD member forming composition contains (A) inorganic powder, (B) binding resin, (C) silyl group containing compound and (D) metal alkoxide and moreover the above binding resin (B) contains (B-1) a (meth)acrylic co-polymer of a weight-average molecular weight of 10,000 to 50,000 having a polyoxyalkylene portion. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an inorganic powder-containing resin composition suitable for forming a panel member of a flat panel display, a transfer film having an inorganic powder-containing resin layer comprising the composition, and a flat panel display using the transfer film The present invention relates to a method for manufacturing a member.

  In recent years, flat panel displays (hereinafter also referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”) as flat fluorescent displays. ) Is attracting attention. A PDP forms a transparent electrode, encloses an inert gas such as argon or neon between two adjacent glass plates, causes plasma discharge to light up the gas, thereby causing phosphors to emit light and display information. It is a display. 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.

  As a method for manufacturing such an FPD dielectric, partition, electrode, phosphor, color filter, and black stripe (matrix), for example, a method of forming an inorganic powder-containing resin layer on a substrate and firing it (see FIG. Patent Document 1) is known.

Transfer in which an inorganic powder-containing resin layer containing an inorganic powder and a binder resin is formed on a flexible support film in the step of forming an inorganic powder-containing resin layer on a substrate by such a method. A method of transferring the inorganic powder-containing resin layer onto a substrate using a film can be suitably used because a panel member excellent in film thickness uniformity and surface uniformity can be formed with good work efficiency. Yes.
JP-A-9-102273

  However, the inorganic powder-containing resin layer in the conventional transfer film does not have sufficient flexibility and transferability (heat adhesion to the substrate, the same applies hereinafter). When the flexibility is insufficient, problems such as cracks occur when the film is wound on a roll, and cracks occur on the surface of the inorganic powder-containing resin layer transferred to the substrate. When the transferability is insufficient, problems such as peeling from the substrate occur when the inorganic powder-containing resin layer is baked.

  In order to solve these problems, the flexibility and transferability can be improved by lowering the glass transition point of the binder resin constituting the inorganic powder-containing resin layer or adding a large amount of plasticizer. Though conceivable, there are problems such as poor handling of the resulting transfer film and difficulty in efficiently transferring and forming the inorganic powder-containing resin layer with high positional accuracy.

  Moreover, in the conventional material design as described above, dispersion failure is likely to occur when preparing the inorganic powder-containing resin paste. When the dispersion failure occurs, there are inorganic powders aggregated in the paste, which causes problems such as pinholes in the transfer film and low surface smoothness and film thickness uniformity.

Further, in the conventional transfer film, there are many air bubbles remaining in the inorganic layer formed by firing the inorganic powder-containing resin layer, which causes a problem of insufficient transparency and strength of the inorganic layer.
Therefore, this invention provides the composition for FPD member formation which can suppress the residual bubble after baking and can form the FPD panel member (inorganic layer) with high surface smoothness and film thickness uniformity. Objective.

  Another object of the present invention is to provide a transfer film that is excellent in flexibility, transferability and handling properties and has an inorganic powder resin layer made of the above composition.

The composition for forming a flat panel display member of the present invention is
(A) inorganic powder;
(B) a binder resin;
(C) a silyl group-containing compound;
(D) A (meth) acrylic polymer containing a metal alkoxide and having a weight average molecular weight of 10,000 to 50,000 having a (B-1) polyoxyalkylene moiety in the binder resin (B). It is characterized by containing.

The polymer (B-1) is
5 to 30% by weight of a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety;
30 to 50% by weight of a structural unit derived from a (meth) acrylate compound having no polyoxyalkylene moiety;
It is preferable to contain 30 to 50% by weight of a structural unit derived from an aromatic vinyl compound.

  The (meth) acrylate compound having a polyoxyalkylene moiety includes polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol ( At least one (meth) acrylate compound selected from meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate and nonylphenoxypolypropylene glycol (meth) acrylate It is preferable that

  The silyl group-containing compound (C) is preferably a compound represented by the following formula (1).

(In Formula (1), p is an integer of 3-20, m is an integer of 1-3, n is an integer of 1-3, a shows the integer of 1-3.)
The metal alkoxide (D) is preferably at least one selected from titanium alkoxide, aluminum alkoxide and magnesium alkoxide.

The composition for forming an FPD member of the present invention preferably further contains a plasticity-imparting substance (E).
The transfer film for forming an FPD member of the present invention has an inorganic powder-containing resin composition layer (hereinafter, also referred to as “FPD member forming composition layer”) on a support film.

The method for producing an FPD member of the present invention (hereinafter also referred to as “FPD production method (I)”) includes a step of transferring an FPD member-forming composition layer formed on a support film onto a substrate,
And a step of firing the composition layer for forming an FPD member.

  The flat panel display member is preferably a dielectric or a partition.

  The transfer film of the present invention in which the inorganic powder-containing resin layer is formed using the composition for forming an FPD member of the present invention is excellent in flexibility and transferability, and also has an excellent handling property. In addition, residual bubbles in the inorganic powder-containing resin layer formed after firing can be reduced. Therefore, by using the transfer film of the present invention, after firing, an FPD panel member (dielectric layer, partition wall, etc.) having excellent surface smoothness and film thickness uniformity, high transmittance and high strength is positioned at a high position. It can be formed efficiently with high accuracy.

Hereinafter, the composition for forming an FPD member, the transfer film, and the method for producing an FPD panel member of the present invention will be described in detail.
[FPD member forming composition]
[Inorganic powder (A)]
The inorganic powder (A) used in the composition for forming an FPD member of the present invention varies depending on the type of panel member to be formed. Hereinafter, it demonstrates for every kind of panel member.

Examples of the inorganic powder used for the dielectric forming material and the partition wall forming material include glass powder, preferably glass powder having a softening point of 400 to 600 ° C.
When the softening point of the glass powder is less than 400 ° C., the glass powder is melted at the stage where the organic substance such as the binder resin is not completely decomposed and removed in the firing process of the inorganic powder-containing resin layer. Part of the organic substance may remain in the formed member, and as a result of the outgas diffusing in the obtained FPD, the lifetime of the phosphor may be reduced. On the other hand, when the softening point of the glass powder exceeds 600 ° C., the inorganic powder-containing resin layer needs to be baked at a temperature higher than 600 ° C., so that the glass substrate that is the transfer target of the resin layer is distorted. May occur.

