WO2008072582A1

WO2008072582A1 - Inorganic-particle-containing resin composition, transfer film, and process for producing flat panel display member

Info

Publication number: WO2008072582A1
Application number: PCT/JP2007/073719
Authority: WO
Inventors: Hiroshi Mashima; Tetsunori Sugawara; Yasutake Inoue; Hiroaki Kuwada; Michihiro Mita
Original assignee: Jsr Corporation
Priority date: 2006-12-07
Filing date: 2007-12-07
Publication date: 2008-06-19

Abstract

[PROBLEMS] An inorganic-particle-containing resin composition for forming FPD panel members. Even when a layer of this inorganic-particle-containing resin is burned simultaneously with a pattern comprising an unburned conductive-particle-containing resin composition, no bubbles generate on the electrodes or between the electrodes. Also provided are: an inorganic-particle-containing resin composition for forming FPD panel members which, after burning, is high in transmittance, reflectance, surface smoothness, and film thickness evenness; a transfer film having an inorganic-particle-containing resin layer made of either of the compositions, the film being excellent in flexibility, transferability, and handleability; and a process for producing an FPD panel member which is high in transmittance and reflectance and excellent in surface smoothness and film thickness evenness. [MEANS FOR SOLVING PROBLEMS] The resin compositions comprise an inorganic powder (A) and a binder resin (B) or comprise an inorganic powder (A), a binder resin (B), a silylated compound (E), and a metal alkoxide (F), wherein the binder resin (B) comprises a (meth)acrylic polymer (B-1) having an Mw of 10,000-50,000 which has a polyoxyalkylene segment.

Description

Specification

Inorganic powder-containing resin composition, transfer film, and method for producing flat panel display member

Technical field

The present invention uses 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 the transfer film. BACKGROUND OF THE INVENTION

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-plate fluorescent displays. .) Is attracting attention. The PDP forms a transparent electrode, encloses an inert gas such as argon or neon between two adjacent glass plates, causes plasma discharge, and emits the gas, thereby emitting light from the phosphor and displaying information. It is a display to show. On the other hand, the FED emits electrons from the cathode into the vacuum by applying an electric field, and irradiates the phosphors on the anode to cause the phosphors to emit light.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In the figure, 1 and 2 are glass substrates opposed to each other, 3 is a partition wall, and cells are partitioned by the glass substrate 1, the glass substrate 2 and the partition wall 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of reducing the resistance of the transparent electrode 4, 6 is an address electrode fixed on the glass substrate 2, and 7 is Fluorescent material held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is a surface of the glass substrate 2 so as to cover the address electrode 6. The dielectric layer 10 is formed of a protective film made of, for example, magnesium oxide.

[0004] Also, in color FPD, a color filter (red, green, blue) or black matrix is provided between the glass substrate and the dielectric layer in order to obtain a high contrast image. Power to provide Sfc.

[0005] Examples of methods for manufacturing such FPD dielectrics, barrier ribs, electrodes, phosphors, color filters, and black stripes (matrix) include:

(1) A method of forming an inorganic powder-containing resin layer on a substrate and firing it (see Patent Document 1)

(2) An inorganic powder-containing resin layer is formed on a substrate, a resist pattern is formed on the resin layer, and the inorganic powder-containing resin layer is etched using this as a mask to form a pattern, which is baked Method (see Patent Documents 2 and 3),

(3) A photosensitive inorganic powder-containing resin layer is formed on a substrate, and this film is irradiated with ultraviolet rays through a photomask and developed to form a pattern on the substrate, which is baked. The method (see Patent Document 4) is known!

[0006] Among the above methods, in the step of forming the inorganic powder-containing resin layer on the substrate, the inorganic powder-containing resin layer containing the inorganic powder and the binder resin on the flexible support film. The method of transferring the inorganic powder-containing resin layer onto the substrate using the transfer film on which the film is formed enables a panel member having excellent film thickness uniformity and surface uniformity to be formed efficiently. Are preferably used.

However, since 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), the film is wound around a roll. In some cases, cracks may occur or cracks may occur on the surface of the inorganic powder-containing resin layer transferred to the substrate. In addition, since the transferability is not sufficient, problems such as peeling off of the substrate force may occur when firing the resin layer containing the inorganic powder.

In order to solve these problems, flexibility and transferability are 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. Forces that could be improved There were 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.

[0009] In addition, the inorganic powder-containing resin layer in the conventional transfer film has low combustibility of organic matter. For this reason, when an inorganic powder-containing resin layer was formed on a substrate and passed through a firing process, many bubbles were generated in the formed inorganic layer. For this reason, there has been a problem that the strength of the member is insufficient due to the decrease in density, and the transmittance or reflectance is lowered depending on the member.

[0010] In the conventional material design, a dispersion failure is likely to occur during the preparation of the inorganic powder-containing resin paste. When poor dispersion occurs, there is an aggregated inorganic powder in the paste, so if there are pinholes in the transfer film, or if surface smoothness and film thickness uniformity are low! /

Patent Document 1: JP-A-9 102273

Patent document 2: Japanese Patent Laid-Open No. 11 162339

Patent Document 3: Japanese Patent Laid-Open No. 11 73875

Patent Document 4: JP-A-11 44949

Disclosure of the invention

Problems to be solved by the invention

[0011] The present invention provides an inorganic powder-containing resin composition capable of forming an FPD panel member (inorganic layer) having high transmittance, reflectance, surface smoothness and film thickness uniformity after firing. aimed to.

[0012] Another object of the present invention is to provide a transfer film that is excellent in flexibility, transferability and nodling properties and has an inorganic powder resin layer comprising the above composition.

[0013] Further, the present invention provides an FPD panel member (dielectric layer, electrode, partition wall, phosphor, resistor, color filter, etc.) that has high transmittance and reflectivity and excellent surface smoothness and film thickness uniformity. It is an object of the present invention to provide a method for manufacturing an FP D capable of efficiently forming a black matrix and the like with high positional accuracy.

Means for solving the problem

[0014] The inorganic powder-containing resin composition of the present invention contains an inorganic powder (A) and a binder resin (B), and the binder resin (B) has a weight-average molecular weight having a polyoxyalkylene moiety. 10,000 to 50,000 (meth) acrylic polymer (B-1), and the polymer (B-1) is added to 0.0 part by weight of 100 parts by weight of the organic powder (A). ; Contained in an amount of ~~ 50 parts by weight [0015] The polymer (B-l) comprises 5 to 30% by weight of a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety, and (meth) acrylate having no polyoxyalkylene moiety. It is preferable to contain 30 to 50% by weight of the structural unit derived from the compound and 30 to 50% by weight of the structural unit derived from the aromatic bur compound.

[0016] The polymer (B-1) includes polyethylene glycol mono (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate. , Nourphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate and noeur phenoxy polypropylene glycol (meth) acrylate It is preferable to have a structural unit derived from at least one (meth) acrylate compound selected from: The inorganic powder-containing resin composition of the present invention preferably further contains a plasticity-imparting substance (C).

[0017] The inorganic powder-containing resin composition of the present invention comprises (D) a photosensitive component, (D-1) multifunctional

It is preferable to further contain (meth) acrylate and (D-2) a radiation polymerization initiator.

Yes

[0018] The transfer film of the present invention is characterized by having an inorganic powder-containing resin layer obtained from the above-mentioned inorganic powder-containing resin composition on a support film.

The transfer film of the present invention is characterized in that it has a laminate comprising a resist layer and an inorganic powder-containing resin layer obtained from the above-mentioned inorganic powder-containing resin composition on a support film.

[0020] The method for producing a flat panel display member of the present invention includes a step of transferring an inorganic powder-containing resin layer formed on the support film and obtained from the inorganic powder-containing resin composition onto a substrate, And a step of baking the inorganic powder-containing resin layer.

[0021] The method for producing a flat panel display member of the present invention includes a step of transferring an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition formed on a support film onto a substrate, Forming a resist layer on the inorganic powder-containing resin layer; A step of exposing the resist layer to form a latent image of the resist pattern, a step of developing the resist layer to reveal the resist pattern, and etching the inorganic powder-containing resin layer to form the resist The method includes a step of forming a pattern corresponding to the pattern, and a step of baking the pattern.

[0022] The method for producing a flat panel display member of the present invention comprises a laminate of a resist layer formed on a support film and an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition. A step of transferring onto a substrate, a step of exposing a resist layer constituting the laminate to form a latent image of a resist pattern, and a step of developing the resist layer to reveal a resist pattern And a step of etching the inorganic powder-containing resin layer to form a pattern corresponding to the resist pattern, and a step of baking the pattern.

[0023] The method for producing a flat panel display member of the present invention includes a step of transferring an inorganic powder-containing resin layer obtained from the above-mentioned inorganic powder-containing resin composition formed on a support film onto a substrate; A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern, a step of developing the inorganic powder-containing resin layer to form a pattern, and a step of baking the pattern It is characterized by including.

[0024] The method for producing a flat panel display member of the present invention comprises a step of transferring an inorganic powder-containing resin layer formed on a support film and obtained from the inorganic powder-containing resin composition onto a substrate; A step of baking the inorganic powder-containing resin layer to form an inorganic film, a step of forming a resist pattern on the inorganic film, and an inorganic pattern corresponding to the resist pattern by etching the inorganic film And a process.

[0025] The flat panel display member is preferably selected from a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color filter, and a black matrix.

[0026] In the method for producing a flat panel display member of the present invention, an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition is formed on a substrate, and the inorganic powder-containing resin layer is fired. A step of forming a dielectric layer on the substrate by the step of forming the inorganic powder-containing resin layer on the substrate using the transfer film. It is characterized by being.

[0027] The method for producing a flat panel display member of the present invention includes a step of forming a pattern containing a conductive powder-containing resin composition on a substrate, and an inorganic powder-containing resin constituting the transfer film on the pattern. The method includes a step of transferring a composition layer to form a laminated film on the substrate, and a step of firing the laminated film.

The invention's effect

[0028] The transfer film in which the inorganic powder-containing resin layer is formed using the inorganic powder-containing resin composition of the present invention can be easily transferred onto a pattern containing an unfired conductive powder-containing resin composition. S, suitable for simultaneous firing of a plurality of members, and excellent in flexibility and transferability.

[0029] The transfer film of the present invention, in which the inorganic powder-containing resin layer is formed using the inorganic powder-containing resin composition of the present invention, is excellent in flexibility and transferability and also in excellent handling properties. Have Therefore, by using the transfer film of the present invention, after firing, an FPD panel member (dielectric layer, electrode, partition wall, excellent surface smoothness and film thickness uniformity, high transmittance or high reflectance). Phosphor, resistor, color filter, black matrix, etc.) can be efficiently formed with high positional accuracy.

Brief Description of Drawings

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP.

FIG. 2 is a schematic view of a structural example of a transfer film of the present invention.

Explanation of symbols

[0031] 1 Glass substrate

2 Glass substrate

3 Bulkhead

4 Transparent electrode

5 Bus electrode

6 Address electrode 10 Protective layer

11 Bulkhead

F1 support film

F2 Material forming material layer

F3 cover film

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the inorganic powder-containing resin composition, transfer film, and method for producing FPD of the present invention will be described in detail.

[Inorganic powder-containing resin composition]

The inorganic powder-containing resin composition of the present invention contains an inorganic powder (A) and a binder resin (B).

[0034] [Inorganic powder (A)]

The inorganic powder (A) used in the inorganic powder-containing resin composition of the present invention can be used for forming various panel members, and is particularly suitable for forming a dielectric layer. Hereinafter, it demonstrates for every kind of panel member.

[0035] Preferred inorganic powders used in the dielectric forming material and the partition wall forming material which are preferred embodiments of the present invention are, for example, glass powder, preferably glass powder having a softening point of 400 to 600 ° C. Can be mentioned.

[0036] When the softening point of the glass powder is less than 00 ° C, organic substances such as the binder resin are not completely decomposed and removed during the firing process of the inorganic powder-containing resin layer! / At this stage, the glass powder melts, so part of the organic substance may remain in the formed member, and as a result of outgas diffusion in the resulting FPD, the lifetime of the phosphor may be reduced. Power. On the other hand, if the softening point of the glass powder exceeds 00 ° C, the inorganic powder-containing resin layer must be baked at a temperature higher than 600 ° C. May occur.

