JP2008007559A - Resin composition containing inorganic powder, transfer film and manufacturing method of flat panel display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition containing inorganic powders, which can suitably form a panel member of a flat panel display excellent in the patterning property and pattern shape and which excels in the film transfer capability. <P>SOLUTION: This inorganic powder-containing resin composition comprises inorganic powders, an acrylic resin containing a monomer represented by formula (1) as a polymerized component, and a solvent. In formula (1), R<SP>1</SP>indicates a hydrogen atom or a methyl group, R<SP>2</SP>indicates a 1-20C alkylene group or a 6-30C arylene group, and B indicates a group that blocks an isocyanate group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an inorganic powder-containing resin composition, a transfer film, and a method for producing a flat panel display member. More specifically, the present invention relates to an inorganic powder-containing resin composition and a transfer film suitable for forming a panel material constituting a flat panel display, and a method for producing a flat panel display member using the transfer film.

  A flat panel display (hereinafter also referred to as “FPD”) such as a field emission display (hereinafter also referred to as “FED”) and a plasma display panel (hereinafter also referred to as “PDP”) is a large panel and can be easily manufactured. In view of the wide viewing angle, the self-luminous type and the high display quality, the flat panel display technology has attracted attention. In particular, color plasma display panels are expected to become the mainstream in the future as display devices for wall-mounted TVs of 20 inches or more.

  The color PDP can perform color display by irradiating phosphors with ultraviolet rays generated by gas discharge. In general, in a color PDP, a phosphor portion for red light emission, a phosphor portion for green light emission, and a phosphor portion for blue light emission are formed on a substrate, so that the light emitting display cells of each color are entirely formed. It is configured in a uniformly mixed state.

  Specifically, a partition made of an insulating material called a barrier rib is provided on the surface of a substrate made of glass or the like, and a large number of display cells are partitioned by the partition, and the inside of the display cell has a plasma action. It becomes space. Then, a phosphor part is provided in the plasma working space, and an electrode for causing plasma to act on the phosphor part is provided, whereby a plasma display panel having each display cell as a display unit is configured. The said electrode is normally comprised by the lamination pattern which has a white color layer containing silver etc., and the dark color layer (black layer) which has a role of an antireflection layer (light-shielding layer) in the lower layer of this white conductive layer. In general, in order to improve the contrast of the PDP, a black matrix or a color filter is provided between the electrode patterns.

  As a method for manufacturing a panel material in such an FPD, (1) a method using an ion sputtering method or an electron beam evaporation method, or (2) an inorganic powder-containing resin layer pattern formed by a photolithography method or a screen printing method is used. A method of baking and removing an organic substance is known (see, for example, Patent Documents 1 to 4). Among them, the method of patterning the inorganic powder-containing resin layer by a photolithography method is preferably used because of high manufacturing efficiency and in principle excellent pattern accuracy. In particular, a method of patterning by using a transfer film in which an inorganic powder-containing resin layer is formed on a flexible support film and transferring the inorganic powder-containing resin layer onto a substrate for patterning is performed. In addition, since a pattern having excellent surface uniformity can be formed, it is preferably used.

  The inorganic powder-containing resin composition used for the formation of the inorganic powder-containing resin layer has the flexibility of a film formed by applying the composition on a support such as a glass substrate or a PET film and drying it. In order to maintain or when used as a transfer film, a polymer having a low glass transition point is used or a plasticizer is added in a large amount in order to obtain good transferability to a substrate such as a glass substrate. There is a need.

However, such an inorganic powder-containing resin composition has a problem in that when a pattern is formed using photolithography or the like and then baked, the resin easily melts and the pattern after baking becomes thick. In addition, line weighting during firing can be avoided by increasing the average weight molecular weight (Mw) of the resin used, but such an inorganic powder-containing resin composition has poor solubility in a developer, There is a problem that there are many residues and the resolution is poor.
Japanese Patent Laid-Open No. 11-162339 JP 2001-84833 A JP 2002-245932 A JP 2003-51250 A

  A first object of the present invention is to suitably form an FPD panel member (for example, a dielectric layer, a partition wall, an electrode, a resistor, a phosphor, a color filter, and a black matrix) excellent in patternability and pattern shape. It is possible to provide an inorganic powder-containing resin composition having excellent film transferability.

  A second object of the present invention is to enable efficient formation of an FPD panel member excellent in patternability and pattern shape, and a transfer film excellent in film transferability and an FPD manufacturing method using the transfer film Is to provide.

  The first inorganic powder-containing resin composition (hereinafter also referred to as “Composition I”) of the present invention comprises (a) inorganic powder and (b) a monomer represented by the following formula (1) (hereinafter “monomer”). (1) ")) as a polymerization component, and (c) a solvent.

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms, and B represents a group that blocks an isocyanate group. Show.

  The second inorganic powder-containing resin composition of the present invention (hereinafter also referred to as “Composition II”) contains (d) a radiation-sensitive component in addition to the components (a), (b) and (c). It is characterized by doing.

  The first transfer film of the present invention (hereinafter also referred to as “transfer film I”) has an inorganic powder-containing resin layer obtained from the composition I or the composition II of the present invention on a support film. To do.

  The second transfer film of the present invention (hereinafter also referred to as “transfer film II”) has a laminated film of a resist film and an inorganic powder-containing resin layer obtained from the composition I of the present invention on a support film. It is characterized by that.

In the first FPD member production method of the present invention (hereinafter also referred to as “FPD production method I”), an inorganic powder-containing resin layer formed on a support film and obtained from the composition I of the present invention is used as a substrate. A step of transferring the resist film, a step of forming a resist film on the inorganic powder-containing resin layer, a step of exposing the resist film to form a latent image of the resist pattern, and developing the resist film to form a resist pattern A step of forming a pattern layer corresponding to the resist pattern by etching the inorganic powder-containing resin layer, and a baking treatment of the pattern layer, so that a dielectric layer, a partition, an electrode, It includes a step of forming a panel member selected from a resistor, a phosphor, a color filter, and a black matrix.