Preferable specific examples of the glass powder include lead oxide, boron oxide, silicon oxide and calcium oxide (PbO—B ₂ O ₃ —SiO ₂ —CaO) system;
Zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₂ —SiO ₂ ) systems;
Lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO—B ₂ O ₃ —SiO ₂ —
Al ₂ O ₃ ) system;
Lead oxide, zinc oxide, boron oxide and silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ )
system;
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 bismuth oxide, boron oxide, and silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ ).

  The average particle size of the glass powder is preferably 0.5 to 2.5 μm. The glass powder may be used by mixing inorganic oxides such as aluminum oxide, chromium oxide, manganese oxide, titanium oxide, zirconium oxide, silicon oxide, cerium oxide and cobalt oxide. The content of the inorganic oxide to be mixed is preferably 40% by weight or less of the total amount of the inorganic powder (glass powder + inorganic oxide).

Examples of the inorganic powder used for the electrode forming material include Ag, Au, Al, Ni, Ag—Pd alloy, Cu, Cr, and Co.
Examples of the inorganic powder used for the resistor forming material include RuO ₂ .

As an inorganic powder used for the phosphor forming material, 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;
Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ :
Green phosphors such as (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 blue phosphors such as S: Ag.

As an inorganic powder used for the color filter forming material, for example,
Red pigments such as Fe ₂ O ₃ , Pb ₃ O ₄ , CdS, CdSe, PbCrO ₄ , PbSO ₄ , Fe (NO ₃ ) ₃ ;
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;
In addition to blue pigments such as 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) · Na ₂ S ₄ ) and CoO—Al ₂ O _3, as inorganic pigments for color correction,
PbCrO ₄ —PbSO ₄ , PbCrO ₄ , PbCrO ₄ —PbO, CdS, TiO ₂ —NiO—
Yellow pigments such as Sb ₂ O ₃ ;
Orange pigments such as Pb (Cr—Mo—S) O ₄ ;
Mention may be made of purple pigments such as Co ₃ (PO ₄ ) ₂ .

[Binder resin (B)]
The binder resin (B) constituting the composition for forming an FPD member of the present invention contains a (meth) acrylic polymer (B-1) having a polyoxyalkylene moiety.

<Polymer (B-1)>
The polymer (B-1) used in the present invention is a (meth) acrylic polymer having a polyoxyalkylene moiety and a weight average molecular weight (Mw) of 10,000 to 50,000. When the polymer (B-1) is contained, the transfer film of the present invention having an inorganic powder-containing resin layer obtained from the composition for forming an FPD member of the present invention is excellent in flexibility and transferability. Become. That is, since the polymer (B-1) functions as a plasticizer, even when the inorganic powder-containing resin film is folded, no minute cracks (cracks) are generated on the surface of the resin layer. Storage stability is good even when wound into a shape and stored.

Moreover, when the composition for forming an FPD member contains the polymer (B-1), the thermal decomposability of the inorganic powder-containing resin paste is improved, and after the inorganic powder-containing resin layer is baked, in the inorganic layer The number of remaining bubbles can be reduced. And since a polymer (B-1) is decomposed | disassembled and removed easily with a heat | fever, the function of the inorganic layer obtained by baking the said inorganic powder containing resin layer does not fall.

  Further, when the polymer (B-1) is contained, the dispersibility and the storage stability of the inorganic powder-containing resin paste are improved, and the inorganic powder-containing resin layer and the inorganic powder-containing resin layer obtained by firing The surface smoothness of the layer is improved.

  The polymer (B-1) constituting the binder resin of the present invention is derived from a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety and a (meth) acrylate compound not having a polyoxyalkylene moiety. It is preferable to contain a structural unit and a structural unit derived from an aromatic vinyl compound. Moreover, the polymer (B-1) may contain the structural unit derived from the other copolymerizable monomer mentioned later besides the said structural unit.

  The polymer (B-1) includes a homopolymer of a (meth) acrylate compound having a polyoxyalkylene moiety (hereinafter also referred to as “specific (meth) acrylate compound”), and the specific (meth) acrylate compound. And a (meth) acrylate compound having no polyoxyalkylene moiety represented by the following general formula (2) (hereinafter also referred to as “(meth) acrylate compound (1)”), an aromatic vinyl compound and other co-polymers. A copolymer with at least one selected from polymer monomers can be mentioned.

(In formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group.)
Below, the compound which forms the unit which comprises a polymer (B-1) is each demonstrated.

  In the composition for forming an FPD member of the present invention, the preferred molecular weight of the polymer (B-1) is a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as “weight average molecular weight” or “Mw” by gel permeation chromatography (GPC)). Is also 10,000 to 50,000, more preferably 20,000 to 40,000.

Specific (meth) acrylate compounds that are constituents of the specific (meth) acrylate compound polymer (B-1) include 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 glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, etc. Is mentioned.

(Meth) acrylate compound (1)
As the (meth) acrylate compound (1) which is a constituent component of the polymer (B-1), alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, Examples thereof include cycloalkyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 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, ethylhexyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl Meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Examples include (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

  Examples of the phenoxyalkyl (meth) acrylate include phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2- And methoxybutyl (meth) acrylate.

  Examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl ( Examples include meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate.

  Preferable examples of the (meth) acrylate compound (1) include butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate. .

The aromatic vinyl compound which is a constituent component of the aromatic vinyl compound polymer (B-1) is not particularly limited as long as it is a compound copolymerizable with the specific (meth) acrylate compound or the (meth) acrylate compound (1). Examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl benzoic acid, vinyl phthalic acid, vinyl benzyl methyl ether, and vinyl toluene; polystyrene having a (meth) acryloyl group at the terminal. These may be used alone or in combination of two or more.