[0037] Specific examples suitable for the glass powder include lead oxide, boron oxide, silicon oxide and calcium oxide (PbO-BO-SiO-CaO) system; Zinc oxide, boron oxide and silicon oxide (ZnO— B ₂ ○ ₂ — Si ○ ₂ ) system; lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO— BO SiO -A1

O) system;

Three

Lead oxide, zinc oxide, boron oxide and silicon oxide (PbO—ZnO—B B—SiO) system; lead oxide, zinc oxide, boron oxide, silicon oxide and titanium oxide (PbO—ZnO—BO)

2 3 SiO-TiO) system;

Examples include bismuth oxide, boron oxide and silicon oxide (Bi O— B O— SiO).

2 3 2 3 2

be able to.

[0038] The average particle size of the glass powder is preferably 0.5 to 2.5 m.

[0039] 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. Good. 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).

[0040] Examples of the inorganic powder used for the electrode forming material include Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr and Co.

[0041] Examples of the inorganic powder used for the resistor forming material include RuO.

[0042] Examples of the inorganic powder used in the phosphor-forming material include:

YO: Eu ³⁺ , Y SiO: Eu ³⁺ , Y Al O: Eu ³⁺ , YVO: Eu ³⁺ , (Y, Gd) BO: Eu ³⁺ , Zn (PO

2 3 2 5 3 5 12 4 3 3

): Red phosphor such as Mn;

4 2

Zn SiO: Mn ゝ BaAl ○: Mn ゝ BaMgAl ○: Mn M LaPO: (Ce, Tb), Y (Al, G

2 4 12 19 14 23 4 3 a) O: green phosphor such as Tb;

5 12

Y SiO: Ce ゝ BaMgAl 〇: Eu ² \ BaMgAl 〇: Eu ² \ (Ca, Sr, Ba) (PO) C

2 5 10 17 14 23 10 4 6 12

: Blue phosphors such as Eu ²⁺ and (Zn, Cd) 2 S: Ag.

[0043] Examples of the inorganic powder used in the color filter forming material include:

Red pigments such as Fe 2 O, Pb 2 O, CdS, CdSe, PbCrO, PbSO, Fe (NO 2);

2 3 3 4 4 4 3 3

Cr O, TiO -CoO- NiO- ZnO, CoO- CrO- TiO -Al O, Co (PO), CoO- ZnO

Green pigments such as 2 3 2 2 2 3 3 4 2; 2 (A1 Na Si O) 'Na S), CoO-Al O and other blue pigments, as well as inorganic for color correction

2 2 3 10 2 4 2 3

As pigment

Yellow face such as PbCrO-PbSO, PbCrO, PbCrO-PbO, CdS, TiO-NiO-SbO

4 4 4 4 2 2 3

Fee;

Orange pigments such as Pb (Cr-Mo-S) 0;

Four

Mention may be made of purple pigments such as Co (PO 4).

3 4 2

[0044] Examples of the inorganic powder used for the black matrix forming material include Mn, Fe, Cr, Ni, Co, and oxides and composite oxides thereof.

[0045] In addition to the inorganic powder described above, the electrode, resistor, phosphor, color filter, and black matrix forming material are used in combination with the glass powder used for the barrier rib forming material and the dielectric forming material. Anyway!

[0046] For example, it is preferable that the content of the glass powder used in combination with the electrode is 30% by weight or less based on the total amount of the inorganic powder, and 20% by weight or less. Is particularly preferred.

[0047] [Binder resin (B)]

The binder resin (B) constituting the resin composition containing the inorganic powder of the present invention is a (meth) acrylic polymer (B 1) having a polyoxyalkylene moiety and a weight average molecular weight of 10,000 to 50,000. And a polymer (B-2) other than the polymer (B-1).

[0048] <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 () 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 inorganic powder-containing resin composition of the present invention is excellent in flexibility and transferability. Become a thing. This is because the polymer (B-1) functions as a plasticizer. Therefore, even if the resin film containing inorganic powder is folded, the surface of the resin layer is not cracked, and the storage stability is good even if it is rolled up and stored. Is

Yes

[0049] Further, since the inorganic powder-containing resin composition contains the polymer (B-1), the thermal decomposability of the inorganic powder-containing resin paste is improved, and after firing the inorganic powder-containing resin layer, In the inorganic layer The number of bubbles remaining in the gas can be reduced. In addition, since the polymer (B-1) is easily decomposed and removed by heat, the function of the inorganic layer obtained by firing the inorganic powder-containing resin layer does not deteriorate.

[0050] Further, when the polymer (B-1) is contained, the dispersibility and 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 are fired. The surface smoothness of the resulting inorganic layer is improved.

[0051] The polymer (B-1) constituting the binder resin of the present invention does not have a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety and a polyoxyalkylene moiety. It is preferable to contain a structural unit derived from a (meth) atallylate compound and a structural unit derived from an aromatic bur compound.

[0052] The polymer (B-1) is a homopolymer of a (meth) acrylate compound having a polyoxyalkylene moiety (hereinafter also referred to as "specific (meth) acrylate compound"), as well as the above-mentioned special polymer. A constant (meth) acrylate compound and a (meth) acrylate compound having no polyoxyalkylene moiety represented by the following general formula (1) (hereinafter also referred to as “(meth) acrylate compound (1)”) And a copolymer with at least one selected from the group of aromatic bur compounds and other copolymer monomers.

[0053] [Chemical 1]

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group.) The units constituting the polymer (B-1) are formed below. Each compound will be explained.

[0055] In the inorganic powder-containing resin composition of the present invention, the polymer (B-1) is an acrylic resin having a weight average molecular weight (Mw) of 10,000-50,000, preferably 20,000-40,000. Contains a polymer.

[0056] Specific (meth) atallylate compound

Specific (meth) acrylate compounds that are constituents of the polymer (B-1) include polyesters. Lenglycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nourphenoxy polyethylene glycol (meth) acrylate, polypropylene Examples include dallicol mono (meth) acrylate, methoxy polypropylene dallicol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate and nourphenoxypolypropylene acrylate (meth) acrylate.

[0057] (Meth) atarylate compound (1)

The (meth) acrylate compound (1), which is a component of the polymer (B-1), includes alkyl (

[0058] Examples of the alkyl (meth) acrylate include methyl (meth) acrylate and ethyl (meth)

) Atalylate, Isobutyl (meth) acrylate, t-Butyl (meth) acrylate, Pentyl (meth) acrylate, Amino (meth) acrylate, Isoamino (meth) acrylate, Hexyl (meth) acrylate Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decdecyl (meth) acrylate, laurinore (meth) ate Rate, stearinole (meth) acrylate and isostearyl (meth) acrylate.

[0059] Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate.

And 4-hydroxybutyl (meth) acrylate.

[0060] Examples of the phenoxyalkyl (meth) acrylate include phenoxycetyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. [0061] Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxy ethyl (meth) acrylate, 2-propoxy cetyl (meth) acrylate, 2-butoxetyl ( And (meth) acrylate and 2-methoxybutyl (meth) acrylate.

[0062] Examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, 4-butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl ( Examples include (meth) acrylate, dicyclopentagenyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate.

[0063] Preferable examples of the (meth) acrylate compound (1) include butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and Examples include 2-ethoxyethyl (meth) acrylate.

[0064] Bulle,

The aromatic bur compound that is a constituent of the polymer (B-1) is an aromatic compound having an ethylenically unsaturated bond, and the above-mentioned specific (meth) acrylate compound and (meth) acrylate compound (1) If you don't fall under this category, you'll need a compound! / There is no particular limitation as long as it is a compound that can be copolymerized with the specific (meth) acrylate compound or the (meth) acrylate compound (1). For example, styrene, α-methyl styrene, butyl benzoic acid, phthalphthalic acid, vinyl Aromatic butyl compounds such as benzyl methyl ether and butyltoluene; polystyrene having a (meth) atalyloyl group at the end. These may be used alone or in combination of two or more.

[0065] Preferable examples of the aromatic bur compound include bulubenzoic acid, burbendyl methyl ether, styrene, and α-methylstyrene.

[0066] Other copolymerizable monomers

The polymer (Β-1) is a copolymerizable monomer other than the specific (meth) acrylate compound, (meth) acrylate compound (1) and aromatic bur compound (hereinafter referred to as “other copolymer”). It may also be reacted with a “monomeric monomer”). Other copolymerizable monomers include aminocarboxylic esters of unsaturated carboxylic acids such as aminoethyl acrylate; glycidyl (meth 1) Unsaturated carboxylic acid glycidyl esters such as acrylate; Carboxylic acid esters such as butyl acetate and propionate; Cyanide butyl compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; 1, 3-butadiene And aliphatic conjugates such as isoprene; unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid; other unsaturated carboxylic acids Bur ethers such as burbendyl methyl ether and burglycidyl ether; and macromonomers such as polymethyl (meth) acrylate, polybutyl (meth) acrylate and polysilicon.

[0067] Preferable examples of other copolymerizable monomers include (meth) acrylic acid, maleic acid, vinyldaricidyl ether, butadiene and isoprene.

[0068] <Polymer (Β-1)>

As described above, the polymer (Β-1) includes the above-mentioned specific (meth) acrylate homopolymer, the specific (meth) acrylate, the (meth) acrylate compound (1), and the aromatic bur. Examples thereof include a copolymer and a copolymer containing at least one selected from other copolymerizable monomers as a constituent component. Preferable specific examples of the copolymer include the specific (meth) acrylate and a copolymer of the (meth) acrylate compound (1) and aromatic bur compounds.

[0069] The composition ratio of the copolymer is usually specified with respect to 100% by weight of the polymer (Β-1).

(Meth) Atari rate 5-30 wt ^_0/0, (meth) Atari Rate Compound (1) 30 to 50 weight ^_0/0, an aromatic Bulle compounds 30-50 wt%, the specific (meth) Atari Rate 10 -25% by weight, (meth) acrylate compound (1) 35-45% by weight, and aromatic bur compounds 35-45% by weight are more preferred. In addition, when other copolymer monomers are contained, the composition ratio of !! to 20% by weight, more preferably 5 to 15% by weight, with respect to 100% by weight of the polymer (Β-1) Power to contain in Inorganic powder containing resin transfer film It is preferable for further improving the flexibility and transferability of the resin transfer film.

[0070] Examples of the polymer (B-1) used in the present invention include polymethylene glycol (meth) ateryl one-to-polybutyl metatalylate copolymer, polyethylene glycol (meth) acrylate, polybutyl metatalylate copolymer , Polypropylene glycol (meth) acrylate Butylmetatalylate copolymer, polyethylene glycol poly (meth) acrylate relay methyl methacrylate, butyl metatalylate copolymer, polyethylene glycol poly (meth) acrylate-methyl methacrylate-butyl (meth) acrylate, styrene copolymer, polyethylene render Recall poly (meth) acrylate-(meth) acrylic acid-styrene copolymer, polypropylene glycol poly (meth) acrylate 2-ethoxyethyl (meth) acrylate styrene copolymer, polymethylene glycol (meta ) Atarylate 2-ethylhexyl acrylate Styrene copolymer Polyethylene glycol (meth) acrylate 2-Ethyl hexyl acrylate Styrene copolymer and polyprorendral acrylate (meth) acrylate 2 — Ethylhexyl acrylate, styrene copolymer and the like.

[0071] The polymer (B-1) is prepared from the specific (meth) acrylate compound and, if necessary, the (meth) acrylate compound (1) and other copolymerizable monomers by a known method. It is obtained by polymerizing. 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.

[0072] The preferred molecular weight of the polymer (B-1) is gel permeation chromatography.

(GPC) polystyrene-reduced weight average molecular weight (hereinafter also simply referred to as “weight average molecular weight” or “Mw”) is 10,000 to 50,000, more preferably 20,000 to 40,000. It is.

[0073] <Polymer (B-2)>

As the polymer (B-2) used in the present invention, any resin other than the above can be used as long as it is other than the polymer (B-1). Of these, a (meth) acrylate polymer (hereinafter also simply referred to as “acrylic resin”) having no polyoxyalkylene moiety is preferred. When the composition of the present invention contains an acrylic resin as the polymer (B-2), the inorganic powder-containing resin layer formed from the composition exhibits excellent (heating) adhesion to the substrate. . Therefore, a transfer film produced by applying the composition of the present invention on a support film has excellent transferability (heat adhesion to a substrate) of the inorganic powder-containing resin layer.