  The second FPD member production method of the present invention (hereinafter also referred to as “FPD production method II”) comprises a resist film formed on a support film and an inorganic powder obtained from the composition I of the present invention. The process of transferring the laminated film with the resin layer onto the substrate, the process of exposing the resist film constituting the laminated film to form a latent image of the resist pattern, and developing the resist film to reveal the resist pattern A step of etching the inorganic powder-containing resin layer to form a pattern layer corresponding to the resist pattern, and a baking treatment of the pattern layer, so that the dielectric layer, the partition, the electrode, the resistor, the fluorescence Forming a panel member selected from a body, a color filter, and a black matrix.

The third FPD member production method of the present invention (hereinafter also referred to as “FPD production method III”) is:
A step of transferring the inorganic powder-containing resin layer formed from the composition II of the present invention formed on the support film onto the substrate, and exposing the inorganic powder-containing resin layer to form a latent image of the pattern A step of developing the inorganic powder-containing resin layer to form a pattern layer, and a baking treatment of the pattern layer to obtain a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color filter, and black It includes a step of forming a panel member selected from a matrix.

  When the inorganic powder-containing resin composition of the present invention is used, a film excellent in linearity can be obtained because the film transferability to a substrate is good and the resin does not melt during firing.

  Hereinafter, the inorganic powder-containing resin composition, transfer film, and FPD manufacturing method according to the present invention will be described in detail.

[Inorganic powder-containing resin composition]
The inorganic powder-containing resin composition of the present invention comprises (a) inorganic powder, (b) an acrylic resin containing the monomer (1) as a polymerization component, (c) a solvent, and (d) as necessary. It contains a radiation sensitive component and can be suitably used for forming an FPD member.

(A) Inorganic powder The inorganic substance constituting the inorganic powder (a) used in the composition of the present invention is not particularly limited, and is used for a sintered body formed by the composition (FPD member). Depending on the type).

Here, the inorganic powder contained in the composition for forming the “dielectric layer” or “partition” constituting the FPD has a softening point in the range of 350 to 700 ° C. (preferably 400 to 620 ° C.). The glass powder inside can be mentioned. When the softening point of the glass powder is less than 400 ° C., in the firing process of the inorganic powder-containing resin layer formed from the composition of the present invention, the organic substance such as the binder resin is not completely decomposed and removed. Since the glass powder is melted, a part of the organic substance remains in the formed dielectric layer. As a result, the dielectric layer is colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 620 ° C., the glass substrate needs to be baked at a temperature higher than 620 ° C., so that the glass substrate is likely to be distorted.

Specific examples of suitable glass powder include
1. A mixture of lead oxide, boron oxide, silicon oxide (PbO-B ₂ O ₃ —SiO ₂ system),
2. A mixture of zinc oxide, boron oxide, silicon oxide (ZnO-B ₂ O ₃ —SiO ₂ system),
3. A mixture of lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ series),
4). 4. A mixture of lead oxide, zinc oxide, boron oxide and silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ system); A mixture of bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system),
6). A mixture of zinc oxide, phosphorus oxide, silicon oxide (ZnO-P ₂ O ₅ —SiO ₂ system),
7). A mixture of zinc oxide, boron oxide, potassium oxide (ZnO-B ₂ O ₃ -K ₂ O system),
8). A mixture of phosphorus oxide, boron oxide, aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system),
9. A mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO-P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ series),
10. A mixture of zinc oxide, phosphorus oxide, titanium oxide (ZnO-P ₂ O ₅ -TiO ₂ system),
11. A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide (ZnO-B ₂ O ₃ —SiO ₂ system—K ₂ O system),
12 Zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide (ZnO-B ₂ O ₃
Mixtures -SiO ₂ -K ₂ O-CaO-based),
13. Examples thereof include a mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, and aluminum oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO—Al ₂ O ₃ system).

  The glass powder may be contained (combined) in a composition for forming a panel member (for example, an electrode, a resistor, a phosphor, a color filter, or a black matrix) other than the dielectric layer and the partition. The content of the glass powder in the inorganic powder-containing resin composition for obtaining these panel members is usually 80% by mass or less, preferably 1 to 70% by mass with respect to the total amount of the inorganic powder.

  Examples of the inorganic powder contained in the composition for forming the “electrode” constituting the FPD include metal particles made of Ag, Au, Al, Ni, Ag—Pd alloy, Cu, Co, Cr, and the like. Can do. When forming an electrode having two layers of a dark color layer (antireflection layer) and a white layer as an electrode, the inorganic powder used for the dark color layer includes Ni, Cu, Fe, Cr, Mn and Those composite oxides, nickel oxide, iron oxide, copper oxide, cobalt oxide, ruthenium oxide and the like are preferably used.

  These metal particles may be contained in the composition for forming the dielectric layer in a form used in combination with glass powder. The content of the metal particles in the dielectric layer forming composition is usually 10% by mass or less, preferably 0.1 to 5% by mass with respect to the total amount of the inorganic powder.

Examples of the inorganic powder contained in the composition for forming the “resistor” constituting the FPD include particles made of RuO ₂ or the like.

As inorganic powders contained in the composition for forming the “phosphor” constituting the FPD, Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : red fluorescent material such as Mn; Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : fluorescent substance for green, such as Tb; Y ₂ SiO ₅ : Ce, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , (Zn, Cd) S: Made of blue fluorescent materials such as Ag Particles can be mentioned.

Inorganic powders contained in the composition for forming the “color filter” constituting the FPD include red materials such as Fe ₂ O ₃ and Pb ₃ O ₄ , green materials such as Cr ₂ O ₃ , Examples thereof include particles made of blue substances such as 2 (Al ₂ Na ₂ Si ₃ O ₁₀ ) and Na ₂ S ₄ .

  Examples of the inorganic powder contained in the composition for forming the “black matrix” constituting the FPD include Mn, Fe, Cr, Co, Ni, oxides thereof, and particles composed of these oxides. be able to.

(B) Acrylic resin The acrylic resin (b) used in the composition of the present invention contains a monomer (1) represented by the following formula (1) as a polymerization component and functions as a binder resin. Moreover, it is preferable that the said acrylic resin (b) has alkali solubility. Here, “alkali-soluble” refers to the property of being dissolved in an alkaline developer and having a solubility to such an extent that the intended development processing is performed.

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms, and B represents a group that blocks an isocyanate group. Show. Specific examples of B include an alkoxy group, a phenoxy group, an active methylene compound residue, a mercaptan compound residue, an acid amide compound residue, an amino group, an imidazole compound residue, an imino group, an oxime compound residue, Examples include lactam compound residues.