Preferable examples of the aromatic vinyl compound include vinyl benzoic acid, vinyl benzyl methyl ether, styrene, and α-methyl styrene.
Other copolymerizable monomer The polymer (B-1) is a copolymerizable monomer other than the specific (meth) acrylate compound, (meth) acrylate compound (1) and aromatic vinyl compound (hereinafter referred to as It may also be reacted with “other copolymerizable monomers”. Other copolymerizable monomers include unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylonitrile and α-chloroacrylonitrile Vinyl cyanide compounds; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid Acids; other unsaturated carboxylic acids; vinyl ethers such as vinyl benzyl methyl ether and vinyl glycidyl ether; and macromonomers such as polymethyl (meth) acrylate, polybutyl (meth) acrylate and polysilicone That.

  Preferred examples of other copolymerizable monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid and vinyl phthalic acid; vinyl glycidyl ether, styrene, butadiene and isoprene.

Polymer (B-1)
As described above, the polymer (B-1) includes the specific (meth) acrylate homopolymer, the specific (meth) acrylate, the (meth) acrylate compound (1), the aromatic vinyl compound, and others. And a copolymer with at least one selected from the copolymerizable monomers. Preferable specific examples of the copolymer include a copolymer of the specific (meth) acrylate, the (meth) acrylate compound (1), and an aromatic vinyl compound.

  The composition ratio of the copolymer is usually 5 to 30% by weight of the specific (meth) acrylate and 30 to 50% by weight of the (meth) acrylate compound (1) with respect to 100% by weight of the polymer (B-1). The aromatic vinyl compounds are 30 to 50% by weight, the specific (meth) acrylate is 10 to 25% by weight, the (meth) acrylate compound (1) is 35 to 45% by weight, and the aromatic vinyl compounds are 35 to 45% by weight. More preferred. Moreover, when it contains another copolymer monomer, it is contained in a composition ratio of 1 to 20% by weight, more preferably 5 to 15% by weight with respect to 100% by weight of the polymer (B-1). It is preferable to further improve the flexibility and transferability of the inorganic powder-containing resin transfer film.

Examples of the polymer (B-1) used in the present invention include polymethylene glycol (meth) acrylate-polybutyl methacrylate copolymer, polyethylene glycol (meth) acrylate-polybutyl methacrylate copolymer, polypropylene glycol (meth) acrylate. -Polybutyl methacrylate copolymer, polyethylene glycol poly (meth) acrylate-methyl methacrylate-butyl methacrylate copolymer, polyethylene glycol poly (meth) acrylate-methyl methacrylate-butyl (meth) acrylate-styrene copolymer, polyethylene glycol poly (Meth) acrylate- (meth) acrylic acid-styrene copolymer, polypropylene glycol poly (meth) acrylate-2-ethoxyethyl (meth) acrylate-styre Copolymer, poly glycol (meth)
Examples include acrylate-2-ethylhexyl acrylate-styrene copolymer, polyethylene glycol (meth) acrylate-2-ethylhexyl acrylate-styrene copolymer, and polyprolene glycol (meth) acrylate-2-ethylhexyl acrylate-styrene copolymer. .

  The polymer (B-1) is obtained by polymerizing the specific (meth) acrylate compound and, if necessary, the (meth) acrylate compound (1) and other copolymerizable monomers by a known method. . The molecular weight of the polymer (B-1) can be adjusted by appropriately adjusting the amount of the polymerization initiator, the polymerization temperature, and the polymerization time.

<Polymer (B-2)>
As long as the polymer (B-2) used in the present invention is other than the polymer (B-1), resins other than those described above can be used without particular limitation. Of these, a (meth) acrylate polymer having no polyoxyalkylene moiety (hereinafter also simply referred to as “acrylic resin”) is preferable. When the composition for forming an FPD member of the present invention contains an acrylic resin as the polymer (B-2), the inorganic powder-containing resin layer formed from the composition for forming an FPD member is excellent for a substrate. Demonstrate (heating) adhesiveness. Therefore, the transfer film produced by applying the composition for forming an FPD member of the present invention on a support film is excellent in transferability (heat adhesion to a substrate) of the inorganic powder-containing resin layer.

  As said acrylic resin, it has moderate adhesiveness, can bind inorganic powder (A), and is completely oxidized and removed by the baking process (400-600 degreeC) of an inorganic powder containing resin layer. A (co) polymer is preferred.

  As such an acrylic resin, a homopolymer of the (meth) acrylate compound (1), a copolymer containing two or more types of the (meth) acrylate compound (1), and the (meth) acrylate compound (1) Copolymers with other copolymerizable monomers are included.

  As the (meth) acrylate compound (1) used for the polymer (B-2), the same compound as the (meth) acrylate compound (1) used as the constituent unit of the polymer (B-1) described above is used. Used. For example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, cycloalkyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate Is mentioned. Specific examples are shown below.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 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, ethylhexyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl Meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Examples include (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Examples of the phenoxyalkyl (meth) acrylate include phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2- And methoxybutyl (meth) acrylate.

  Examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl ( Examples include meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate.

In these, it is preferable that the group shown by R < ² > in the said General formula (2) is a group containing an alkyl group or an oxyalkylene group, Especially preferably, as a (meth) acrylate compound, butyl ( Examples include meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate.

  Examples of the other copolymerizable monomers are not particularly limited as long as they are compounds that can be copolymerized with the (meth) acrylate compound (1), but (meth) acrylic acid, vinylbenzoic acid, malein Examples thereof include unsaturated carboxylic acids such as 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.

  In the polymer (B-2) constituting the composition for forming an FPD member of the present invention, the copolymer component derived from the (meth) acrylate compound represented by the general formula (2) is usually 70% by weight or more, preferably Is 90% by weight or more.

  Specific examples of preferable acrylic resins include polymethyl methacrylate, polybutyl methacrylate and methyl methacrylate-butyl methacrylate copolymer, butyl methacrylate-2-ethylhexyl methacrylate-2-hydroxypropyl methacrylate copolymer, and the like.

  The molecular weight of the polymer (B-2) constituting the composition for forming an FPD member of the present invention is 4,000 to 300,000, preferably 10,000 to 200,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). It is.

<Binder resin (B) content>
The binder resin (B-2) is used in an amount of 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the inorganic powder (A). If the amount of the binder resin (B-2) is too small, the inorganic powder may not be securely bound and held. Meanwhile, binder resin (B-2)
If the amount is too large, the firing process may take a long time, or the formed sintered body (for example, the dielectric layer) may not have sufficient strength and film thickness.