[0074] As the acrylic resin, an inorganic powder can be bound with appropriate adhesiveness, and it is completely oxidized and removed by baking treatment (400 to 600 ° C) of the inorganic powder-containing resin layer. ( Co) polymers are preferred.

[0075] Examples of the acrylic resin include a homopolymer of the (meth) acrylate compound (1), a copolymer containing two or more of the (meth) acrylate compound (1), and the (meth) acrylate. Copolymers of the rate compound (1) and other copolymerizable monomers are included.

[0076] The (meth) acrylate compound (1) used in the polymer (B-2) is, for example,

Examples include attalylate, cycloalkyl (meth) acrylate, benzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. More specific examples are shown below.

[0077] Examples of the alkyl (meth) acrylate include methyl (meth) acrylate and ethyl (meth

[0078] Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate.

And 4-hydroxybutyl (meth) acrylate.

[0079] Examples of the phenoxyalkyl (meth) acrylate include phenoxychetyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

[0080] Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxy cetyl (meth) acrylate. And 2-butoxychetyl (meth) acrylate and 2-methoxybutyl (meth) acrylate.

[0081] Examples of the alkyl glycidyl (meth) acrylate include glycidyl (meth) acrylate and / 3-methyldaricidyl (meth) acrylate.

[0082] Examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, 4-butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl ( Examples include (meth) acrylate, dicyclopentagenyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate.

More preferably, alkyl (meth) acrylate is used, and particularly preferably, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate. Rate and 2-ethoxyethyl (meth) acrylate are used.

[0084] 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, but (meth) acrylic acid, bull benzoic acid, malein. Unsaturated carboxylic acids such as acids and bullphthalic acid;

Examples include bur group-containing radically polymerizable compounds such as burbendyl methyl ether, burglycidyl ether, styrene, α-methyl styrene, butadiene and isoprene.

[0085] In the polymer (Β-2) constituting the composition of the present invention, the copolymer component derived from the (meth) acrylate compound (1) represented by the general formula (1) is usually 70% by weight. Above, preferably 90% by weight or more.

[0086] Specific examples of preferred acrylic resins include polymethyl methacrylate, polybutyl methacrylate, methyl methacrylate-butyl methacrylate copolymer and butyl methacrylate 2-to-hexyl hexyl methacrylate 2-hydroxypropyl. And metatalylate copolymers. [0087] The Mw of the polymer (B-2) constituting the composition of the present invention is 4,000 to 300,000, preferably <10,000 to 200,000.

[0088] <Binder resin (B) content>

The binder resin (B) is 5 to 80 parts by weight, preferably 10 in total of the polymer (B-1) and the polymer (B-2) with respect to 100 parts by weight of the inorganic powder (A). Used in an amount of ~ 50 parts by weight. If the amount of the binder resin (B) is too small, the inorganic powder may not be securely bound and held. On the other hand, if the amount of the binder resin (B) is excessive, the firing process takes a long time and the formed sintered body (for example, the dielectric layer) has sufficient strength and film thickness. May not.

[0089] The polymer (B-1) is usually used in an amount of 0.0;! To 50 parts by weight, preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of the inorganic powder (A). It is done. If 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 resin layer (heat adhesion to the substrate) may be inferior. is there. On the other hand, if the amount of the polymer (B-1) is more than the above range, the adhesion and transferability of the formed inorganic powder-containing resin layer at the time of transfer become excessive, and it becomes difficult to peel off the support film. Or a transfer film having the resin layer may be inferior in handleability.

[0090] [Plasticizer (C)]

The inorganic powder-containing resin composition of the present invention may contain a plasticity-imparting substance (C) 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 composition containing the plasticity-imparting substance (C) has sufficient flexibility.

[0091] Examples of the plasticizing substance (C) include a compound represented by the following general formula (2), a plasticizer selected from the group consisting of a compound represented by the following general formula (3), polypropylene glycol, and Examples thereof include copolymerizable monomers such as the (meth) acrylate compound described above, and those having a boiling point of 150 ° C. or higher are preferred. Such plasticizing substances (C) may be used alone or in combination of two or more! /.

[0092] [Chemical 2]

(In the formula (2), 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 And a methylene group or a divalent chain hydrocarbon group having 2 to 30 carbon atoms, s is an integer of 0 to 5, and t is an integer of 1 to 10).

[0094] [Chemical 3]

H I I Π

H ₃ C— C— C—〇一 C— R ⁷ ... (3)

OH H ○

(In the formula (3), R ⁷ represents a monovalent chain hydrocarbon group having carbon number;! To 30.)

In the general formula (2), the monovalent chain hydrocarbon group represented by R ³ or R ⁵ is a linear or branched alkyl group (saturated group) or alkenyl group (unsaturated group), The chain hydrocarbon group has a carbon number of !! to 30, preferably 2 to 20, more preferably 4 to 10; If the number of carbon atoms in the chain hydrocarbon group is more than the above range, dissolve resistance is low in the solvent to be described later, is that the force ^s difficult to provide good flexibility inorganic powder-containing resin layer .

[0096] 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).

[0097] Examples of the compound represented by the general formula (2) include dibutyl adipate, diisobutyl adipate, di-2-ethenorehexino rare dipate, di-2-ethenorehexinorezelate, dibutyl sebacate, and dibutyl diacetate. Examples include glycol adipate.

In the above general formula (3), the monovalent chain hydrocarbon group represented by R ⁷ is a linear or branched alkyl group (saturated group) or alkenyl group (unsaturated group), The chain hydrocarbon group has a carbon number of !!-30, preferably 2-20, more preferably 10--18.

[0099] Examples of the compound represented by the general formula (3) include propylene glycol monolaurate. And propylene glycol monooleate.

[0100] When polypropylene glycol is used as the plasticizing substance (C), the weight average molecular weight (Mw) of the polypropylene glycol is preferably in the range of 200-3,000. A range of 2,000 is particularly preferred. 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 resin layer may be transferred from the support film to the glass substrate. In this case, when the support film is peeled off from the resin layer heat-bonded to the glass substrate, the resin layer may cause cohesive failure. On the other hand, if Mw exceeds 3,000, an inorganic powder-containing resin layer having good heat adhesion to the glass substrate as the transferred body may not be obtained.

[0101] In addition, when etching the inorganic powder-containing resin layer by sandblasting using the composition of the present invention in the FPD production method (II), the plasticity-imparting substance (C) has 10 or 10 carbon atoms. It is preferred to use 12 long chain alkyl (meth) acrylates. The use of the plasticizing substance (C) can provide sufficient flexibility as a dry film and is easily decomposed or volatilized by a post-beta described later, and is therefore an essential property for sandblasting. This is because brittleness can be imparted.

[0102] Examples of the long-chain alkyl (meth) acrylate include forces such as isodecyl (meth) acrylate and lauryl (meth) acrylate, particularly isodecyl and lauryl methacrylate. preferable.

[0103] The plasticizer (C) is 3% by weight of the total components excluding the solvent from the composition of the present invention.

% Or more, preferably 4 to 15% by weight. When the content of the plasticity-imparting substance (C) is too small, it may be difficult to give good flexibility to the transfer film to be formed.

[0104] [Photosensitive component (D)]

The composition of the present invention may be a photosensitive composition containing, as the photosensitive component (D), a polyfunctional (meth) acrylate (D-1) and a radiation polymerization initiator (D-2). Yo! / The polyfunctional (meth) acrylate (D-1) is polymerized by exposure to make the exposed part insoluble in alkali or hardly soluble in alkali. [0105] Highly multifunctional (meth) atarylate (D— 1)>

Examples of the polyfunctional (meth) acrylate (D-1) include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Di (meth) acrylates of both end hydroxylated polymers such as both end hydroxypolybutadiene, both end hydroxypolyisoprene and both end hydroxypoly force prolatatone; glycerin, 1, 2, 4 butanetriol, trimethylolalkane, tetramethylol Trivalent or higher polyvalent alcohols such as alkane, pentaerythritol and dipentaerythritol

Poly (meth) atrelates of polyalkylene glycol adducts of polyhydric alcohols with 3 or more valences;

Cyclic poliopolyesters such as 1,4-cyclohexanediol and 1,4 benzenediols (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin Examples thereof include oligo (meth) acrylates such as (meth) acrylate and spirane resin (meth) acrylate. These may be used alone or in combination of two or more. Among these, trimethylolpropane tritalylate, tripropylene glycol ditalylate and the like are particularly preferably used.

[0106] The molecular weight of the polyfunctional (meth) acrylate (D-1) is preferably 100 to 2,000. The polyfunctional (meth) acrylate (D-1) is usually used in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the inorganic powder (A).

[0107] <Radiation polymerization initiator (D-2)>

Examples of the radiation polymerization initiator (D-2) used in the present invention include benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-1-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexane. Xylphenylketone, 2,2-dimethoxy-2-phenylacetophenone, 2 methyl- [4 '(methylthio) phenyl] -2 morpholino — 1—propanone, 2—benzyl 2—dimethylamino 1— (4-morpholinophenol) butane 1 on and 1 [9-ethyl-6- (2 methylbenzoyl) 9 · Η · —force nolevazol 3—inole] ethane 1 onoxime Carbonate compounds such as acetate;

Azo and azide compounds such as azoisobutyronitrile and 4 azidobenzaldehyde;

Organic sulfur compounds such as mercabtan disulfide;

Organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl hydride peroxide, cumene hydride oxyperoxide and paraffin hydride oxyperoxide;

1, 3 Bis (trichloromethyl) 5— (2, monocyclic phenyl) 1, 3, 5 triazine and 2— [2- (2 furaninole) ethylenyl] 4, 6 Bis (trichloromethyl) 1 , 3, 5 Trihalomethanes such as triazine;

Examples include imidazole dimers such as 2, 2, 1bis (2-black mouth phenol) 4, 5, 4,, 5, monotetraphenol 1, 2, and 1 imidazole. These can be used alone or in combination of two or more.

[0108] The radiation polymerization initiator (D-2) is usually 0.;! To 50.0 parts by weight, preferably 100 parts by weight of the polyfunctional (meth) acrylate (D-1). 1. 0-30. 0 parts by weight used

[0109] [Solvent]

The composition of the present invention usually contains a solvent. As such a solvent, the affinity for inorganic powder and the solubility of the binder resin are good, and it is possible to impart an appropriate viscosity to the composition, and it can be easily evaporated by drying treatment. It is preferable that it can be removed.

[0110] Also, 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. The power S

[0111] Examples of the specific solvent include methyl ethyl ketone, jetyl ketone, methyl butyl keto , Ketones such as dipropyl ketone and cyclohexanone;

Anoleconoles such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetonanoreconole;

Ether-based alcohols such as ethylene glycol monomethino ethenole, ethylene glycol monomethino ree tenole, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; n-butyl acetate and Saturated aliphatic monocarboxylic acid alkyl esters such as amyl acetate;

Examples thereof include lactic acid esters such as ethyl lactate and n-butyl lactate; etherol esters such as methinoreethenoleacetate and ethinoleyl 3-ethoxypropionate. Among these, methyl butyl ketone, cyclohexanone, diacetone alcoholone, ethylene glycol methanol monobutinoate ethere, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropylone are preferred. These specific solvents may be used alone or in combination of two or more.

[0112] Examples of usable solvents other than the above-mentioned specific solvents include turpentine oil, ethenorecello sonoleb, methinorecero sonoleb, tenorepineo monore, butinorecanorebitonoreacetate, butinorecanorebitonore, Use force S to list isopropyl alcohol and benzyl alcohol.

[0113] From the viewpoint of maintaining the viscosity of the composition within a suitable range, the solvent is used in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the inorganic powder (A). It is done. The ratio of the specific solvent to the total solvent is 50% by weight or more, preferably 70% by weight or more.