  The monomer (1) preferably has a blocked isocyanate group and a polymerizable unsaturated group, and does not have any other functional group (for example, a hydroxyl group). The monomer (1) can be deblocked by heat treatment to regenerate active isocyanate groups as shown in the following reaction formula.

Thus, upon firing, to react with substituent regenerated isocyanate groups having an active hydrogen in the polymer (-COOH, -OH, -NH _2, etc.), to induce thermal crosslinking, occurs molecular weight of the polymer Further, it is possible to suppress the deformation and thickness of the pattern due to the resin melt. Further, at normal temperature, the isocyanate group is not unblocked and does not react with active hydrogen. Therefore, the polymer cannot have a high molecular weight and is excellent in storage stability. Therefore, by using the monomer (1), an inorganic powder-containing resin composition having excellent flexibility and transferability can be obtained, and the melt of the resin during firing can be suppressed, and there is no line weight and excellent shape. Pattern can be obtained.

The blocked isocyanate (—NHCO—B) group in the monomer (1) can be formed by treating a free isocyanate group with a known blocking method using a known blocking agent (H—B). it can. As said blocking agent, the compound generally used conventionally as a blocking agent of an isocyanate group is mentioned.

  Specific examples of the blocking agent (H-B) include alcohol compounds such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol, and furfuryl alcohol; Phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, α-naphthol, β-naphthol, p-nitrophenol, p-chlorophenol Active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, ethyl acetoacetate; butyl mercaptan, dodecyl mercaptan, Mercaptan compounds such as thiophenol; acid amide compounds such as acetanilide, acetanisidide, acetylamide, benzamide; amine compounds such as diphenylamine, aniline, carbazole; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, etc. Imidazole compounds of the above; imine compounds such as ethyleneimine; oxime compounds such as formaldoxime, acetoaldoxime, methylethylketoxime, cyclohexanone oxime; lactams such as ε-caprolactam, δ-valerolactam, β-propiolactam A compound etc. can be mentioned. Among these, alcohol compounds, phenol compounds, active methylene compound compounds, oxime compounds, and lactam compounds are preferable, and oxime compounds are more preferable.

As said monomer (1), it is preferable to use 1 type, or 2 or more types of monomers obtained by blocking the isocyanate group of 2-isocyanatoethyl methacrylate. Specific examples of the monomer (1) include 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Showa Denko: Karenz MOI-BM), 2-[(3.5 -Dimethylpyrazolyl) carboxyamino] ethyl (Showa Denko: Karenz MOI-BP) and the like.

  The acrylic resin (b) may be a copolymer of the monomer (1), a monomer having another (meth) acryloyl group, and a monomer having another polymerizable unsaturated group as necessary. desirable. The acrylic resin (b) may be any of a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer. The polymerization ratio of the monomer (1) in the acrylic resin (b) is preferably 0.1 to 70 parts by weight, particularly preferably 1 to 50 parts by weight.

  Preferred examples of the monomer having the other (meth) acryloyl group include the following monomers (i), (ii), and (iii).

Monomers (i) include carboxyl group-containing monomers, and specifically include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid. Examples include acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.

  Examples of the monomer (ii) include OH-containing monomers, specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the like. Hydroxyl group-containing monomers: o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc .; phenolic hydroxyl group-containing monomers; polyalkylene glycol mono (meth) acrylates (Blemmer PE, Blemmer AE, Blemmer PP series: Japan And the like.

Examples of the monomer (iii) include other copolymerizable monomers. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) (Meth) acrylic other than monomer (i) such as 2-ethylhexyl acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate Acid esters; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated dienes such as butadiene and isoprene; polystyrene, poly (meth) acrylate, poly (meth) ethyl acrylate, poly (meth) A polymer having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as benzyl acrylate Monomers; alkyl group-terminated polyalkylene glycol mono (meth) acrylates (BLEMMER PME, Blemmer AME, Blenmer PSE Series: manufactured by NOF Corporation) and the like.

The monomer (1), the copolymer of the monomer (i) and the monomer (iii), and the copolymer of the monomer (1), the monomer (i), the monomer (ii) and the monomer (iii) are the monomer (i ), The presence of the copolymerization component results in alkali solubility. Among these, the copolymer of monomer (1), monomer (i), monomer (ii) and monomer (iii) is from the viewpoint of dispersion stability of inorganic powder (a) and solubility in an alkali developer described later. Particularly preferred. The content of the copolymer component derived from the monomer (i) in this copolymer is preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass, and the content of the copolymer component derived from the monomer (ii) The content is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass.

  The acrylic resin (b) has a weight average molecular weight (Mw) of preferably 5,000 to 5,000,000, more preferably 10,000 to 300,000.

  Further, the content ratio of the acrylic resin (b) in the composition of the present invention is usually 1 to 200 parts by mass, preferably 5 to 150 parts by mass, particularly preferably 100 parts by mass of the inorganic powder (a). Is 10 to 120 parts by mass.

(C) Solvent The inorganic powder-containing resin composition of the present invention usually contains a solvent in order to impart appropriate fluidity or plasticity and good film forming properties. As the solvent used, it has good affinity with inorganic powder and good solubility of binder resin, can give moderate viscosity to the resin composition containing inorganic powder, and easily evaporates by drying. It is preferable that it can be removed.

  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 100 to 200 ° C.

  Specific examples of the specific solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol. Ether ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; saturated aliphatic monocarboxylic acids such as n-butyl acetate and amyl acetate Alkyl esters; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Acetate, ethyl-3 and ether-based esters such as ethoxy propionate.

  Among the above, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate and the like are preferable. The said specific solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

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

  The content ratio of the solvent in the inorganic powder-containing resin composition of the present invention can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) are obtained.

(D) Radiation-sensitive component The inorganic powder-containing resin composition of the present invention may be a radiation-sensitive inorganic powder-containing resin composition containing a radiation-sensitive component. Preferred examples of the radiation-sensitive component include 1) a combination of a polyfunctional monomer and a radiation polymerization initiator, and 2) a combination of a melamine resin and a photoacid generator that forms an acid by irradiation. can do. Among the combinations of 1), a combination of a polyfunctional (meth) acrylate and a radiation polymerization initiator is particularly preferable.