The polymer (B-1) is usually 0.01 to 50 parts by weight, preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the inorganic powder (A). Part by weight is used. When the amount of the polymer (B-1) is less than the above range, the handling property at room temperature of the inorganic powder-containing resin layer and the transferability of the inorganic powder-containing resin layer (heat adhesion to the substrate) are poor. There is. Moreover, when there are more amounts of a polymer (B-1) than the said range, the adhesiveness and transferability at the time of transcription | transfer of the inorganic powder containing resin layer formed will become excessive, and it will become difficult to peel a support film. The transferability of the transfer film having the inorganic powder-containing resin layer may be inferior.

[Silyl group-containing compound (C)]
The silyl group-containing compound (C) used in the present invention is a compound represented by the following formula (1).

(In Formula (1), p is an integer of 3-20, m is an integer of 1-3, n is an integer of 1-3, a shows the integer of 1-3.)
Even when a saturated alkyl group-containing (alkyl) alkoxysilane having a p value of less than 3 is contained, the resulting inorganic powder-containing resin layer may not exhibit sufficient flexibility. On the other hand, since the saturated alkyl group-containing (alkyl) alkoxysilane having a p value exceeding 20 has a high decomposition temperature, the silyl group-containing compound (C) is not completely decomposed and removed in the firing step of the inorganic powder-containing resin layer. In some cases, the glass frit melts at a stage, and a part of the organic substance remains in the formed dielectric layer, so that the light transmittance of the dielectric layer may be lowered.

Specific examples used as the silyl group-containing compound (C) are shown below.
Examples of the saturated alkyldimethylmethoxysilane (a = 1, m = 1, n = 1) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, and n-hexadecyldimethyl. Examples include methoxysilane and n-icosanedimethylmethoxysilane.

  Examples of saturated alkyldiethylmethoxysilanes (a = 1, m = 1, n = 2) include n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, and n-hexadecyldiethylmethoxy. Examples thereof include silane and n-icosanediethylmethoxysilane.

  Examples of saturated alkyldipropylmethoxysilanes (a = 1, m = 1, n = 3) include n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n -Icosanedipropylmethoxysilane and the like.

  Examples of saturated alkyldimethylethoxysilanes (a = 1, m = 2, n = 1) include, for example, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, and n-hexadecyldimethylethoxy. Examples thereof include silane and n-icosanedimethylethoxysilane.

  Examples of saturated alkyldiethylethoxysilanes (a = 1, m = 2, n = 2) include, for example, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxy. Silane, n-icosane diethylethoxysilane, etc. are mentioned.

  As saturated alkyldipropylethoxysilanes (a = 1, m = 2, n = 3), for example, n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n -Icosanedipropylethoxysilane and the like.

  Examples of saturated alkyldimethylpropoxysilanes (a = 1, m = 3, n = 1) include, for example, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, and n-hexadecyldimethylpropoxy. Silane, n-icosane dimethylpropoxysilane, etc. are mentioned.

  Examples of saturated alkyldiethylpropoxysilanes (a = 1, m = 3, n = 2) include, for example, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxy Examples thereof include silane and n-icosanediethylpropoxysilane.

  As saturated alkyldipropylpropoxysilanes (a = 1, m = 3, n = 3), for example, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n -Icosanedipropylpropoxysilane and the like.

  Saturated alkylmethyldimethoxysilanes (a = 2, m = 1, n = 1) include, for example, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxy Examples thereof include silane and n-icosanemethyldimethoxysilane.

  Examples of saturated alkylethyldimethoxysilanes (a = 2, m = 1, n = 2) include n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, and n-hexadecylethyldimethoxy. Silane, n-icosaneethyldimethoxysilane and the like are mentioned.

  Saturated alkylpropyldimethoxysilanes (a = 2, m = 1, n = 3) include, for example, n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosampropyl Examples include dimethoxysilane.

  Saturated alkylmethyldiethoxysilanes (a = 2, m = 2, n = 1) include, for example, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n- Examples include hexadecylmethyldiethoxysilane and n-icosanemethyldiethoxysilane.

  Examples of saturated alkylethyldiethoxysilanes (a = 2, m = 2, n = 2) include n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n- Examples include hexadecylethyldiethoxysilane and n-icosaneethyldiethoxysilane.

  As saturated alkylpropyldiethoxysilanes (a = 2, m = 2, n = 3), for example, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n -Icosanepropyldiethoxysilane and the like.

  Saturated alkylmethyldipropoxysilanes (a = 2, m = 3, n = 1) include, for example, n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n- Examples include hexadecylmethyldipropoxysilane and n-icosanemethyldipropoxysilane.

  Examples of saturated alkylethyldipropoxysilanes (a = 2, m = 3, n = 2) include n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n- Hexadecyl ethyl dipropoxy silane, n-icosane ethyl dipropoxy silane, etc. are mentioned.

  Saturated alkylpropyl dipropoxysilanes (a = 2, m = 3, n = 3) include, for example, n-butylpropyl dipropoxysilane, n-decylpropyl dipropoxysilane, n-hexadecylpropyl dipropoxysilane, n -Icosanpropyl dipropoxysilane and the like.

  Examples of saturated alkyltrimethoxysilanes (a = 3, m = 1) include n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n- Examples include icosanetrimethoxysilane.

  Saturated alkyltriethoxysilanes (a = 3, m = 2) include, for example, n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n- Examples include icosane triethoxysilane.

  Examples of saturated alkyltripropoxysilanes (a = 3, m = 3) include, for example, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n- Examples include icosan tripropoxysilane.

  As a content rate of the silyl group containing compound (C) of this invention, it is preferable that it is 0.01-10 weight part with respect to 100 weight part of inorganic powder (A), More preferably, it is 0.1-5. Parts by weight. When the ratio of the silyl group-containing compound (C) is too small, the surface smoothness of the inorganic powder-containing resin layer is reduced, or the transparency of the fired film obtained by firing the inorganic powder-containing resin layer is low. May be lower. On the other hand, when this ratio is excessive, the storage stability of the inorganic powder-containing resin composition may decrease, or the handling property of the resulting transfer film may decrease.