[0114] [Various additives]

The composition of the present invention includes, as optional components, a dispersant, a development accelerator, an adhesion assistant, a halation inhibitor, a leveling agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a sensitizer. Various additives such as an agent or a chain transfer agent may be contained. [0115] [Preparation method of resin composition containing inorganic powder]

The inorganic powder-containing resin composition of the present invention comprises the above-mentioned inorganic powder (A), binder resin (B), if necessary, a plasticizer (C), and a polyfunctional (meth) acrylate (D-1). ), A radiation polymerization initiator (D-2), a solvent and various additives can be prepared by kneading using a kneader and a disperser such as a roll kneader, a mixer, a homomixer, or a sand mill. . The viscosity of the composition of the present invention prepared as described above is preferably 0.3 to 30 Pa ′s.

[0116] [Transfer film]

The transfer film of the present invention has an inorganic powder-containing resin layer obtained from the above-described inorganic powder-containing resin composition of the present invention on a support film.

[0117] The transfer film of the present invention may be one having a laminated film of a resist film and the inorganic powder-containing resin layer on a supporting film (laminated transfer film).

[0118] If necessary, a cover film may be provided on the surface of the inorganic powder-containing resin layer.

[0119] Each component of the transfer film will be specifically described below.

(1) Support film

The transfer film of the present invention has a support film that supports the 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 is flexible, the inorganic powder-containing resin composition can be applied to the surface of the support film with a roll coater or a blade coater, and the resulting transfer film is wound into a roll. It is possible to save or supply the product in a state of being stored.

[0120] Examples of the resin for forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinylenoreconole, fluorine-containing resins such as polychlorinated butyl and polyfluoroethylene, nylon In addition, it is possible to raise the cell mouth.

[0121] The thickness of the support film is 20 to 100 m. In addition, it is preferable that the surface of the support film has been subjected to a release treatment, so that in the transfer process to the glass substrate, The peeling operation of the support film can be easily performed.

(2) Cover film

In the transfer film of the present invention, a cover film may be provided on the surface of the resin layer in order to protect the surface of the inorganic powder-containing resin layer. This cover film is preferably a resin film having flexibility, whereby the transfer film obtained can be stored or supplied in a roll shape.

[0122] Examples of the resin constituting the cover film include a polyethylene terephthalate film, a polyethylene film, and a polybulualcohol-based film.

[0123] The thickness of the cover film is 20 to 100 mm. Further, it is preferable that the surface of the cover film has a smaller adhesion to the inorganic powder-containing resin layer than the support film, which may be subjected to a release treatment.

(3) Resin layer containing inorganic powder

The inorganic powder-containing resin layer is usually formed by coating the inorganic powder-containing resin composition on a support film, drying the resulting coating film, and removing all or part of the solvent.

[0124] As a method for applying the inorganic powder-containing resin composition onto a support film, a coating film with high uniformity in film thickness and large film thickness (for example, 10 πι or more) is formed with high efficiency. The force S is a method that can be applied S Preferably, 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 a force S depending on the height of the panel member to be formed, usually 10 to 300 111.

[0125] The drying condition of the coating film is, for example, 50 to; at 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 within 2% by weight.

(4) Resist layer

The resist film used for the laminated transfer film of the present invention is usually a resist assembly containing a binder polymer, a polyfunctional monomer (D-1) and a radiation polymerization initiator (D-2). The composition is formed by coating on a support film.

[0126] The binder polymer used in the resist composition needs to be an alkali-soluble resin in the case of an alkali development type, and has an ethylenically unsaturated group having at least one carboxynole group in the molecule. It is a carboxyl group-containing copolymer obtained by polymerizing a monomer composition containing a carboxyl group-containing monomer and a copolymerizable monomer copolymerizable with the carboxyl group-containing monomer. Is preferred.

[0127] The copolymerization ratio of the carboxyl group-containing monomer in the binder polymer is 5 to 50% by weight, preferably 10 to 40% by weight, based on the total amount of the monomer. If the copolymerization ratio of the carboxyl group-containing monomer is lower than the above range, the resulting resist composition tends to be less soluble in an alkali developer. On the other hand, when the copolymerization ratio of the carboxyl group-containing monomer exceeds the above range, the resist pattern tends to fall off from the inorganic powder paste layer during development.

[0128] The copolymer having a structural unit derived from the carboxyl group-containing monomer has alkali solubility, and in particular, the copolymer having the structural unit in an amount within the above range is an alkaline developer. Excellent solubility. For this reason, by using such a copolymer as a binder polymer in the resist composition, the amount of undissolved material in the alkaline developer is essentially reduced. The occurrence of dirt and film residue can be reduced.

[0129] Further, the resist pattern obtained from the resist composition containing the copolymer as a binder polymer has excellent adhesion to a resin layer containing an inorganic powder that does not excessively dissolve in an alkali developer. Therefore, it is difficult for the resin layer to fall off.

[0130] Examples of the carboxyl group-containing monomer include (i) unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, and (ii) unsaturated compounds such as itaconic acid, maleic acid and fumaric acid. Examples include dicarboxylic acids and (iii) other unsaturated carboxylic acids. These may be used alone or in combination of two or more.

[0131] Further, as the copolymerizable monomer, for example,

Aromatic butyl compounds such as styrene, α-methylstyrene and butyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydride Unsaturated carboxylic acid alkyl esters such as loxochetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyleno (meth) acrylate and cyclohexyl (meth) acrylate;

Unsaturated carboxylic acid aminoamino esters such as aminoethyl acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; carboxylic acid bis esters such as acetic acid and propionic acid;

Cyanide bur compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;

1, 3, 3-aliphatic conjugates such as butadiene and isoprene;

Examples thereof include macromonomers such as polystyrene, polymethyl (meth) acrylate, polybutyl (meth) acrylate and poly-silicone having a (meth) attaroyl group at the terminal. These can be used alone or in combination of two or more.

[0132] The binder polymer has an Mw of 3,000-300,000, preferably 5,000-200,000. By using a binder polymer having such a molecular weight, a resist composition having high image clarity can be obtained, whereby a resist pattern having sharp pattern edges can be formed, and a panel having a uniform pattern can be formed. Parts can be formed.

[0133] As the polyfunctional monomer used in the resist composition, the above-mentioned polyfunctional (meta) acrylate (D-1) is preferably used. The polyfunctional monomer is usually used in an amount of 5 to 100 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the binder polymer. If the amount of the polyfunctional monomer is lower than the above range, the resist pattern strength tends to be insufficient, and if the amount exceeds the above range, the alkali resolution decreases or the portion other than the resist pattern forming portion. Soiling and film residue may occur.

[0134] Examples of the radiation polymerization initiator used in the resist composition include the radiation polymerization initiator (D-2) described above.

[0135] The resist composition usually contains a solvent in order to impart appropriate fluidity or plasticity or good film-forming properties. As such a solvent, the specific solvent mentioned above etc. which are not specifically limited are used preferably. [0136] The resist composition includes, as optional components, a development accelerator, an adhesion assistant, a halation inhibitor, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a filler, a phosphor, Contains various additives such as pigments and / or dyes! /, May!

[0137] In the laminated transfer film, a resist composition is formed on a support film or an inorganic powder-containing resin layer to form a resist film, and the composition of the present invention is applied on the resist film. It is obtained by forming an inorganic powder-containing resin layer. In addition, the laminated transfer film forms an inorganic powder-containing resin layer on the support film or the inorganic powder-containing resin layer, and forms a resist film on the protective film separately from the resin film surface. It can also be suitably formed by a method in which the resist film surface and the resist film surface are overlapped and pressure-bonded.

[0138] As a method for applying and drying the resist composition, the above-described method for applying and drying the inorganic powder-containing resin composition can be used.

[0139] The thickness of the resist film to be formed is preferably 5 to 15 m.

[0140] The transfer film of the present invention is usually stored in a rolled state.

[0141] [Method for manufacturing FPD member]

Preferred embodiments of the method for producing the FPD member of the present invention are as follows.

[1] A panel member by a method comprising a step of transferring an inorganic powder-containing resin layer of a 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 dielectric 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 step A dielectric layer, an electrode, a partition, a phosphor, a resistor, which is a panel member, by a method including a step of etching a resin layer to form a pattern corresponding to a resist pattern and a step of baking the pattern A method of forming at least one selected from a color filter and a black matrix (FPD production method (II)).

[3] A step of transferring a laminated film of a laminated transfer film on a 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 a resist pattern Forming a latent image, developing the resist film to reveal the resist pattern, etching the inorganic powder-containing resin layer, and forming a resist pattern Selected from a dielectric layer, an electrode, a barrier rib, a phosphor, a resistor, a color filter, and a black matrix, which are panel members, by a method including a step of forming a pattern corresponding to the pattern and a step of baking the pattern. A method of forming at least one kind (FPD manufacturing method (111)).

[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, A dielectric layer, an electrode, a partition wall, a phosphor, a resistor, which is a panel member, by a method including a step of developing a machine powder-containing resin layer to form a pattern and a step of firing the pattern. A method of forming at least one selected from a color filter and a black matrix (FPD manufacturing 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, and a resistor, which are panel members, by a method including a step of forming a resist pattern thereon and a step of etching the inorganic film to form a pattern corresponding to the resist pattern And a method of forming at least one selected from a color filter and a black matrix (FPD production method (V)).

[0142] Each aspect will be described below.

[0143] <FPD manufacturing method (I)>

An example of the transfer process in the FPD manufacturing method (I) 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) After removing the cover film as necessary from the surface of the inorganic powder-containing resin layer in the cut transfer film, 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) The heating roller is moved on the transfer film superimposed on the substrate and thermocompression bonded.

(4) The support film is peeled off from the inorganic powder-containing resin layer fixed to the substrate by thermocompression bonding.

[0144] By the operation as described above, the inorganic powder-containing resin layer on the support film is transferred onto the substrate. It is. As the 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 10 Om / Minutes. Such an operation (transfer process) can be performed by a laminator apparatus. Note that the preheating temperature at which the substrate may be preheated is, for example, 40 to 100 ° C.

[0145] 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 is a force that varies depending on the melting temperature of the substrate and the constituent materials in the inorganic powder-containing resin layer, for example, 300 to 800 ° C, preferably 400 to 620 ° C.

[0146] The method for producing a flat panel display (FPD) member of the present invention comprises a step of forming a pattern containing a conductive powder-containing resin composition on a substrate, and an inorganic powder constituting the transfer film on the pattern. A step of transferring the body-containing resin composition layer to form a laminated film on the substrate; and a step of firing the laminated film.

[0147] f † Half ^ ^ J Composition 1 ^ »Development of patterns including,

As the conductive powder-containing resin composition used in the present invention, a composition used for forming a general electrode can be used.

[0148] Examples of the conductive powder include Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr, and Co.

[0149] The conductive powder-containing resin composition forms a film by screen printing or photosensitive paste, and is subjected to exposure and development to form a pattern. The film thickness of the conductive powder-containing resin layer is usually 5 to 100 μm.

[0150] Boiled rice cakes ^: Bine {Bake of 本, 本

The inorganic powder-containing resin layer transferred and formed on the surface of the substrate on which the pattern containing the unfired conductive powder-containing resin composition is formed is fired to form a conductive sintered body (electrode layer) and inorganic sintering. It becomes a laminated structure of a body (dielectric layer). As a firing method, unfired conductive And a method in which a substrate on which an inorganic powder-containing resin layer is transferred and formed on a pattern containing a conductive powder-containing resin composition is placed in a high-temperature atmosphere. By the firing treatment, the organic substances contained in the conductive powder-containing resin layer and the inorganic powder-containing resin layer are decomposed and removed, and the conductive powder and the inorganic powder are melted and sintered.

[0151] <FPD manufacturing method (II)>

The FPD production method (II) includes 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 forming a resist pattern on the transferred inorganic powder-containing resin layer. And a step of etching the inorganic powder-containing resin layer to form a pattern corresponding to the resist pattern, and a step of baking the pattern.

Hereinafter, a method for forming “partition walls”, which are constituent elements of FPD, on the surface of the back substrate will be described. In this method, (1) an inorganic powder-containing resin layer transfer step, (2) a resist pattern forming step, (3) an inorganic powder-containing resin layer etching step, and (4) an inorganic powder A partition wall is formed on the surface of the substrate by a process including a firing process of the containing resin pattern.

[0153] In the present invention, the mode of transferring the inorganic powder-containing resin layer onto the substrate is not limited to the mode of transferring onto the surface of the glass substrate, but is transferred onto the surface of the dielectric layer. Various embodiments are also included.