  Specific examples of the polyfunctional (meth) acrylate include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; Di (meth) acrylates of hydroxylated polymers at both ends such as terminal hydroxypolybutadiene, both ends hydroxypolyisoprene, and both ends hydroxypolycaprolactone; glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as pentaerythritol and dipentaerythritol; polyalkylene glycol adducts of trihydric or higher polyhydric alcohols (Meth) acrylates; poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, Examples include oligo (meth) acrylates such as alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. These may be used alone or in combination of two or more.

  The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.

  Content of polyfunctional (meth) acrylate in the composition of this invention is 20-80 mass parts normally with respect to 100 mass parts of inorganic powder (a), Preferably it is 30-60 mass parts.

Specific examples of the radiation polymerization initiator include benzyl, benzoin, benzophenone, bis (N, N-dimethylamino) benzophenone, bis (N, N-diethylamino) benzophenone, camphorquinone, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propanone, 2- Carbonyl compounds such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; mercaptan disulfide, mercaptobenzo Organic such as thiazole Sulfur compounds; organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, paraffin hydroperoxide; 1,3-bis (trichloromethyl) -5- ( 2'-chlorophenyl) -1,3,5-triazine, trihalomethanes such as 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine; 2 , 2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl1,2′-biimidazole and other imidazole dimers. These may be used alone or in combination of two or more.

  The content of the radiation polymerization initiator in the composition of the present invention is usually 0.01 to 50.0 parts by mass, preferably 0.1 to 30.30 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate. 0 parts by mass.

<Composition example>
As an example of the composition of the present invention, if an example of a preferred electrode forming composition is shown, 100 parts by mass of nickel powder and 1 to 30 parts by mass of glass powder as inorganic powder (a), and blemmer as acrylic resin (b) 10 to 150 parts by mass of PME-100 / n-butyl methacrylate / methacrylic acid / 2-hydroxypropyl methacrylate / methacrylic acid 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl copolymer; Examples of the solvent (c) include a composition containing 5 to 30 parts by mass of propylene glycol monomethyl ether and / or ethyl-3-ethoxypropionate.

  In addition, the inorganic powder-containing resin composition of the present invention includes, as optional components, a silane coupling agent, a plasticizer, a dispersant, a development accelerator, an adhesion assistant, an antihalation agent, a leveling agent, a storage stabilizer, Various additives such as a foaming agent, an antioxidant, an ultraviolet absorber, a sensitizer, a chain transfer agent, a tackifier, and a surface tension modifier may be contained.

<Preparation of composition>
The inorganic powder-containing resin composition of the present invention is prepared by roll kneading the inorganic powder (a), the acrylic resin (b), the solvent (c) and, if necessary, the radiation-sensitive component (d) and the optional component. It can be prepared by kneading using a kneader such as a machine, a mixer, a homomixer, a ball mill, or a bead mill.

  The inorganic powder-containing resin composition prepared as described above is a paste-like composition having fluidity suitable for coating, and its viscosity is usually 100 to 1,000,000 cP, preferably 300. ~ 300,000 cP.

[Transfer film]
The transfer film of the present invention is a composite film suitably used in the process of forming an FPD member, and is formed by applying the composition of the present invention on a support film and drying the coating film. It comprises a containing resin layer.

  That is, the 1st transfer film of this invention has an inorganic powder containing resin layer containing inorganic powder (a), an acrylic resin (b), and a solvent (c) on a support film. The first transfer film of the present invention may be a radiation-sensitive transfer film in which the radiation-sensitive component (d) is further contained in the inorganic powder-containing resin layer.

The second transfer film of the present invention is formed by applying a composition of the present invention on a resist film formed on the support film, the resist film formed on the support film, and drying the coating film. And a laminated film with the inorganic powder-containing resin layer.

  The inorganic powder-containing resin layer on the support film is collectively transferred to the surface of the substrate. According to the transfer film of the present invention, since the inorganic powder-containing resin layer can be reliably formed on the glass substrate by such a simple operation, the process improvement (high efficiency) in the formation process of the FPD member can be achieved. It is possible to improve the quality of the formed member (for example, to develop stable line resistance in the electrode).

<Configuration of transfer film>
FIG. 1 (a) is a schematic cross-sectional view showing the transfer film of the present invention wound in a roll shape, and FIG. 1 (b) is a cross-sectional view showing the layer structure of the transfer film [part of FIG. Detailed view].

  The transfer film shown in FIG. 1 is a composite film as an example of the transfer film of the present invention, and is usually a support film F1 and an inorganic powder-containing resin layer F2 formed on the surface of the support film F1 so as to be peelable. And a cover film F3 which is easily provided on the surface of the inorganic powder-containing resin layer F2. The cover film F3 may not be used depending on the properties of the inorganic powder-containing resin layer F2. In addition, a resist film may be formed between the support film F1 and the inorganic powder-containing resin layer F2, and the inorganic powder-containing resin layer F2 is a laminate in which two or more layers of the same kind are laminated. But you can.

  The support film F1 constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film F1 has flexibility, a paste-like composition (composition of the present invention) can be applied using a roll coater, a blade coater, or the like, whereby an inorganic powder having a uniform film thickness can be applied. The body-containing resin layer can be formed, and the formed inorganic powder-containing resin layer can be stored and supplied in a state of being wound in a roll.

  Examples of the resin constituting the support film F1 include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. . The thickness of the support film F1 is, for example, 20 to 100 μm.

  The inorganic powder-containing resin layer F2 constituting the transfer film is a layer that becomes an inorganic sintered body (FPD member) when fired, and contains inorganic powder (a) and acrylic resin (b) as essential components. Has been.

  The thickness of the inorganic powder-containing resin layer F2 is, for example, 5 to 200 μm, although it varies depending on the type of member to be formed, the content of the inorganic powder, the type and size of the panel.

  The cover film F3 constituting the transfer film is a film for protecting the surface of the inorganic powder-containing resin layer F2 (contact surface with the substrate). This cover film F3 is also preferably a flexible resin film. As resin which forms cover film F3, resin illustrated as what forms support film F1 can be mentioned. The thickness of the cover film F3 is, for example, 20 to 100 μm.