[Metal alkoxide (D)]
The inorganic powder-containing resin layer of the present invention contains a metal alkoxide (D). The metal alkoxide (D) reacts quickly with the hydroxyl group contained in the glass powder that is the inorganic powder (A), and then efficiently undergoes a substitution reaction with the silyl group-containing compound (C). Therefore, the effect of the further improvement of the dispersibility of glass powder and the improvement of the surface smoothness in the film forming material layer formed is expressed. Since the silyl group-containing compound alone is not sufficiently reacted with the glass powder, improvement in dispersibility cannot be expected so much.

  Examples of the metal alkoxide (D) used in the present invention include titanium alkoxide, aluminum alkoxide, and magnesium alkoxide. Of these, titanium alkoxide is particularly preferably used from the viewpoint of reactivity.

As a specific example of the metal alkoxide used in the present invention, a compound represented by the following formula (3) is preferable.
R _s M (OR ') _ts (3)
(In Formula (3), M is a metal atom such as aluminum, titanium, or magnesium, R is a monovalent organic group having 1 to 8 carbon atoms, and R ′ is an alkyl group having 1 to 6 carbon atoms. , T is the valence of M, and s is an integer of 0 to t-1, and when a plurality of R or R ′ are present, they may be the same or different.
In the formula (3), examples of the monovalent organic group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, alkyl groups such as t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group and trioyl group ; Acyloxyl group such as acetoxyl group, propionyloxyl group, butyryloxyl group, valeryloxyl group, benzoyloxyl group, trioyloxyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group, (meth) acryloxy Group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc. Some or all of the hydrogen atoms contained in the group are halogen atoms, substituted or unsubstituted amino groups, hydroxyl groups, mercapto groups, isocyanate groups, glycidoxy groups, 3,4-epoxycyclohexyl groups, (meth) acryloxy groups , A ureido group, a group substituted by an ammonium base, and the like.

  Moreover, as a C1-C6 alkyl group of R ', a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, An n-hexyl group etc. are mentioned.

  Examples of such metal alkoxides include titanium alkoxides such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide; aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide. And aluminum alkoxides such as aluminum tributoxide; and magnesium alkoxides such as magnesium dimethoxide and magnesium diethoxide. These metal alkoxides are used alone or in combination of two or more.

  The content ratio of the metal alkoxide (D) in the composition for forming an FPD member of the present invention is preferably 0.001 to 10 parts by weight, more preferably 100 parts by weight of the inorganic powder (A). 0.01 to 1 part by weight. If the proportion of the metal alkoxide (D) is too small, the effect of improving the dispersibility of the glass powder and the effect of improving the surface smoothness of the film-forming material layer to be formed may not be sufficiently exhibited. On the other hand, if this ratio is excessive, the viscosity of the composition for forming an FPD member of the present invention increases over time, or a reaction occurs between the metal alkoxides (D). It may cause a decrease in light transmittance.

[Plasticity-imparting substance (E)]
The composition for forming an FPD member of the present invention may contain a plasticity-imparting substance (E) as an auxiliary agent for the binder resin (B) in order to give the transfer film good flexibility. The inorganic powder-containing resin layer formed from the FPD member forming composition containing the plasticity-imparting substance (E) has sufficient flexibility.

Examples of the plasticizer (E) include a compound represented by the following general formula (4), a plasticizer selected from the group consisting of a compound represented by the following general formula (5), polypropylene glycol, ) A copolymerizable monomer such as an acrylate compound and a solvent which will be described later. Among them, those having a boiling point of 150 ° C. or higher are preferable. Such plasticity-imparting substances (E) may be used singly or in combination of two or more.

(In Formula (4), R ³ and R ⁶ each independently represent a monovalent chain hydrocarbon group having 1 to 30 carbon atoms, and R ⁴ and R ⁵ are each independently a methylene group or A divalent chain hydrocarbon group having 2 to 30 carbon atoms is shown, s is an integer of 0 to 5, and t is an integer of 1 to 10.)
In the general formula (4), the monovalent chain hydrocarbon group represented by R ³ or R ⁶ is a linear or branched alkyl group (saturated group) or alkenyl group (unsaturated group), The chain hydrocarbon group has 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 4 to 10 carbon atoms. When the number of carbon atoms of the chain hydrocarbon group exceeds the above range, the solubility in a solvent described later becomes low, and it may be difficult to give good flexibility to the inorganic powder-containing resin layer.

The divalent chain hydrocarbon group represented by R ⁴ or R ⁵ is a linear or branched alkylene group (saturated group) or alkenylene group (unsaturated group).
Examples of the compound represented by the general formula (4) include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate and dibutyl diglycol adipate.

(In the formula (5), R ⁷ represents a monovalent chain hydrocarbon group having 1 to 30 carbon atoms.)
In the general formula (5), the monovalent chain hydrocarbon group represented by R ⁷ is a linear or branched alkyl group (saturated group) or alkenyl group (unsaturated group). The carbon number of the hydrogen group is 1-30, preferably 2-20, more preferably 10-18.

Examples of the compound represented by the general formula (5) include propylene glycol monolaurate and propylene glycol monooleate.
When polypropylene glycol is used as the plasticity-imparting substance (E), the weight average molecular weight (Mw) in terms of polystyrene of the polypropylene glycol is preferably in the range of 200 to 3,000, and in the range of 300 to 2,000. It is particularly preferable that If Mw is less than 200, it may be difficult to form an inorganic powder-containing resin layer having a high film strength on the support film, and the inorganic powder-containing resin layer is transferred from the support film to the glass substrate. In the process, when the support film is peeled off from the inorganic powder-containing resin layer heat-bonded to the glass substrate, the resin layer may cause cohesive failure. On the other hand, Mw is 3,000.
If it exceeds 1, an inorganic powder-containing resin layer having good heat-adhesiveness with a glass substrate that is a transfer target may not be obtained.

  The plasticity-imparting substance (E) is used in an amount of 3% by weight or more, preferably 4 to 15% by weight, based on all components excluding the solvent from the FPD member forming composition of the present invention. When the content of the plasticity-imparting substance (E) is too small, it may be difficult to give good flexibility to the transfer film to be formed.