(1) Transfer process of resin layer containing inorganic powder

The transfer process of the inorganic powder-containing resin layer is the same as the transfer process in the FPD manufacturing method (I) described above.

(2) Resist pattern formation process

A method for forming a resist pattern on the inorganic powder-containing resin layer is not particularly limited, but a resist pattern is preferably formed through steps of forming a resist film, exposing and developing.

[0154] The resist film may be formed by applying the above-described resist composition onto the inorganic powder-containing resin layer and drying it, or applying the resist composition onto a support film and drying it. The resulting transfer film may be used to transfer and form a resist film on the inorganic powder-containing resin layer. However, considering the simplicity of the process, formation by transfer is preferred. [0155] In the exposure of the resist film, the surface of the formed resist film is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a latent image of the resist pattern. The ultraviolet irradiation apparatus used for exposure is not particularly limited, and the ultraviolet irradiation apparatus generally used in the photolithography method, the exposure apparatus used when manufacturing semiconductors and liquid crystal display devices, etc. Is mentioned. Further, exposure may be performed by drawing laser light or the like without using an exposure mask. Note that it is preferable to perform the exposure process in a state where the resist film is coated on the resist film and not peeled, and peeled after the exposure.

[0156] The development of the resist film is a process for revealing a resist pattern (latent image) in the exposed resist film. The development processing conditions include the type of developer, composition, concentration, development time, development temperature, development method (for example, dipping method, rocking method, shower method, spray method or paddle method) depending on the type of resist film. ) Or a developing device or the like can be selected as appropriate. By this development step, a resist pattern (pattern corresponding to the exposure mask) composed of the resist remaining portion and the resist removal portion is formed.

[0157] This resist pattern acts as an etching mask in the next step (etching step of the inorganic powder-containing resin layer), and the constituent material (photocured resist) of the remaining resist portion contains inorganic powder. It is necessary that the dissolution rate in the developer used in the next step is lower than that of the constituent material of the resin layer.

(3) Inorganic powder-containing resin layer etching process

In this step, the inorganic powder-containing resin layer is etched to form a partition pattern layer corresponding to the resist pattern. That is, the portion corresponding to the resist removal portion of the resist pattern in the inorganic powder-containing resin layer is selectively removed. Then, a predetermined portion of the inorganic powder-containing resin layer is completely removed, and the dielectric layer is exposed. As a result, an inorganic powder-containing resin pattern composed of the resin layer residual portion and the resin layer removal portion is formed.

[0158] As the etching method, a force S that can be appropriately selected according to the type of the inorganic powder-containing resin layer, an alkali development treatment or a sand blast treatment is preferably used.

[0159] When the alkali development treatment is performed, the developer used for developing the resist film described above is used. However, it is preferable to continuously develop the resist film and the inorganic powder-containing resin layer under the same development conditions. The type, composition, concentration, processing time, processing temperature, processing method (for example, dipping method, rocking method, shower method, spray method or paddle method) or processing device of the developing solution or the like can be appropriately selected. The resist remaining portion constituting the resist pattern is gradually dissolved during the image processing, and is completely removed at the stage where the inorganic powder-containing resin pattern is formed (at the end of the image processing). It is preferable. Even if a part or all of the resist residue remains after the etching (development) process, the resist residue is removed in the next baking step.

[0160] In the case of sandblasting, the inorganic powder-containing resin layer is formed by using a transfer film containing plasticity-imparting substance (C), particularly, a long-chain alkyl (meth) acrylate, in the inorganic powder-containing resin layer. It is preferable to perform post-transfer treatment after the transfer. By performing post-baking, the residual solvent and plasticity-imparting substance (C) in the resin layer can be removed, and sandblasting (brittleness) can be imparted to the resin layer. Here, the post-beta treatment conditions are, for example, a treatment temperature of 100 to 300 ° C. and a treatment time of 15 to 120 minutes. After that, a resist pattern is formed on the resin layer, and the exposed portion of the inorganic powder-containing resin layer after the post-beta treatment is mainly removed by sandblasting using a sandblasting device, whereby a pattern having a desired form is obtained. Form. Even if a part or all of the resist residue remains after the etching process, the resist residue is removed in the next baking step.

(4) Inorganic powder-containing resin pattern firing process

In this process, the partition walls are formed by baking the inorganic powder-containing resin pattern. As a result, in the panel material in which the organic material in the resin layer remaining portion is burned out to form a partition and the partition is formed on the surface of the dielectric layer, the space partitioned by the partition (derived from the resin layer removal portion) Space) is a plasma action space.

[0161] The temperature of the baking treatment is required to be a temperature at which the organic substance is burned off, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

[0162] <Method for producing FPD (III)>

FPD production method (III) is a preferred embodiment of FPD production method (II), in particular, This is a preferred embodiment when the strike film and the inorganic powder-containing resin layer are etched by alkali development.

[0163] In the FPD manufacturing method (III), the laminated film of the resist film and the inorganic powder-containing resin layer is transferred onto the substrate. An example of the transfer process is as follows.

[0164] After the cover film of the transfer film is peeled off, the transfer film is superimposed on the surface of the dielectric layer so that the surface of the inorganic powder-containing resin layer is in contact with the surface of the dielectric layer. Thermocompression bonding. As a result, the laminated film of the inorganic powder-containing resin layer and the resist film is transferred and adhered to the surface of the dielectric layer. As the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C., the roller pressure by the heating roller is 1 to 5 kg / cm ^2, and the moving speed of the heating roller is 0.;! To 10. Om / min . Further, the glass substrate may be preheated, and the preheating temperature may be, for example, 40 to 100 ° C.

[0165] The process after transfer of the laminated film in the FPD manufacturing method (III) is the same as the steps (2) to (4) in the FPD manufacturing method (II) (in particular, the resist film and the inorganic powder-containing resin layer). In the case of alkali development).

[0166] <Method for manufacturing FPD (IV)>

The FPD production method (IV) transfers an inorganic powder-containing resin layer constituting the photosensitive transfer film of the present invention onto a substrate and exposes the resin layer to form a latent image of a pattern. The process of forming a panel member selected from a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color filter, and a black matrix by developing the oil layer to form a pattern and firing the pattern. Including.

In this method, for example, when a partition wall is formed, after the “transfer process of the inorganic powder-containing resin layer” in the FPD manufacturing method (II), the “resist film exposure step” and “resist An inorganic powder-containing resin pattern is formed by a method and conditions according to the “development process of the film”, and then a partition wall is formed on the surface of the substrate by the “firing process of the inorganic powder-containing resin pattern”.

[0168] <FPD manufacturing method (V)>

In the FPD manufacturing method (V), the inorganic powder-containing resin layer constituting the transfer film of the present invention is transferred onto a substrate, the resin layer is baked to form an inorganic film, and a resist pattern is formed on the inorganic film. A panel material such as a partition is formed by forming a film and etching the inorganic film to form an inorganic film pattern corresponding to the resist pattern.

[0169] In this method, for example, when a partition wall is formed, after the "transfer process of the inorganic powder-containing resin layer" in the FPD manufacturing method (II), the "calculation process of the inorganic powder-containing resin pattern" First, an inorganic film is formed, a resist pattern is formed on the inorganic film under the conditions in accordance with the “resist pattern forming step”, and then the inorganic film is etched using the resist pattern as a mask. Thereby, a partition is formed on the surface of the substrate. Note that the resist remaining on the partition wall surface is usually stripped using a stripping solution or the like.

[0170] As the etching solution for the inorganic film, an acid solution such as nitric acid, hydrochloric acid and sulfuric acid is usually used, and nitric acid is particularly preferably used. The concentration of the etching solution is usually 0.2;! To 10% by weight, preferably 0.2 to 2% by weight. The etching step is preferably performed by spraying an etching solution onto the inorganic film by spraying or the like, for example, spray pressure;! To 5 MPa, temperature 20 to 60 ° C., and etching time 5 to 20 minutes.

[Example]

Examples of the present invention are shown below, but the present invention is not limited to these examples. In the following, “part” means “part by weight”.

[0172] <Synthesis example;!>

Charge 40 parts of polyethylene glycol methacrylate, 40 parts of 2-ethylhexyl acrylate, 20 parts of styrene, and 0.75 part of N, N, -azobisisobutyronitrile into an autoclave with a stirrer, and a nitrogen atmosphere. Under stirring at room temperature until homogeneous. After stirring, polymerize at 80 ° C for 3 hours, further add 0.25 part of N, N'-azobisisobutyronitrile, polymerize for 1 hour, and continue the polymerization reaction at 100 ° C for 1 hour. Then, it was cooled to room temperature to obtain a polymer solution. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter also referred to as “resin (1)”) was 30,000.

[Synthesis Example 2]

Charge 40 parts of polyethylene glycol methacrylate, 40 parts of 2-ethylhexyl acrylate, 20 parts of styrene, and 5.0 parts of N, N, -azobisisobutyronitrile into an autoclave with a stirrer and a nitrogen atmosphere. Under stirring at room temperature until homogeneous. After stirring, Polymerize at 90 ° C for 1 hour, add N, Ν'-azobisisobutyronitrile 1 · 0 parts, polymerize for 1 hour, continue polymerization reaction at 100 ° C for 1 hour, then to room temperature The polymer solution was obtained by cooling. The resulting polymer solution had a polymerization rate of 98%, and the copolymer precipitated from this polymer solution (hereinafter also referred to as “resin (2)”) had a Mw of 1,000.

[0174] <Synthesis Example 3>

Charge 40 parts of polyethylene glycol methacrylate, 40 parts of 2-ethylhexyl acrylate, 20 parts of styrene, and 0.50 part of N, N, -azobisisobutyronitrile into an autoclave equipped with a stirrer, under a nitrogen atmosphere. At room temperature until homogeneous. After stirring, polymerize at 65 ° C for 4 hours, further add 0.25 part of N, N'-azobisisobutyronitrile, polymerize for 2 hours, and continue the polymerization reaction at 100 ° C for 1 hour. Then, it was cooled to room temperature to obtain a polymer solution. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter also referred to as “resin (3)”) was 200,000.

[0175] <Synthesis Example 4>

240 parts propylene glycol monomethyl ether, 60 parts n-butyl methacrylate, 120 parts 2-ethylhexyl methacrylate, 20 parts 2-hydroxypropyl methacrylate, and 1 part azobisisoptyronitrile The mixture was placed in a crepe and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, polymerization was carried out at 75 ° C. for 3 hours, and the polymerization reaction was further continued at 80 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter also referred to as “resin (4)”) was 100,000.

[0176] <Synthesis Example 5>

Propylene glycol monomethyl ether 240 parts, n-butyl methacrylate, 120 parts, 2-ethylhexyl methacrylate, 20 parts, 2-ethoxyethyl methacrylate, 1 part, and azobisisobutyronitrile, 1 part The mixture was placed in an autoclave and stirred under a nitrogen atmosphere until it was uniform at room temperature. After stirring, polymerization was carried out at 75 ° C. for 3 hours, and further, the polymerization reaction was continued at 80 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer (hereinafter, also referred to as “resin (5)”) from which this polymer solution strength was deposited was 100,000. [0177] <Synthesis Example 6>

240 parts propylene glycol monomethyl ether, 60 parts n-butyl methacrylate, 120 parts 2-ethylhexyl methacrylate, 10 parts 2-hydroxypropyl methacrylate, 10 parts glycidyl methacrylate, and azobisisobutyrate One part of ronitrile was charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, polymerization was carried out at 75 ° C. for 3 hours, and further the polymerization reaction was continued at 80 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter also referred to as “resin (6)”) was 100,000.

[0178] [Example 1]

(1) Preparation of glass paste composition (resin composition containing inorganic powder)

100 parts of a PbO-BO SiO-based mixture (softening point 500 ° C) 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)) Resin (1) 10 parts as polymer (B-1), Resin (4) 20 parts as polymer (B-2), Bis (2-ethylhexyl) azelate 3 parts as plasticizer (C) As a solvent, 35 parts of propylene glycol monomethyl ether was kneaded using a disperser to prepare a composition having a viscosity of 3 Pa's.