<Production method of transfer film>
In the transfer film of the present invention, the inorganic powder-containing resin layer (F2) is formed on the support film (F1), and the cover film (F3) is provided (crimped) on the inorganic powder-containing resin layer (F2). Can be manufactured.

  As a method of applying the composition of the present invention on a support film, a roll coater is used from the viewpoint of efficiently forming a coating film having a large film thickness (for example, 20 μm or more) and excellent film thickness uniformity. Preferable examples include a coating method, a coating method using a blade coater such as a doctor blade, a coating method using a curtain coater, a coating method using a wire coater, and a coating method using a die coater.

  In addition, it is preferable that the mold release process is given to the surface of the support film with which the composition of this invention is apply | coated. Thereby, after transferring the inorganic powder-containing resin layer, the support film can be easily peeled from the inorganic powder-containing resin layer.

  The coating film of the composition of the present invention formed on the support film is dried to remove a part or all of the solvent, thereby forming an inorganic powder-containing resin layer constituting the transfer film. As drying conditions of the coating film by the composition of this invention, it is about 0.1 to 30 minutes at 40-150 degreeC, for example. The residual ratio of the solvent after drying (the content ratio of the solvent in the inorganic powder-containing resin layer) is usually 10% by mass or less, and exhibits adhesiveness to the substrate and appropriate shape retention in the inorganic powder-containing resin layer. It is preferable that it is 0.1-5 mass% from a viewpoint to make it do.

  It is preferable that the surface of the cover film (usually thermocompression-bonded) provided on the inorganic powder-containing resin layer formed as described above is also subjected to a release treatment. Thereby, before transferring an inorganic powder containing resin layer, a cover film can be easily peeled from the said inorganic powder containing resin layer.

[Method of manufacturing FPD]
In the FPD manufacturing method of the present invention, at least one panel member selected from a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color filter, and a black matrix is formed using the transfer film of the present invention. It is characterized by.

An example of the transfer process of the inorganic powder-containing resin layer by the transfer film having the structure as shown in FIG. 1 is as follows.
1. The transfer film wound on the roll is cut into a size corresponding to the area of the substrate. 2. After peeling the cover film (F3) from the surface of the inorganic powder-containing resin layer (F2) in the cut transfer film, the transfer film is overlaid so that the surface of the inorganic powder-containing resin layer (F2) contacts the surface of the substrate. Match.
3. A heat roller is moved on the transfer film superimposed on the substrate and thermocompression bonded.
4). The support film (F1) is peeled and removed from the inorganic powder-containing resin layer (F2) fixed to the substrate by thermocompression bonding.

  By the operations 1 to 4 as described above, the inorganic powder-containing resin layer (F2) on the support film (F1) is transferred onto the substrate. The inorganic powder-containing resin layer (F2) transferred and formed on the surface of the substrate is fired to become an inorganic sintered body. Examples of the firing method include a method in which the substrate on which the inorganic powder-containing resin layer (F2) is transferred is placed in a high temperature atmosphere. Thereby, the organic substance (for example, binder resin, residual solvent, nonionic surfactant, various additives) contained in the inorganic powder-containing resin layer (F2) is decomposed and removed, and the inorganic powder Melts and sets. The firing temperature is, for example, 300 to 800 ° C., preferably 400 to 620 ° C., although it varies depending on the melting temperature of the substrate and the constituent materials in the inorganic powder-containing resin layer.

<Method for manufacturing FPD I>
FPD manufacturing method I of the present invention includes a step of transferring an inorganic powder-containing resin layer constituting the transfer film of the present invention onto a substrate, a step of forming a resist film on the transferred inorganic powder-containing resin layer, A step of exposing the resist film to form a latent image of the resist pattern; a step of developing the resist film to expose the resist pattern; and etching the inorganic powder-containing resin layer to form the resist pattern. A step of forming a corresponding pattern layer, and a step 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 firing the pattern layer.

  The resist film is formed by a method using the transfer film of the present invention in which a laminated film of a resist film and an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition of the present invention is formed on a support film. It may be formed by batch transfer onto the substrate together with the powder-containing resin layer. This method will be described later as FPD production method II which is a preferred embodiment utilizing a photoresist method.

  Hereinafter, a method of forming “electrodes” which are panel members of the FPD on the surface of the back substrate will be described as an example. In this method, [1] a transfer process of an inorganic powder-containing resin layer, [2] a resist film formation process, [3] a resist film exposure process, [4] a resist film development process, [5] inorganic powder An electrode is formed on the surface of the substrate by the etching process of the body-containing resin layer and [6] the baking process of the inorganic powder-containing resin pattern.

[1] Transfer process of inorganic powder-containing resin layer In this process, the inorganic powder-containing resin layer of the transfer film of the present invention is transferred and formed on a substrate. An example of the transfer process of the inorganic powder-containing resin layer is as follows.

  After peeling the cover film of the transfer film, the transfer film is overlaid on the substrate surface so that the surface of the inorganic powder-containing resin layer is in contact, and the transfer film is thermocompression bonded with a heating roller, etc. The support film is peeled off from the powder-containing resin layer. As a result, the inorganic powder-containing resin layer is transferred and adhered to the surface of the substrate. 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, and the moving speed of the heating roller is 0.1 to 10.0 m / min. The substrate may be preheated, and the preheating temperature is, for example, 40 to 100 ° C.

[2] Formation process of resist film In this process, a resist film is formed on the surface of the transferred inorganic powder-containing resin layer. The resist constituting the resist film may be either a positive resist or a negative resist. As an example of a preferable resist used in the present invention, a resist composition containing the polyfunctional (meth) acrylate that is the radiation-sensitive component described above, a radiation polymerization initiator, and an acrylic resin as a binder resin can be exemplified. .

  The resist film can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method, and then drying the coating film. The drying temperature of a coating film is about 60-130 degreeC normally.

  Moreover, you may form by transferring the resist film formed on the support film to the surface of an inorganic powder containing resin layer. According to such a forming method, the number of steps of forming the resist film can be reduced, and the film thickness uniformity of the resulting resist is excellent, so that the resist film development process and the inorganic powder-containing resin layer The etching process is uniformly performed, and the height and shape of the formed electrode are uniform. The thickness of the resist film is usually 0.1 to 40 μm, preferably 0.5 to 20 μm.