<Solvent>
The composition for forming an FPD member of the present invention usually contains a solvent. As such a solvent, the affinity with the inorganic powder (A) and the solubility of the binder resin (B) are good, and an appropriate viscosity can be imparted to the composition for forming an FPD member. It is preferable that it can be easily removed by evaporation if it is dried.

  Particularly preferred solvents include ketones, alcohols and esters (hereinafter referred to as “specific solvents”) having a normal boiling point (boiling point at 1 atm) of 60 to 200 ° C.

Examples of the specific solvent include ketones such as methyl ethyl ketone, diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone;
alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol;
Ether based alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Saturated aliphatic monocarboxylic acid alkyl esters such as n-butyl acetate and amyl acetate; lactic esters such as ethyl lactate and n-butyl lactate;
Examples thereof include ether type esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate. Among these, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are preferable. These specific solvents may be used alone or in combination of two or more.

  Examples of usable solvents other than the specific solvent include turpentine oil, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, and benzyl alcohol.

  From the viewpoint of maintaining the viscosity of the composition for forming an FPD member within a suitable range, the solvent is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the inorganic powder (A). Used. Moreover, the ratio of the specific solvent with respect to all the solvents is 50 weight% or more, Preferably it is 70 weight% or more. Moreover, it is preferable that the viscosity of the composition for forming an FPD member is usually in a range of 2,000 to 200,000 cps.

[Various additives]
The composition for forming an FPD member of the present invention includes, as an optional component, a dispersant, a development accelerator, an adhesion assistant, an antihalation agent, a leveling agent, a storage stabilizer, an antifoaming agent, an antioxidant and / or a chain transfer agent. Various additives such as may be contained.

[Transfer film]
The transfer film for forming an FPD member of the present invention (hereinafter also simply referred to as “transfer film”) has an inorganic powder (A), a binder resin (B), a silyl group-containing compound (C), and a support film. It has the inorganic powder containing resin layer formed from the composition for FPD member formation containing a metal alkoxide (D). The FPD member forming composition may contain a plasticity-imparting substance (E).

The transfer film of the present invention may have a laminated film of a resist film and the inorganic powder-containing resin layer (laminated transfer film) on a support film.
Moreover, you may have a cover film on the surface of an inorganic powder containing resin layer as needed.

Hereinafter, each component of the transfer film will be specifically described.
(1) Support film The transfer film of this invention has a support film which supports an inorganic powder containing resin layer. The support film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the composition for forming an FPD member can be applied to the surface of the support film by a roll coater or a blade coater, and the resulting transfer film is wound in a roll shape. Can be stored or supplied.

  Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.

  The thickness of the support film is 20 to 100 μm. Moreover, it is preferable that the surface of the support film is subjected to a mold release treatment, whereby the support film can be easily peeled off in the transfer step to the glass substrate.

(2) Cover film In the transfer film of the present invention, a cover film may be provided on the surface of the inorganic powder-containing resin layer in order to protect the surface of the inorganic powder-containing resin layer. This cover film is preferably a flexible resin film, whereby the obtained transfer film can be stored or supplied in a rolled state.

  Examples of the resin constituting the cover film include a polyethylene terephthalate film, a polyethylene film, and a polyvinyl alcohol film.

  The cover film has a thickness of 20 to 100 μm. Moreover, the surface of the cover film may be subjected to a release treatment, and the adhesion with the inorganic powder-containing resin layer is preferably smaller than that of the support film.

(3) Inorganic powder-containing resin layer The inorganic powder-containing resin layer (FPD member-forming composition layer) is usually obtained by coating the FPD member-forming composition on a support film and drying the resulting coating film. It is formed by removing all or part of the solvent.

As a method of applying the FPD member forming composition on a support film, it is a method capable of forming a coating film with high uniformity of film thickness and a large film thickness (for example, 10 μm or more) with high efficiency. Specifically, specific examples include a coating method using a roll coater, a coating method using a blade coater, a coating method using a curtain coater, and a coating method using a wire coater. The film thickness of the inorganic powder-containing resin layer is usually 10 to 300 μm although it depends on the height of the panel member to be formed.

  The drying condition of the coating film is, for example, about 50 to 150 ° C. for about 0.5 to 30 minutes, and the residual ratio of the solvent after drying (content in the inorganic powder-containing resin layer) is usually 2 wt. %.

[Method of manufacturing FPD]
The following aspects are mentioned as a manufacturing method of FPD of this invention.
[1] A dielectric that is a panel member by a method comprising a step of transferring the inorganic powder-containing resin layer of the transfer film of the present invention onto a substrate and a step of firing the transferred inorganic powder-containing resin layer. A method of forming a layer (FPD manufacturing method (I)).
[2] A step of transferring the inorganic powder-containing resin layer of the transfer film of the present invention onto a substrate, a step of forming a resist pattern on the transferred inorganic powder-containing resin layer, and an inorganic powder-containing resin layer A dielectric layer, an electrode, a barrier rib, a phosphor, a resistor, and a color filter, which are panel members, by a method including a step of etching the substrate to form a pattern corresponding to the resist pattern and a step of baking the pattern And a method of forming at least one selected from a black matrix (FPD production method (II)).
[3] A step of transferring the laminated film of the laminated transfer film onto the substrate so that the inorganic powder-containing resin layer is in contact with the substrate, and exposing the resist film in the transferred laminated film to expose the latent resist pattern. A step of forming an image, a step of developing a resist film to reveal a resist pattern, a step of etching an inorganic powder-containing resin layer to form a pattern corresponding to the resist pattern, and baking the pattern A method of forming at least one selected from a dielectric layer, an electrode, a partition, a phosphor, a resistor, a color filter, and a black matrix as a panel member (FPD production method (III)) .
[4] A step of transferring an inorganic powder-containing resin layer of a photosensitive transfer film onto a substrate, a step of exposing the transferred inorganic powder-containing resin layer to form a latent image of a pattern, and the inorganic A dielectric layer, an electrode, a partition, a phosphor, a resistor, and a color filter, which are panel members, by a method including a step of developing a powder-containing resin layer to form a pattern and a step of firing the pattern And a method of forming at least one selected from black matrices (FPD production method (IV)).
[5] A step of transferring the inorganic powder-containing resin layer of the transfer film of the present invention onto a substrate, a step of baking the transferred inorganic powder-containing resin layer to form an inorganic film, and the inorganic film A dielectric layer, an electrode, a partition, a phosphor, a resistor, which are panel members, by a method including a step of forming a resist pattern on the substrate and a step of etching the inorganic film to form a pattern corresponding to the resist pattern. A method (V) for forming at least one selected from a color filter and a black matrix.