[0179] (2) Manufacture and evaluation of transfer film (flexibility and nodling)

The composition prepared in the above (1) was coated 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 ^ 111 on the support film. Next, a cover film (width 400 mm, length 30 m, thickness 25 mm) made of PET that had been subjected to release treatment in advance was placed on the inorganic powder-containing resin layer, as shown in FIG. A transfer film of the present invention having such a structure was produced.

[0180] The obtained transfer film had flexibility and could easily be wound up into a roll. In addition, even if this transfer film is bent, the resin layer does not cause cracks (bending cracks) on the surface of the inorganic powder-containing resin layer. The resin layer has excellent flexibility. Met.

[0181] Further, after peeling the cover film from the transfer film and superposing 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 was peeled off from the surface of the glass substrate. As a result, the resin layer exhibits 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 a thing.

[0182] (3) Transferability of resin layer containing inorganic powder

After peeling the cover film from the transfer film obtained in (2) above, the surface of the glass substrate for 21-inch panel on which the pattern containing the resin composition containing unfired conductive powder is formed (bus electrode The transfer film was superposed on the fixing surface of the resin layer so that the surface of the inorganic powder-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 was 110 ° C, the roll pressure was 3 kg / cm ^2, and the moving speed of the heating roll was 1 _m / min.

[0183] In this transfer step, when the support film was peeled off, the resin layer had a sufficiently large film strength without causing the agglomeration failure of the resin layer containing inorganic powder. Furthermore, the transferred inorganic powder-containing resin layer had good adhesion to the pattern surface including the conductive powder-containing resin composition, and also had good embedding between patterns.

[0184] The results are shown in Table 1. Good film transferability is indicated by ◯, and poor film transfer is indicated by X.

[0185] (4) Firing process

The glass substrate on which the inorganic powder-containing resin is transferred and formed on the pattern containing the unfired conductive powder-containing resin composition according to (3) above is placed in a firing furnace, and the temperature in the furnace is reduced to 590 ° C. After the temperature was raised at a rate of 10 ° C, the electrode was made of a glass sintered body and a dielectric layer on the surface of the glass substrate by firing at 590 ° C for 20 minutes. The obtained layer was observed with an optical microscope (X6UW-NR, manufactured by Nihon Kogyo Co., Ltd.) at a magnification of 50 times. The fact that stratification was obtained was a component. [0186] Table 1 shows the result of microscopic observation of the generation of bubbles on or between the electrodes on the substrate after firing. The force when a bubble of 20 m or more is not observed is indicated by ◯, and when observed, X is indicated.

[0187] [Example 2]

A composition was prepared in the same manner as in Example 1 except that the resin (5) was used instead of the resin (4) to produce a transfer film. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[Example 3]

A composition was prepared in the same manner as in Example 1 except that the resin (6) was used instead of the resin (4) to produce a transfer film. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[0189] [Comparative Example 1]

A transfer film was produced by obtaining a composition in the same manner as in Example 1, except that the resin (1) was not used. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[0190] [Comparative Example 2]

A composition was prepared in the same manner as in Example 1 except that the resin (2) was used instead of the resin (1) to produce a transfer film. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[0191] [Comparative Example 3]

A composition was prepared in the same manner as in Example 1 except that the resin (3) was used instead of the resin (1) to produce a transfer film. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[0192] [Comparative Example 4]

Resin (1) A composition was prepared in the same manner as in Example 1 except that 0.005 part of resin (1) was used instead of 10 part, and a transfer film was produced. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[0193] [Comparative Example 5] A composition was prepared in the same manner as in Example 1 except that 100 parts of the resin (1) was used instead of 10 parts of the resin (1), and a transfer film was produced. The obtained transfer film was transferred onto a substrate in the same manner as in Example 1 and baked. The results are shown in Table 1.

[table 1]

I 1 j

[Example 4]

(1) Preparation of glass paste composition (composition containing inorganic powder)

Glass powder (inorganic powder (A)), PbO-B 2 O—SiO-based mixture (softening point 455 ° C, average particle size 2.6 ^ 111) 100 parts, polymer (B-1) resin ( 1) 10 parts, polymer (B-2) as butyl methacrylate / 2-ethylhexyl methacrylate / 2-hydroxypropyl methacrylate copolymer (weight ratio: 30/60/10, Mw: 100) , 000) 20 parts, 3 parts of bis (2-ethylhexyl) azelate as plasticizing substance (C) and 35 parts of propylene glycol monomethyl ether as a solvent are kneaded using a disperser. A composition of S was prepared.

(2) Production and evaluation of transfer film (flexibility and handling)

In the same manner as in Example 1, a transfer film was produced and evaluated for flexibility and handleability.

(3) Transfer of resin layer containing inorganic powder The inorganic powder-containing resin layer was transferred in the same manner as in Example 1 except that the surface temperature of the heating roll during thermocompression bonding of the transfer film was 90 ° C.

(4) Inorganic powder-containing resin layer firing step

The inorganic powder-containing resin layer was fired in the same manner as in Example 1 except that the temperature in the firing furnace was 520 ° C. The obtained dielectric layer had high transparency and high surface smoothness.

[0196] [Example 5]

The composition was the same as in Example 1 except that a PbO—B 2 O—SiO-based mixture (softening point 455 ° C., average particle size 3.9 111) was used as the glass powder (inorganic powder). Was prepared. The viscosity of this composition was 3 Pa · s.

[0197] When the same operation as (4) in Example 4 (2) was performed, the transfer film of the inorganic powder-containing organic composition showed sufficient transferability with respect to the glass substrate, and was easy to handle. It was also good. The obtained dielectric layer had high transmittance and high surface smoothness.

[0198] [Example 6]

The composition was the same as in Example 1 except that a PbO—B 2 O—SiO-based mixture (softening point 455 ° C., average particle size 2. 0 111) was used as the glass powder (inorganic powder). Was prepared. The viscosity of this composition was 3 Pa · s.

[0199] In the same manner as in Example 4 (2) (4), the transfer film of the inorganic powder-containing organic composition showed sufficient transferability to the glass substrate, and was easy to handle. It was also good. The obtained dielectric layer had high transmittance and high surface smoothness.

[0200] [Example 7]

As in Example 1, except that a PbO—B 2 O 3 —SiO-based mixture (softening point 505 ° C., average particle size 2.6 111) was used as the glass powder (inorganic powder (A)), A composition was prepared. This The viscosity of this composition was 3 Pa's.

[0201] When the same operation as in Example 4 (2) (4) was performed, the transfer film of the organic composition containing inorganic powder showed sufficient transferability to the glass substrate, and was easy to handle. It was also good. The obtained dielectric layer had high transmittance and high surface smoothness.

[0202] [Example 8]

As a glass powder (inorganic powder (A)), a PbO-B 2 O—SiO-based mixture (softening point 410 ° C

The composition was prepared in the same manner as in Example 1 except that the average particle size 2.6 111) was used. The viscosity of this composition was 3 Pa's.

[0203] In the same manner as in Example 4 (2) (4), the transfer film of the inorganic powder-containing organic composition showed sufficient transferability to the glass substrate, and was easy to handle. It was also good. The obtained dielectric layer had high transmittance and high surface smoothness.

[0204] [Comparative Example 6]

As glass powder (inorganic powder (A)), PbO-B 2 O-SiO series mixture (softening point 455 ° C, average particle size 2.6 m) 100 parts, binder resin with butyl metatalylate / 2 Ethyl hexyl metatalylate copolymer (weight ratio: 50/50 Mw: 100,000) 20 parts, plasticizer (C) 3 parts bis (2-ethylhexyl) azelate, and propylene solvent A composition having a viscosity of 3 Pa.s was prepared by kneading 35 parts of glycol monomethyl ether using a disperser.

[0205] When the operations of (2) and (4) of Example 4 were performed, the dielectric layer obtained from the transfer film of the organic composition containing inorganic powder had a transparency that was poor in surface smoothness. It was inferior.

[Example 9]

(1) Preparation of resin composition containing inorganic powder

As the inorganic powder (A), silver powder (average particle diameter 2.2 111, specific surface area 0. 5 cm ² / g and power strips density 4 · 6g / cm ³⁾ 100 parts, Bi O -BO-SiO glass Frit (average particle size 3 m, amorphous, softening point 520 ° C and a thermal expansion coefficient ^{^{ϋϋ = 87 Χ 10- 7 / °}} C) 3 parts, 10 parts of the resin (1) as the polymer (B -1), the polymer (B- 2) Methacrylic acid / succinic acid mono (2-methacryloyl quichetil) / methacrylic acid 2-hydroxypropyl / n-butyl methacrylate copolymer (weight ratio 20/15/25/40 and weight average molecular weight 90, 000) 15 The present invention has a viscosity of 3,400 cp by kneading 10 parts of dipentaerythritol hexatalylate as plasticizing substance (C) and 9 parts of propylene glycol monomethyl ether acetate as solvent using a disperser. A composition was prepared.

(2) Production of transfer film

Using a blade coater on a support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET) that has been pre-released from the composition of the present invention prepared in (1) above. The solvent was removed by drying the formed coating film at 80 ° C. for 5 minutes, thereby forming an inorganic powder-containing resin layer having a thickness of 12 πι on the support film. Next, a transfer film was manufactured by pasting a cover film (width 400 mm, length 30 m, thickness 38 m) made of PET, which had been subjected to release treatment in advance, on the inorganic powder-containing resin layer.

(3) Transfer of resin layer containing inorganic powder

After peeling the cover film from the transfer film obtained in the above (2), the transfer film (in which the surface of the inorganic powder-containing resin layer is brought into contact with the surface of the 21-inch panel glass substrate) A laminate of a support film and an inorganic powder-containing resin layer) was laminated, and this transfer film was thermocompression bonded with a heating roll. Here, as the pressure bonding conditions, the surface temperature of the heating roll was 90 ° C, the roll pressure was 2 kg / cm ^2, and the moving speed of the heating roll was 0.6 m / min.

After the thermocompression treatment, the support film was peeled off from the inorganic powder-containing resin layer fixed (heat bonded) to the surface of the glass substrate, and the transfer of the inorganic powder-containing resin layer was completed.

Yes

(4) Preparation of resist composition

Benzyl methacrylate / methacrylic acid = 75/25 (wt%) copolymer (weight average molecular weight 30,000) as binder resin 60 parts, tripropylene as multifunctional monomer (D-1) 40 parts of diglycol ditalylate, 20 parts of 2 benzyl-2-dimethylamino-1 (4 morpholinophenyl) butane as a photopolymerization initiator (D-2) and 100 parts of propylene glycol monomethyl ether acetate as a solvent After kneading, an alkali development type radiation sensitive resist composition (hereinafter referred to as “resist composition”) was prepared by filtering with a cartridge filter (2 μm diameter).

(5) Manufacture of resist film

The resist composition prepared in (4) above was coated on a support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET), which had been pre-released, using a blade coater. Then, the solvent was removed by drying the formed coating film at 80 ° C. for 5 minutes, thereby forming a resist film having a thickness of 10 m on the support film. Next, a resist film was manufactured by shelling a cover film (width 40 Omm, length 30 m, thickness 38 m) made of PET that had been subjected to mold release treatment on the resist film in advance.

(6) Transfer of resist Finolem

After removing the cover film from the resist film obtained in (5) above, the surface of the resist film abuts on the inorganic powder-containing resin layer formed on the 21-inch glass substrate prepared in (3) above. The resist film (support film and resist film) was overlaid as described above, and this transfer film was thermocompression bonded with a heating roll. Here, as the pressure bonding conditions, the surface temperature of the heating roll was 90 ° C., the roll pressure was 2 kg / cm ^2, and the moving speed of the heating roll was 0.6 m / min.

After completion of thermocompression treatment, the support film is peeled off from the laminated film of the inorganic powder-containing resin layer and resist film fixed (heat bonded) to the surface of the glass substrate, and the transfer of the inorganic powder-containing resin layer is completed. did.

(7) Resist film exposure process

An ultra-high pressure mercury lamp is passed through a striped negative exposure mask with a line width of 100 μm and a space width of 400 μm against the laminated film of the inorganic powder-containing resin layer and resist film formed on the glass substrate. Were irradiated with mixed light of g-line (436 nm), h-line (405 nm) and i-line (365 nm). The exposure amount at that time is 200 mJ in terms of illuminance measured with a 365 nm sensor. (8) Development process' Etching process

The exposed resist film was developed by a shower method using a 0.3% by mass sodium carbonate aqueous solution as a developer at a liquid temperature of 30 ° C. The etching process was performed for 90 seconds. Subsequently, the water washing process by ultrapure water was performed. Thus, a resist pattern was formed, and then an inorganic powder-containing resin pattern corresponding to the resist pattern was formed. When the obtained inorganic powder-containing resin pattern was observed with an optical microscope, no development residue was observed on the substrate in the resist unexposed area, and no pattern chipping was observed.