[3] Exposure process of resist film In this process, the surface of the resist film formed on the inorganic powder-containing resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask. Thus, a latent image of the resist pattern is formed. In addition, when the resist film is formed by transfer, it is preferable to perform the exposure step without peeling off the support film coated on the resist film.

  The ultraviolet irradiation apparatus used in the exposure process is not particularly limited, such as an ultraviolet irradiation apparatus used in a conventional photolithography method and an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device.

[4] Step of developing resist film In this step, the exposed resist film is developed to reveal a resist pattern (latent image).

  The development processing conditions include, depending on the type of resist film, the type / composition / concentration of developer, development time, development temperature, development method (for example, dipping method, rocking method, shower method, spray method, paddle method) ), A developing device and the like can be appropriately selected.

  By this development process, a resist pattern (pattern corresponding to an exposure mask) composed of a resist remaining portion and a resist removal portion is formed.

  This resist pattern acts as an etching mask in the next process (etching process), and the constituent material of the resist remaining portion (photocured resist) is more resistant to the etching solution than the constituent material of the inorganic powder-containing resin layer. A low dissolution rate is required.

[5] Inorganic powder-containing resin layer etching step In this step, the inorganic powder-containing resin layer is etched to form an inorganic powder-containing resin pattern layer corresponding to the resist pattern. That is, in the inorganic powder-containing resin layer, a portion corresponding to the resist removal portion of the resist pattern is dissolved in the etching solution and selectively removed. And the predetermined part in an inorganic powder containing resin layer is removed completely, and a board | substrate is exposed. Thereby, the inorganic powder containing resin pattern layer comprised from the resin layer residual part and the resin layer removal part is formed.

  Etching conditions include the type / composition / concentration of the etchant, treatment time, treatment temperature, treatment method (eg, dipping method, rocking method, shower method, spraying) depending on the type of the inorganic powder-containing resin layer. Method, paddle method), processing apparatus, and the like can be selected as appropriate. In addition, the development process and the etching process are continuously performed by selecting the type of the resist film and the inorganic powder-containing resin layer so that the same solution as that used in the development process can be used as the etching liquid. Therefore, the manufacturing efficiency can be improved by simplifying the process.

  Here, the resist remaining portion constituting the resist pattern is gradually dissolved during the etching process and is completely removed at the stage where the inorganic powder-containing resin pattern is formed (at the end of the etching process). It is preferable. Even if a part or all of the remaining resist portion remains after the etching process, the remaining resist portion is removed in the next baking step.

[6] Inorganic powder-containing resin pattern firing step In this step, the inorganic powder-containing resin pattern layer is fired. As a result, the organic material in the resin layer remaining portion is burned away, and an electrode is formed.

  The temperature of the baking treatment needs to be a temperature at which the organic material in the resin layer residual portion is burned off, and is usually 400 to 600 ° C. The firing time is usually 10 to 90 minutes.

<Preferred Embodiment in FPD Production Method I>
As a particularly preferred method (FPD production method II) in the FPD production method I of the present invention using a photoresist method, there can be mentioned a formation method according to the following steps (1) to (3).

  (1) After forming a resist film on the support film, the inorganic powder-containing resin layer is laminated and formed by applying and drying the inorganic powder-containing resin composition of the present invention on the resist film. When forming the resist film and the inorganic powder-containing resin layer, a roll coater or the like can be used, whereby a laminated film having excellent film thickness uniformity can be formed on the support film.

  (2) The laminated film of the resist film and the inorganic powder-containing resin layer formed on the support film is transferred onto the substrate. The transfer conditions may be the same as those in [1] Transfer step of the inorganic powder-containing resin layer.

  (3) The same as [3] resist film exposure step, [4] resist film development step, [5] inorganic powder-containing resin layer etching step, and [6] inorganic powder-containing resin pattern firing step. Perform the operation. At that time, as described above, the resist film developer and the inorganic powder-containing resin layer etching solution are the same solution, and [4] the resist film development step and [5] the inorganic powder-containing resin layer. It is preferable to continuously perform the etching step.

  According to the above method, since the inorganic powder-containing resin layer and the resist film are collectively transferred onto the substrate, the production efficiency can be further improved by simplifying the process.

<FPD production method III>
The FPD production method III of the present invention comprises a step of transferring an inorganic powder-containing resin layer constituting the radiation-sensitive transfer film of the present invention onto a substrate, and exposing the inorganic powder-containing resin layer to a latent pattern. A step of forming an image, a step of developing the inorganic powder-containing resin layer to form a pattern layer, and a baking treatment of the pattern layer, so that a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color Forming a panel member selected from a filter and a black matrix.

  In this method, for example, when an electrode forming method is taken as an example, after [1] the transfer process of the inorganic powder-containing resin layer, [3] a resist film exposure process, and [4] a resist film development process. An electrode is formed on the surface of the substrate by forming a pattern layer under the same conditions and then performing a baking treatment in the same manner as in [6] baking process of the inorganic powder-containing resin pattern.

In the above description of each process of the FPD manufacturing methods I, II, and III of the present invention, the method of forming the “electrode” as the FPD member has been described. The dielectric layer, partition wall, A resistor, a phosphor, a color filter, a black matrix, and the like can be formed.

[Example]
Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.

[Example 1]
(1) Preparation of Resin Composition 1 Containing Inorganic Powder for Antireflection Film Formation As inorganic powder, 100 parts of nickel powder (average particle size 0.2 μm) and Bi ₂ O ₃ —O—
10 parts of B ₂ O ₃ —SiO ₂ glass frit (softening point 560 ° C., average particle size 2.0 μm), as binder resin, Blemmer PME-100 / n-butyl methacrylate / methacrylic acid / 2-hydroxy methacrylate Propyl / methacrylic acid 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl = 20/35/15/20/10 (mass%) copolymer (weight average molecular weight: 90,000) 90 parts , 30 parts of trimethylolpropane triacrylate as a plasticizer, 1 part of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent, 3 parts of oleic acid as a dispersant, 20 parts of propylene glycol monomethyl ether as a solvent, using a disperser And kneading to prepare an inorganic powder-containing resin composition 1 for forming an antireflection film.