Hereinafter, the manufacturing method (I) of FPD of this invention is demonstrated.
<Method for manufacturing FPD member (I)>
An example of the transfer process in the manufacturing method (I) of the FPD member is as follows.

(1) The transfer film wound in a roll shape is cut into a size corresponding to the area of the substrate.
(2) The cover film is peeled off as necessary from the surface of the inorganic powder-containing resin layer in the cut transfer film, and then the transfer film is overlaid so that the surface of the inorganic powder-containing resin layer is in contact with the surface of the substrate.

(3) A heating roller is moved on the transfer film superimposed on the substrate and thermocompression bonded.
(4) The support film is peeled and removed from the inorganic powder-containing resin layer fixed to the substrate by thermocompression bonding.

By the operation as described above, the inorganic powder-containing resin layer on the support film is transferred onto the substrate. As transfer conditions at this time, for example, the surface temperature of the heating roller is 60 to 120 ° C., the roll pressure by the heating roller is 1 to 5 kg / cm ^2, and the moving speed of the heating roller is 0.2 to 1.
0.0 m / min. Such an operation (transfer process) can be performed by a laminator apparatus. In addition, the board | substrate may be preheated and can be 40-100 degreeC as preheating temperature, for example.

  The inorganic powder-containing resin layer transferred and formed on the surface of the substrate is fired to form an inorganic sintered body (dielectric layer). Examples of the firing method include a method in which the substrate on which the inorganic powder-containing resin layer is transferred and formed is placed in a high-temperature atmosphere. By the baking treatment, the organic substance contained in the inorganic powder-containing resin layer is decomposed and removed, and the inorganic powder is melted and sintered. The firing temperature varies depending on the melting temperature of the substrate and the constituent materials in the inorganic powder-containing resin layer, but is, for example, 300 to 800 ° C, preferably 400 to 620 ° C.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples. In the following, “part” means “part by weight”.

<Synthesis Example 1>
40 parts of polyethylene glycol methacrylate (hereinafter also referred to as “PEGMA”), 40 parts of 2-ethylhexyl acrylate (hereinafter also referred to as “EHA”), 20 parts of styrene (hereinafter also referred to as “ST”) and N, N 0.75 part of '-azobisisobutyronitrile was charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, the mixture is polymerized at 80 ° C. for 3 hours, further added with 0.25 part of N, N′-azobisisobutyronitrile and polymerized for 1 hour, and the polymerization reaction is continued at 100 ° C. for 1 hour, and then to room temperature. Upon cooling, a polymer solution was obtained. The obtained polymer solution had a polymerization rate of 98%, and the Mw of the polymer (B-1) (hereinafter referred to as “resin (1)”) precipitated from the polymer solution was 30,000. The results are shown in Table 1.

Further, in Synthesis Example 1, resins (2) to (5) were synthesized in the same manner as in Synthesis Example 1 except that the monomers were used in the amounts shown in Table 1.
<Synthesis Example 6>
20 parts of PEGMA, 40 parts of EHA, 40 parts of ST and 1.5 parts of N, N′-azobisisobutyronitrile were charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, the mixture is polymerized at 90 ° C. for 3 hours, 0.5 part of N, N′-azobisisobutyronitrile is further added for polymerization for 1 hour, and the polymerization reaction is continued at 100 ° C. for 1 hour, and then to room temperature. Upon cooling, a polymer solution was obtained. The obtained polymer solution had a polymerization rate of 96%, and the Mw of the resin (6) precipitated from this polymer solution was 10,000. The results are shown in Table 1.

<Synthesis Example 7>
20 parts of PEGMA, 40 parts of EHA, 40 parts of ST and 0.5 part of N, N′-azobisisobutyronitrile were charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, the mixture is polymerized at 75 ° C. for 4 hours, further added with 0.25 part of N, N′-azobisisobutyronitrile, polymerized for 2 hours, and the polymerization reaction is continued at 100 ° C. for 1 hour. Upon cooling, a polymer solution was obtained. The obtained polymer solution had a polymerization rate of 98%, and the Mw of the resin (7) deposited from this polymer solution was 50,000. The results are shown in Table 1.

[Example 1]
(1) Preparation of glass paste composition (FPD member forming composition) PbO having a composition of 70% by weight of lead oxide, 10% by weight of boron oxide and 20% by weight of silicon oxide as glass powder (inorganic powder (A)) —B ₂ O ₃ —SiO ₂ -based mixture (softening point 50
0 part), 10 parts of polymer (B-1) as binder resin (B), 20 parts of polymer (B-2), n-decyltrimethoxysilane as silyl group-containing compound (C) (Hereinafter also referred to as “nDTMS”) 5 parts, titanium tetraisopropoxide (hereinafter also referred to as “TTiPO”) as metal alkoxide (D) and 1 part as plasticizer (E) bis (2- The composition for forming an FPD member having a viscosity of 3 Pa · s is obtained by kneading 3 parts of ethylhexyl) azelate (hereinafter also referred to as “EHAz”) and 35 parts of propylene glycol monomethyl ether using a disperser. Prepared.

(2) Production and evaluation of transfer film (flexibility and handling)
The composition for forming an FPD member prepared in the above (1) was applied on a support film (width 400 mm; length 30 m; thickness 38 μm) made of polyethylene terephthalate (PET), which had been subjected to release treatment in advance, using a blade coater. The formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, thereby forming an inorganic powder-containing resin layer having a thickness of 50 μm on the support film. Next, a cover film (width 400 mm; length 30 m; thickness 25 μm) made of PET, which has been subjected to a release treatment in advance, is adhered onto the inorganic powder-containing resin layer, thereby having a structure as shown in FIG. A transfer film of the present invention was produced.