(9) Firing process

The glass substrate on which the inorganic powder-containing resin pattern was formed was baked in a baking furnace for 30 minutes in a temperature atmosphere of 590 ° C. As a result, a panel material in which an electrode having a pattern width of 100 μm and a thickness of 6 Hm was formed on the surface of the glass substrate could be obtained.

[Example 10]

(1) Preparation of resin composition containing inorganic powder

As inorganic powder (A), 100 parts of Ag powder having a specific surface area of 0.5 m ² / g, average particle size of 2.3 m, and Bi O—BO—SiO glass frit with an average particle size of 3 111 (indeterminate, (Softening point 520 ° C) 10

2 3 2 3 2

Part, polymer (B-1) as resin (1) 10 parts, polymer (B-2) as methacrylic acid / succinic acid mono (2-methacryloyl quichetil) / methacrylic acid 2-hydroxypropyl / methacrylic acid n —Butyl copolymer (weight ratio 20/15/25/40 and weight average molecular weight 90,000) 15 parts, oleic acid 1 part as a dispersant, 10 parts of pentaerythritol tritalylate as a plasticizer, and propylene glycol as a solvent After kneading 100 parts of monomethyl ether with a bead mill, an inorganic powder-containing resin composition (conductive paste composition) was prepared by filtering with a stainless mesh (400 mesh, 38 m diameter).

(2) Preparation of resist composition

Benzyl methacrylate / methacrylic acid = 75/25 (wt%) copolymer (weight average molecular weight 30, 000) 60 parts as binder resin, trimethylolpropane tritalylate 40 parts as multifunctional monomer (D-1), Photopolymerization initiator (D-2) 2, 2, 1-bis 2-chloro Phenyl 4,4 5,5 Tetraphenylbiimidazole (compound (i)) 6 parts, 4, 4 Bis (jetylamino) benzophenone (compound (ii)) 3 parts, 2-mercaptobenzozothiazole (compound (iii) ) l. 5 parts, 3,3'-carbonylbis (7-jetylamino) coumarin as a photosensitizer, 0.55 parts, and 100 parts of propylene glycol monomethyl ether acetate as a solvent were kneaded, and then a cartridge filter (2, 1 m diameter) to prepare an alkali-developable radiation-sensitive resist composition (hereinafter referred to as “resist composition”).

(3) Preparation of transfer film

The electrode film-forming transfer film of the present invention in which a laminated film obtained by laminating a resist film and an inorganic powder-containing resin layer in this order is formed on a support film by the operations (i) and (c) below. did.

(Ii) Apply the resist composition prepared in (2) onto a support film (I) consisting of a PET film with a thickness of 38 m using a blade cutter, and dry the coating at 100 ° C for 3 minutes. The solvent was removed, and a resist film having a thickness of 8 am was formed on the support film.

(Mouth) The inorganic powder-containing resin composition prepared in (1) was applied onto a support film (Π) made of PET film with a film thickness of 38, im using a blade turret. The solvent was removed by drying for minutes, and a 12 m thick resin layer containing inorganic powder was formed on the support film.

(C) The transfer film was overlaid so that the surfaces of the resist film prepared in (i) and (mouth) and the inorganic powder-containing resin layer were in contact with each other, and thermocompression bonded with a heating roller. Here, the pressing conditions were such that the surface temperature of the heating roller was 90 ° C, the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. As a result, a transfer film was produced in which a laminated film having a resist film and an inorganic powder-containing resin layer was formed between support films.

(4) Transfer process of laminated film

The transfer film was superposed on the surface of the glass substrate so that the surface of the inorganic powder-containing resin layer of the transfer film prepared in (3) was in contact, and this transfer film was hot-pressed on a heating roller. Here, the pressing conditions were such that the surface temperature of the heating roller was 90 ° C, the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. Thereby, the surface of the glass substrate The transfer film was transferred to and became in close contact.

(5) Resist film exposure processDevelopment process

In the above (4), the resist film in the laminated film formed on the glass substrate was irradiated with a laser beam having a wavelength of 405 nm from the support film to the portion where the pattern was to be formed. At that time, the amount of laser beam irradiation energy was set to lOmj / cm ² . After the irradiation, the support film on the resist film is peeled off, and then the resist film by a shower method using a 0.3% by mass sodium carbonate aqueous solution (30 ° C.) as a developing solution is applied to the exposed resist film. The development process was performed for 120 seconds.

[0210] Thus, the uncured resist that was not irradiated with ultraviolet rays was removed, and a resist pattern was formed. The resist pattern had a uniform pattern shape and a good shape with excellent pattern edge linearity.

(6) Etching process of inorganic powder-containing resin layer

The inorganic powder-containing resin layer was etched for 60 seconds by a shower method using a 0.3% by mass sodium carbonate aqueous solution (30 ° C.) as an etching solution, following the above steps.

[0211] Next, washing with ultrapure water and drying were performed. Thereby, an inorganic powder-containing resin layer pattern was formed.

(7) Pattern firing process

The glass substrate on which the pattern of the inorganic powder-containing resin layer was formed was baked at 560 ° C. for 10 minutes in the atmosphere in the baking furnace. As a result, an electrode pattern with a thickness of 4 μm was formed on the surface of the glass substrate.

(8) Pattern evaluation

The obtained electrode pattern had an excellent shape free from cracks and chips.

[0212] [Example 11]

(1) Preparation of resin composition containing inorganic powder

2 3 2 3 2

Part, polymer (B-1) as resin (1) 10 parts, polymer (B-2) as benzyl metatalylate / methacrylic acid / 2-hydroxypropyl metatalylate = 60/20/20 (mass) %) Copolymerization (Mw = 50, 000) 200 parts, photopolymerizable monomer (D-l) as trimethylolpropane tritalylate 200 parts, photopolymerization initiator (D-2) as 2-benzyl-1-dimethylamino-1 5 parts of (4-morpholinophenyl) 1-butane 1-one, 1 part of 3-methacryloxypropylmethoxysilane as a silane coupling agent, 1 part of oleic acid as a dispersant, and 200 parts of propylene glycol monomethyl ether as a solvent After kneading with a bead mill, the inorganic powder-containing resin composition (I) was prepared by filtering with a stainless mesh (500 mesh, 25 m diameter).

(2) Preparation of transfer film

The inorganic powder-containing resin composition (I) prepared in (1) above was applied onto a support film made of a PET film having a film thickness of 38 Hm, which had been subjected to a release treatment in advance, using a blade coater. The transfer film of the present invention was produced by drying at 3 ° C. for 3 minutes to remove the solvent and forming a 7 μm-thick inorganic powder-containing resin layer on the support film.

(3) Transfer film transfer process

Using the transfer film produced in (2) above, the transfer film was superposed and thermocompression bonded with a heating roller so that the surface of the inorganic powder-containing resin layer was brought into contact with the surface of the glass substrate. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 100 ° C, the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. As a result, the transfer film was transferred to and adhered to the surface of the glass substrate.

(4) Inorganic powder-containing resin layer exposure processDevelopment process

The resin layer containing inorganic powder formed on the glass substrate is irradiated with i-rays (ultraviolet light with a wavelength of 365 nm) from the support film with an ultrahigh pressure mercury lamp through an exposure mask (5 cm x 5 cm). Then, a latent image of the pattern was formed on the inorganic powder-containing resin layer. Here, the dose was 20 Omj / cm ² . After exposure, the support film is peeled off and then developed for 30 seconds by a shower method using a 0.3 mass% sodium carbonate aqueous solution at a liquid temperature of 30 ° C. as a developer, followed by using ultrapure water. And washed with water.

As a result, the inorganic powder-containing resin in the portion not irradiated with ultraviolet rays was removed, and an inorganic powder-containing resin pattern was formed.

(5) Firing process The glass substrate on which the inorganic powder-containing resin pattern was formed was baked for 30 minutes in a temperature atmosphere of 580 ° C. As a result, an electrode pattern having a thickness of 4 m was formed on the surface of the glass substrate. The obtained electrode pattern had an excellent shape with no cracks or chips.

[Example 12]

(1) Preparation of resin composition containing inorganic powder

PbO-BO-SiO-CaO glass (thermal softening point) as glass powder (inorganic powder (A))

2 3 2

530. C and average particle size 1.6) 80 parts, filler ZnO (average particle size 1. 0 111) 20 parts, polymer (B-1) 10 parts resin (1), polymer (B-2 ) As butyl metatalylate / 2-ethylhexyl metatalylate / hydroxypropyl metatalylate copolymer (weight ratio: 30/60/10 and Mw: 100,000) 20 parts, as plasticizer (C) A paste-like inorganic particle-containing resin composition was prepared by kneading 6 parts of 2-ethylhexylazelate and 50 parts of propylene glycol monomethyl ether as a solvent.

Yes

(2) Production of transfer film

The composition prepared in (1) is applied onto a support film (width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film, which has been subjected to release treatment in advance, using a roll coater. A film was formed. The formed coating film was dried at 100 ° C. for 10 minutes to remove the solvent, thereby producing a transfer film in which an inorganic particle-containing resin layer having a thickness of 260 m was formed on the supporting fin.

(3) Transfer of inorganic powder-containing resin composition

The transfer film was thermocompression bonded to the surface of a glass substrate for a 6-inch panel in which electrodes (100 m wide) for generating plasma were arranged by a heating roller. Here, the pressing conditions were such that the surface temperature of the heating roller was 100 ° C, the roll pressure was 4 kg / cm, and the moving speed of the heating roller was 0.5 m / min. After completion of the thermocompression treatment, the support film was peeled off from the inorganic particle-containing resin layer (1). As a result, after the inorganic particle-containing resin layer (1) was laminated on the surface of the glass substrate, it was transferred and brought into close contact. When the film thickness of the laminated film of the inorganic particle-containing resin layer (1) was measured, it was in the range of 260 m ± 2 m. It was.

(4) Firing process of resin composition containing inorganic powder

The glass substrate on which the inorganic particle-containing resin layer was formed was baked for 15 minutes in a temperature atmosphere of 560 ° C. As a result, a glass sintered body was formed on the glass substrate.

(5) Resist pattern formation process

A transfer film was superimposed on the surface of the glass sintered body so that the surface of the resist film was in contact with this, and this transfer film was thermocompression bonded with a heating roller under the same pressure bonding conditions as described above. After completion of the thermocompression treatment, the support film was peeled off from the resist film. As a result, the resist film was transferred and adhered to the surface of the glass sintered body. When the film thickness of the resist film transferred to the surface of the sintered glass was measured, it was in the range of 20 m ± 1 m.

[0215] The resist film formed on the glass sintered body is irradiated with i-rays (ultraviolet light with a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (100 Hm stripe pattern). did. Here, the irradiation dose was 400 mj / cm ² . The exposed resist film was developed for 30 seconds by a shower method using a 0.3 wt% aqueous sodium carbonate solution (30 ° C.) as a developer. Subsequently, a water washing treatment with ultrapure water was performed, whereby ultraviolet rays were irradiated to remove the resist and the uncured resist, and a resist pattern was formed.

(6) Etching process of inorganic particle-containing resin layer

Continuing with the above steps, an etching process was performed for 10 minutes by the shattering method using a 1 wt% nitric acid aqueous solution (40 ° C.) as an etching solution. Next, washing with ultrapure water and drying were performed. As a result, a partition wall pattern composed of the material layer remaining portion and the material layer removal portion was formed. Finally, a resist stripping process was performed for 60 seconds using the sodium carbonate method using sodium carbonate 1% (30 ° C) as a stripping solution. Subsequently, the water washing process by ultrapure water was performed and the partition pattern was formed by this.