(2) Preparation of Inorganic Powder Resin Composition for Forming Conductive Film 100 parts of silver powder (average particle size 2.2 μm) as conductive particles and Bi ₂ O ₃ —O—B ₂ O ₃ —SiO ₂ glass frit ( Softening point 520 ° C., average particle size 2.0 μm) 10 parts, binder resin benzyl methacrylate / 2-ethylhexyl methacrylate / 2-hydroxypropyl methacrylate / methacrylic acid / succinic acid (2- (meth) acryloyloxy) Ethyl) = 20/20/20/20/20 (mass%) copolymer (weight average molecular weight: 90,000) 15 parts, polypropylene glycol diacrylate (n = 12) 10 parts as a plasticizer, olein as a dispersant An inorganic powder resin composition for forming a conductive film was prepared by kneading 1 part of acid and 9 parts of propylene glycol monomethyl ether as a solvent using a disperser. It was.

(3) Preparation of resist composition 60 parts of benzyl methacrylate / methacrylic acid = 75/25 (mass%) copolymer (weight average molecular weight: 30,000) as binder resin, polypropylene glycol diacrylate (polyfunctional monomer) n = 12) 40 parts, 20 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as a photopolymerization initiator and 100 parts 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).

(4) Production of transfer film for electrode formation A laminated film having a resist film, an inorganic powder resin layer for forming a conductive film, and an inorganic powder resin layer for forming an antireflective film (hereinafter referred to as “hereinafter referred to as“ antireflection film ”) An electrode-forming transfer film in which an electrode-forming laminated film is also formed on a support film was prepared.

i) PET having a film thickness of 38 μm obtained by previously releasing the resist composition prepared in (3) above.
The film was applied onto a support film made of a film using a roll coater, and the coating film was dried at 100 ° C. for 5 minutes to completely remove the solvent, thereby forming a resist film having a thickness of 5 μm on the support film.

ii) Apply the inorganic powder resin composition for forming a conductive film prepared in (2) above onto the resist film prepared in i) above using a roll coater, and dry the coating film at 100 ° C. for 5 minutes. The solvent was completely removed, and a 20 μm thick inorganic powder resin layer for forming a conductive film was formed on the resist film.

iii) Applying the inorganic powder resin composition for forming an antireflection film prepared in (1) above onto the inorganic powder resin layer for forming a conductive film formed in ii) above using a roll coater, The solvent was completely removed by drying at 100 ° C. for 5 minutes, and an antireflection film-forming inorganic powder resin layer having a thickness of 8 μm was formed on the conductive film-forming inorganic powder resin layer.

(5) Transfer of electrode forming transfer film The above (4) so that the surface of the inorganic powder resin layer for forming an antireflection film is brought into contact with the surface of a glass substrate previously heated to 80 ° C. on a hot plate. The electrode-forming transfer film prepared in 1 was superposed, and the transfer film was thermocompression bonded to a heating roller. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 100 ° C., the roll pressure was 2 kg / cm, and the moving speed of the heating roller was 0.5 m / min. After the thermocompression treatment, the support film was peeled off from the transfer film (resist film surface), and the electrode-forming laminated film was transferred. After the transfer, as an index of film transferability, that is, adhesion between the substrate and the film, a cutter blade was inserted between the substrate and the film, and a test was performed to determine whether the film peeled off. As an index, “X” indicates a case where peeling easily, and “B” indicates a case where peeling does not occur.

(6) Resist film exposure process The resist film of the electrode-forming laminated film formed on the glass substrate is subjected to an ultrahigh pressure mercury lamp through a striped negative exposure mask having a line width of 100 μm and a space width of 400 μm. Irradiated with mixed light of g-line (436 nm), h-line (405 nm), and i-line (365 nm). The exposure amount at that time was 200 mJ / cm ^{2 in} terms of illuminance measured by a 365 nm sensor.

(7) Development process / etching process The exposed resist film is developed by a shower method using a 0.3% by mass sodium carbonate aqueous solution at a liquid temperature of 30 ° C. as a developer, and then an inorganic powder-containing resin layer. The etching process was performed for 90 seconds, and then washed with ultrapure water. As a result, a resist pattern was formed, and an inorganic powder-containing resin pattern corresponding to the resist pattern was formed. About the obtained inorganic powder containing resin pattern, it was confirmed with an optical microscope whether there was a resolution abnormality, a residue, etc. As an index of pattern resolution, “X” was given when abnormal resolution or residue was seen, and “◯” was given when no pattern was seen.

(8) Firing step The glass substrate on which the inorganic powder-containing resin pattern was formed was baked for 30 minutes in a firing furnace in a temperature atmosphere of 590 ° C. Thus, a panel material in which an electrode having a pattern width of 100 μm and a thickness of 10 μm was formed on the surface of the glass substrate could be obtained. The formed electrode pattern was observed using a microscope, and it was confirmed whether there was any pattern thickening or linearity abnormality. As an indicator of line thickening and linearity (hereinafter referred to as “pattern linearity”) of the pattern after firing, “x” is indicated when the weight is abnormal or linearity is abnormal, and “◯” is indicated when the abnormality is not observed.

[Comparative Example 1]
(1) Preparation of inorganic powder-containing resin composition 2 for forming antireflection film 100 parts of nickel powder (average particle size 0.2 μm) as inorganic powder and Bi ₂ O ₃ —O—B ₂ O ₃ —SiO ₂ system 10 parts of glass frit (softening point 560 ° C., average particle size 2.0 μm), as binder resin, Blemmer PME-100 / n-butyl methacrylate / methacrylic acid / 2-hydroxypropyl methacrylate = 10/50/25 / 90 parts of a 20 (mass%) copolymer (weight average molecular weight: 90,000), 30 parts of trimethylolpropane triacrylate as a plasticizer, 1 part of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent, as a dispersant Anti-reflective coating by kneading 3 parts oleic acid and 20 parts propylene glycol monomethyl ether as solvent using a disperser A forming inorganic powder-containing resin composition 2 was prepared.

Hereinafter, instead of using the inorganic powder-containing resin composition 1 for forming an antireflection film in Example 1, the inorganic powder-containing resin composition 2 for forming an antireflection film obtained in the above (1) was used. In the same manner as in Example 1, (2) Preparation of an inorganic powder resin composition for forming a conductive film, (3) Preparation of a resist composition, (4) Preparation of a transfer film for forming an electrode, (5) Formation of an electrode Operation and evaluation of transfer film transfer, (6) resist film exposure process, (7) development process / etching process, and (8) baking process were performed.