  The obtained transfer film was flexible and could be easily wound up into a roll. Moreover, even if this transfer film was bent, the surface of the inorganic powder-containing resin layer was not cracked (bent crack), and the resin layer had excellent flexibility.

  Further, after peeling the cover film from the transfer film and overlaying the transfer film without applying pressure so that the surface of the inorganic powder-containing resin layer is in contact with the surface of the glass substrate, the transfer film is I peeled it off the surface of the glass substrate. As a result, the resin layer shows moderate adhesiveness to the glass substrate, and the transfer film can be peeled off without causing cohesive failure of the resin layer, and the handling property as a transfer film is good. It was something.

(3) Transfer of inorganic powder-containing resin layer After peeling the cover film from the transfer film obtained in (2) above, the inorganic powder is applied to the surface of the glass substrate for 20-inch panels (fixing surface of the bus electrode) The transfer film was overlaid so that the surface of the containing resin layer was in contact, and the transfer film was thermocompression bonded with a heating roll. As the pressure bonding conditions, the surface temperature of the heating roll is 110 ° C., and the roll pressure is 3 kg / cm ^2.
The moving speed of the heating roll was 1 m / min.

After completion of the thermocompression treatment, the support film was peeled and removed from the inorganic powder-containing resin layer fixed (heat bonded) to the surface of the glass substrate to complete the transfer of the resin layer.
In this transfer step, the inorganic powder-containing resin layer did not cause cohesive failure when the support film was peeled off, and the resin layer had a sufficiently large film strength. Furthermore, the transferred inorganic powder-containing resin layer had good adhesion to the surface of the glass substrate. The results are shown in Table 2.

(4) Baking process of inorganic powder-containing resin layer As described above, the inorganic powder-containing resin fixed (heat bonded) to the surface of the glass substrate is baked in a baking furnace in a temperature atmosphere of 590 ° C. for 20 minutes. Processed. Thereby, the panel member by which the dielectric material with a thickness of 40 micrometers was formed in the surface of the glass substrate was able to be obtained. The results are shown in Table 2.

<Evaluation method of transfer film>
The method for evaluating the transfer film of the present invention is shown below.
(1) Flexibility When the transfer film was folded, the surface of the inorganic powder-containing resin layer where no cracks (bending cracks) occurred was marked with ◯, and when the cracked film was marked with x.
(2) Residual bubbles The inorganic layer obtained after firing was observed with a transmission optical microscope, and the average diameter of the bubbles remaining in the inorganic layer was measured. Residual bubbles were measured based on the following evaluation criteria.
A: Less than 5 μm B: 5 μm or more and less than 10 μm C: 10 μm or more (3) Surface smoothness Measurement range 500 μm × 500 μm using a non-contact three-dimensional shape measuring device (model number: NH-3 Mitaka Koki Co., Ltd.) Measurement was performed under the condition of a pitch of 10 μm, and the 10-point average roughness (Rz) was defined as the surface roughness. The surface roughness was performed based on the following evaluation criteria.
○: Less than 0.01 μm ×: 0.01 μm or more [Examples 2 to 9]
In Example 1, an FPD member-forming composition and a transfer film were prepared in the same manner as in Example 1 except that the FPD member-forming composition shown in Table 2 was used. The results are shown in Table 2.

[Comparative Example 1]
In Example 3, an FPD member-forming composition and a transfer film were prepared in the same manner as in Example 3 except that the polymer (B-1) was not used. The results are shown in Table 2.

[Comparative Example 2]
In Example 3, an FPD member-forming composition and a transfer film were prepared in the same manner as in Example 3 except that n-decyltrimethoxysilane (silyl group-containing compound (C)) was not used. The results are shown in Table 2.

[Comparative Example 3]
In Example 3, a composition for forming an FPD member and a transfer film were prepared in the same manner as in Example 3 except that titanium tetraisopropoxide (metal alkoxide (D)) was not used. The results are shown in Table 2.

It is a schematic diagram which shows the cross-sectional shape of alternating current type PDP. It is the schematic of the structural example of the transfer film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer 10 Protective layer 11 Partition F1 Support film F2 Member formation material layer F3 Cover film

Claims (9)

(A) inorganic powder;
(B) a binder resin;
(C) a silyl group-containing compound;
(D) A (meth) acrylic polymer containing a metal alkoxide and having a weight average molecular weight of 10,000 to 50,000 having a (B-1) polyoxyalkylene moiety in the binder resin (B). A composition for forming a flat panel display member, comprising: The polymer (B-1) is
5 to 30% by weight of a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety;
30 to 50% by weight of a structural unit derived from a (meth) acrylate compound having no polyoxyalkylene moiety;
The composition for forming a flat panel display member according to claim 1, comprising 30 to 50% by weight of a structural unit derived from an aromatic vinyl compound.   The (meth) acrylate compound having a polyoxyalkylene moiety is a polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol ( At least one (meth) acrylate compound selected from meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate and nonylphenoxypolypropylene glycol (meth) acrylate The flat panel display according to claim 2, wherein Play member forming composition. The said silyl group containing compound (C) is a compound represented by following formula (1), The composition for flat panel display member formation in any one of Claims 1-3.

(In Formula (1), p is an integer of 3-20, m is an integer of 1-3, n is an integer of 1-3, a shows the integer of 1-3.)   The said metal alkoxide (D) is at least 1 type chosen from titanium alkoxide, aluminum alkoxide, and magnesium alkoxide, The composition for flat panel display member formation in any one of Claims 1-4.   The composition for forming a flat panel display member according to any one of claims 1 to 5, further comprising a plasticity-imparting substance (E). A flat panel display member-forming transfer, comprising a flat panel display member-forming composition layer obtained from the flat panel display member-forming composition according to any one of claims 1 to 6 on a support film. the film. Transferring the flat panel display member forming composition layer obtained from the flat panel display member forming composition according to any one of claims 1 to 6 formed on the support film onto the substrate;
And a step of firing the composition layer for forming a flat panel display member. A method for producing a flat panel display member.   The method for manufacturing a flat panel display member according to claim 8, wherein the flat panel display member is a dielectric or a partition wall.

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