[0216] <Synthesis Examples 7 and 13; 13>

Resins (7) to (; 13) were synthesized in the same manner as in Synthesis Example 1 except that the monomers were used in the amounts shown in Table 3 in Synthesis Example 1. [0217] <Synthesis Example 14>

20 parts of PEGMA, 40 parts of EHA, 40 parts of ST and 1.5 parts of N, N, monoazobisisobutyronitrile were charged into an autoclave equipped with a stirrer and stirred at room temperature in a nitrogen atmosphere until uniform. After stirring, polymerize at 90 ° C for 3 hours, further add 0.5 part of N, N'-azobisisobutyronitrile, polymerize for 1 hour, continue the polymerization reaction at 100 ° C for 1 hour, and then cool to room temperature. Thus, a polymer solution was obtained. The obtained polymer solution had a polymerization rate of 96%, and the Mw of the resin (14) precipitated from this polymer solution was 10,000. The results are shown in Table 2.

[0218] <Synthesis Example 15>

Charge 20 parts of PEGMA “EHA 40 parts, 3 c. 40 parts” and 0.5 parts of N, N, 1-azobisisobutyronitrile into an autoclave with a stirrer, and stir until uniform at room temperature in a nitrogen atmosphere. After stirring, polymerize at 75 ° C for 4 hours, further add 0.25 part of N, N'-azobisisobutyronitrile for 2 hours, continue polymerization at 100 ° C for 1 hour, and then reach room temperature. The polymer solution was cooled to a polymerization rate of 98%, and the Mw of the resin (15) deposited from this polymer solution was 50,000, and the results are shown in Table 2.

[0219] [Table 2]

[Table 2]

[0220] [Example 13]

(1) Preparation of glass paste composition (resin composition containing inorganic powder) As a glass powder (inorganic powder) (A), a PbO—BO SiO-based mixture (softening point 500 ° C) 100 parts having a composition of 70% by weight of lead oxide, 10% by weight of boron oxide and 20% by weight of silicon oxide Polymer (B-1) as resin (1) 10 parts, Polymer (B-2) as butyl methacrylate / 2-ethylhexyl methacrylate / 2-hydroxypropyl methacrylate copolymer (weight) Ratio: 30/60/10 and Mw: 100,000) 20 parts, as plasticizer (C), 3 parts of bis (2-ethylhexyl) azelate (hereinafter also referred to as “DOAz”) and as solvent A composition having a viscosity of 3 Pa ′s was prepared by kneading 35 parts of propylene glycol monomethyl ether (hereinafter also referred to as “PGME”) using a disperser.

(2) Production and evaluation of transfer film (flexibility and handling)

Apply the composition prepared in (1) above onto a support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET), which has 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 ^ 111 on the support film. Next, a cover film (width 400 mm, length 30 m, thickness 25 mm) made of PET that had been subjected to release treatment in advance was placed on the inorganic powder-containing resin layer, as shown in FIG. A transfer film of the present invention having such a structure was produced.

[0221] The obtained transfer film was flexible and could easily be wound into a roll. Further, even when this transfer film was bent, the resin layer had excellent flexibility without causing cracks (bending cracks) on the surface of the inorganic powder-containing resin layer.

[0222] Further, after peeling the cover film from the transfer film and superimposing 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 was peeled off from the surface of the glass substrate. As a result, the resin layer exhibits moderate adhesiveness to the glass substrate, and the transfer film can be peeled off without causing cohesive failure of the resin layer. ), And the result was good.

(3) Transfer of resin layer containing inorganic powder

After peeling the cover film from the transfer film obtained in (2) above, The transfer film was superposed on the surface of the glass substrate for the panel (fixing surface of the bus electrode) so that the surface of the resin layer containing the inorganic powder was in contact, and this transfer film was thermocompression bonded with a heating roll. As the pressure bonding conditions, the surface temperature of the heating roll was 110 ° C., the roll pressure was 3 kg / cm ^2, and the moving speed of the heating roll was lm / min.

[0223] 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.

[0224] In this transfer step, when the support film was peeled off, the inorganic powder-containing resin layer did not cause agglomeration failure, 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.

(4) Inorganic powder-containing resin layer firing step

As described above, the inorganic powder-containing resin fixed (heat-bonded) to the surface of the glass substrate was baked for 20 minutes in a baking furnace in a temperature atmosphere of 590 ° C. As a result, it was possible to obtain a panel material in which a dielectric having a thickness of 40 am was formed on the surface of the glass substrate.

[Examples 14 to 24]

In Example 13, a composition was prepared in the same manner as in Example 13 except that the polymer (B-1) was used in the amount and amount of resin shown in Table 2, and a transfer film and a panel material were produced.

[0226] [Comparative Example 7]

In Example 13, the same force as in Example 13 was used, except that the polymer (B-1) was not used.

Then, an inorganic powder-containing resin composition was prepared, and a transfer film was produced, baked and evaluated.

[0227] [Comparative Example 8]

Charge 20 parts of polyethylene glycol methacrylate, 40 parts of 2-ethylhexyl acrylate, 40 parts of styrene, and 0.40 part of N, N, -azobisisobutyronitrile into an autoclave with a stirrer, and a nitrogen atmosphere. Under stirring at room temperature until homogeneous. After stirring, polymerize at 75 ° C for 5 hours, further add 0.25 part of N, N'-azobisisobutyronitrile, polymerize for 3 hours, and continue the polymerization reaction at 100 ° C for 1 hour. Cool to room temperature, polymer One solution was obtained. The resulting polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “resin (16)”) was 70,000.

[0228] Inorganic powders were obtained in the same manner as in Example 13, except that the polymer (B-1) was replaced with the resin (16) instead of the resin (1). A contained resin composition was prepared, and a transfer film was prepared, baked and evaluated.

[0229] [Comparative Example 9]

In Example 13, an inorganic powder-containing resin composition was prepared in the same manner as in Example 13 except that the resin (2) was used instead of the resin (1) as the polymer (B-1). The transfer film was prepared, baked and evaluated.

[0230] [Comparative Example 10]

Charge 40 parts of polyethylene glycol methacrylate, 40 parts of 2-ethylhexyl acrylate, 20 parts of styrene, and 0.20 part of N, N, -azobisisobutyronitrile into an autoclave with a stirrer, and a nitrogen atmosphere. Under stirring at room temperature until homogeneous. After stirring, polymerize at 75 ° C for 8 hours, further add 0.25 part of N, N'-azobisisobutyronitrile, polymerize for 3 hours, and continue the polymerization reaction at 100 ° C for 1 hour. Then, it was cooled to room temperature to obtain a polymer solution. The obtained polymer solution had a polymerization rate of 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “resin (17)”) was 200,000.

[0231] In Example 13, an inorganic powder-containing resin composition was prepared in the same manner as in Example 13, except that the resin (17) was used instead of the resin (1) as the polymer (B-1). The transfer film was prepared, fired and evaluated.

[0232] [Comparative Example 11]

In Example 13, an inorganic powder-containing resin composition was prepared in the same manner as in Example 13 except that 0.005 part by weight of the resin (1) was used as the polymer (B-1). Fabrication, firing and evaluation were performed.

[0233] [Comparative Example 12]

In Example 13, an inorganic powder-containing resin composition was prepared in the same manner as in Example 13 except that 100 parts by weight of the resin (1) was used as the polymer (B-1), and a transfer film was produced. Calcination and evaluation were performed. [0234] <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 that did not have cracks (bending cracks) was marked with ◯, and that with cracks was marked with X.

(2) Storage stability

The paste before film coating is stored at 5 ° C, and the phase that has not been phase-separated after 30 days or more is △, the phase that has been phase-separated for 10 days or more but less than 30 days is △, the phase is less than 10 days The separated one was designated as X.

(3) Transparency

The linear transmittance (measurement wavelength: 550 nm) of the dielectric layer formed on the fired panel was measured with a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). The case where the transmittance was 70% or more was rated as ◯, the transmittance exceeding 65% and less than 70% as Δ, and the transmittance as less than 65% as X.

(4) Transparency (stability)

10 panels are fired, the difference between the maximum and minimum values of the above linear transmittance is less than 2% ○, more than 2% and less than 10% △, more than 10% X It was.

(5) Surface smoothness

Using a non-contact three-dimensional shape measuring device (model number: NH-3 Mitaka Kogyo Co., Ltd.), the measurement range is 500 m X 500 m, the measurement pitch is 10 μm, and the 10-point average roughness (Rz ) Is the surface roughness. The surface roughness was performed based on the following evaluation criteria.

0: Less than 0. Ol m

Δ: 0. Ol ^ u m or more, less than 0 l ^ u m

X: 0.1 μm or more

Tables 3 to 4 show the results of Examples 13 to 24 and Comparative Examples 7 to 12;

[0235] [Table 3] [Table 3]

D0362 [Table 4]

Claims

The scope of the claims

[1] contains an inorganic powder (A) and a binder resin (B),

The binder resin (B) includes a (meth) acrylic polymer (B-1) having a weight average molecular weight of 10,000 to 50,000 having a polyoxyalkylene moiety,

And an inorganic powder-containing resin composition comprising 0.0;! To 50 parts by weight of the polymer (B-1) with respect to 100 parts by weight of the inorganic powder (A).

[2] The polymer (B-1) is

5 to 30% by weight of a structural unit derived from a (meth) acrylate compound having a polyoxyalkylene moiety;

No polyoxyalkylene moiety! /, 30-50% by weight of a structural unit derived from a (meth) acrylate compound,

30-50% by weight of structural units derived from aromatic bur compound

The inorganic powder-containing resin composition according to claim 1, comprising:

[3] The polymer (B-1) is a polyethylene glycol mono (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate. , Nourphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate and noeur phenoxy polypropylene glycol (meth) acrylate 3. The inorganic powder-containing resin composition according to claim 1, comprising a structural unit derived from at least one (meth) acrylate compound selected from the group consisting of:

[4] The inorganic powder-containing resin composition according to any one of claims 1 to 3, further comprising a plasticity-imparting substance (C).

5. The composition according to any one of claims 1 to 4, further comprising (D-1) a polyfunctional (meth) acrylate and (D-2) a radiation polymerization initiator as the photosensitive component (D). An inorganic powder-containing resin composition according to claim 1.

[6] A transfer film comprising an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims;! To 5 on a support film.

[7] A laminate comprising a resist layer and an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims;! To 5 on a support film. Transfer film.

[8] A step of transferring an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims;! To 5 formed on a support film onto a substrate;

Baking the inorganic powder-containing resin layer;

The manufacturing method of the flat panel display member characterized by including.

[9] A step of transferring an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims 5 to 6 onto a substrate, formed on a support film;

Forming a resist layer on the inorganic powder-containing resin layer;

A step of exposing the resist layer to form a latent image of a resist pattern; a step of developing the resist layer to reveal a resist pattern;

Etching the inorganic powder-containing resin layer to form a pattern corresponding to the resist pattern;

A step of firing the pattern;

[10] A laminate of a resist layer formed on a support film and an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims 1 to 5 on a substrate A transfer process;

A step of exposing a resist layer constituting the laminate to form a latent image of a resist pattern; and

Developing the resist layer to reveal the resist pattern; and

A step of firing the pattern;

[11] A step of transferring an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 5 formed on a support film onto a substrate; A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern; a step of developing the inorganic powder-containing resin layer to form a pattern;

A step of firing the pattern;

[12] A step of transferring an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims;! To 5 formed on a support film onto a substrate;

Baking the inorganic powder-containing resin layer to form an inorganic film;

Forming a resist pattern on the inorganic film;

Etching the inorganic film to form an inorganic pattern corresponding to the resist pattern; and

[13] The flat panel display member is selected from a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color filter, and a black matrix. Manufacturing method of flat panel display member.

[14] Claim: By forming an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to any one of claims 4 to 4 on a substrate, and firing the inorganic powder-containing resin layer A method for producing a flat panel display member, comprising a step of forming a dielectric layer on the substrate.

[15] The flat panel display member according to claim 14, wherein the inorganic powder-containing resin layer is formed by transfer on the substrate using the transfer film according to claim 6. Manufacturing method.

[16] A step of forming a pattern including a conductive powder-containing resin composition on a substrate, and an inorganic powder-containing resin composition layer constituting the transfer film according to claim 5 is transferred onto the pattern to transfer the pattern. A method for producing a flat panel display member, comprising: a step of forming a laminated film on a substrate; and a step of firing the laminated film.