[Comparative Example 2]
(1) Preparation of Resin Composition 3 Containing Inorganic Powder for Antireflection Film Formation As inorganic powder, 100 parts of nickel powder (average particle size 0.2 μm) and Bi ₂ O ₃ —O—B ₂ O ₃ —SiO ₂ -Based glass frit (softening point 560 ° C., average particle size 2.0 μm), as binder resin, Blemmer PME-100 / n-butyl methacrylate / methacrylic acid / 2-hydroxypropyl methacrylate = 20/45/15 / 20 (mass%) copolymer (weight average molecular weight: 90,000) 90 parts, 30 parts of trimethylolpropane triacrylate as plasticizer, 1 part of 3-methacryloxypropyltrimethoxysilane as silane coupling agent, dispersant Anti-reflection by kneading 3 parts oleic acid as a solvent and 20 parts propylene glycol monomethyl ether as a solvent using a disperser An inorganic powder-containing resin composition 3 for film formation was prepared.

  Hereinafter, in place of the inorganic powder-containing resin composition 1 for forming an antireflection film in Example 1, except that the inorganic powder-containing resin composition 3 for forming an antireflection film obtained in the above (1) was used. In the same manner as in Example 1, (2) Preparation of an inorganic powder resin composition for forming a conductive film, (3) Preparation of a resist composition, (4) Preparation of a transfer film for forming an electrode, (5) Formation of an electrode Operation and evaluation of transfer film transfer, (6) resist film exposure process, (7) development process / etching process, and (8) baking process were performed.

[Comparative Example 3]
(1) Preparation of Resin Composition 4 Containing Inorganic Powder for Antireflection Film Formation As inorganic powder, 100 parts of nickel powder (average particle size 0.2 μm) and Bi ₂ O ₃ —O—B ₂ O ₃ —SiO ₂ -Based glass frit (softening point 560 ° C., average particle size 2.0 μm), as binder resin, Blemmer PME-100 / n-butyl methacrylate / methacrylic acid / 2-hydroxypropyl methacrylate = 20/40/20 / 20 (mass%) copolymer (weight average molecular weight: 150,000) 90 parts, 30 parts of trimethylolpropane triacrylate as a plasticizer, 1 part of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent, dispersant Anti-reflective by kneading 3 parts oleic acid as a solvent and 20 parts propylene glycol monomethyl ether as a solvent using a disperser An inorganic powder-containing resin composition 4 for forming a stop film was prepared.

  Hereinafter, instead of using the inorganic powder-containing resin composition 1 for forming an antireflective film in Example 1, the inorganic powder-containing resin composition 4 for forming an antireflective film obtained in the above (1) was used. In the same manner as in Example 1, (2) Preparation of an inorganic powder resin composition for forming a conductive film, (3) Preparation of a resist composition, (4) Preparation of a transfer film for forming an electrode, (5) Formation of an electrode Operation and evaluation of transfer film transfer, (6) resist film exposure process, (7) development process / etching process, and (8) baking process were performed.

  The evaluation results of Example 1 and Comparative Examples 1 to 3 are shown in Table 1.

  As shown in Table 1, when the inorganic powder-containing resin composition of the present invention is used, the film transferability to the substrate is good, and there is no resin melt at the time of firing, so the pattern has excellent linearity. Can be obtained.

  On the other hand, when an inorganic powder-containing resin composition prepared using a resin not containing the monomer (1) is used, for example, a resin having a high glass transition point as in Comparative Example 1 Although a melt hardly occurs and a pattern with excellent linearity can be obtained, there is a problem that transferability to a substrate is inferior because the film is stiff. Moreover, although the thing with the low glass transition point of resin like the comparative example 2 was excellent in transferability, the melt of the resin at the time of baking was large, and resulted in inferior pattern linearity. Further, the line thickening at the time of baking can be avoided by increasing the molecular weight (Mw) of the resin used as in Comparative Example 3, but the solubility in the developer is poor, many residues are found after development, and the resolution is also high. It was a bad result.

(A) is a schematic sectional drawing which shows the transfer film of this invention, (b) is sectional drawing which shows the layer structure of the said transfer film.

Explanation of symbols

F1 Support film F2 Inorganic powder-containing resin layer F3 Cover film

Claims (8)

An inorganic powder-containing resin composition comprising (a) inorganic powder, (b) an acrylic resin containing a monomer represented by the following formula (1) as a polymerization component, and (c) a solvent. object.

[In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms, and B represents a group that blocks an isocyanate group. Indicates. ]   The inorganic powder-containing resin composition according to claim 1, further comprising (d) a radiation-sensitive component. The monomer represented by the formula (1) is 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate. The inorganic powder-containing resin composition according to claim 1, wherein the resin composition is at least one selected from the group consisting of:   A transfer film comprising an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 1 on a support film.   A transfer film comprising a laminated film of a resist film and an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 1 on a support film. Transferring the inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 1 formed on the support film onto the substrate;
Forming a resist film on the inorganic powder-containing resin layer;
A step of exposing the resist film to form a latent image of a resist pattern;
Developing the resist film to reveal a resist pattern;
Etching the inorganic powder-containing resin layer to form a pattern layer corresponding to the resist pattern, and firing the pattern layer, so that a dielectric layer, a partition, an electrode, a resistor, a phosphor, A method for producing a flat panel display member, comprising a step of forming a panel member selected from a color filter and a black matrix. Transferring the laminated film of the resist film formed on the support film and the inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 1 onto a substrate;
A step of exposing the resist film constituting the laminated film to form a latent image of the resist pattern, a step of developing the resist film to reveal the resist pattern,
Etching the inorganic powder-containing resin layer to form a pattern layer corresponding to the resist pattern, and firing the pattern layer, so that a dielectric layer, a partition, an electrode, a resistor, a phosphor, a color The manufacturing method of the flat panel display member characterized by including the process of forming the panel member chosen from a filter and a black matrix. Transferring the inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition according to claim 2 formed on the support film onto the 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 layer, and firing the pattern layer, so that the dielectric layer, partition walls, electrodes, resistors, phosphors, color filters, and black matrix The manufacturing method of the flat panel display member characterized by including the process of forming the selected panel member.

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