JP2008239778A - Inorganic powder-containing resin composition, transfer film, and method for manufacturing flat panel display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic powder-containing resin composition capable of forming a black matrix with good sensitivity, a transfer film having an inorganic powder-containing resin layer comprising the inorganic powder-containing resin composition, and a method for manufacturing a flat panel display capable of forming a black matrix which is flat and smooth, has no warpage, and has good patterning performance. <P>SOLUTION: The transfer film having the inorganic powder-containing resin layer comprising the inorganic powder-containing resin composition of the present invention obtained by using a specific photoinitiator can provide the flat panel display capable of forming a black matrix which is flat and smooth, has no warpage, and has excellent patterning performance. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In recent years, flat panel displays (hereinafter also referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”) as flat fluorescent displays. ) Is attracting attention. A PDP forms a transparent electrode, encloses an inert gas such as argon or neon between two adjacent glass plates, causes plasma discharge to light up the gas, thereby causing phosphors to emit light and display information. It is a display. On the other hand, the FED is a display that displays information by causing a phosphor to emit light by emitting electrons from a cathode into a vacuum by applying an electric field and irradiating the electrons on the anode.

  FIG. 1 is an example of a schematic diagram showing a cross-sectional shape of an AC type PDP. In the figure, 1 and 2 are glass substrates facing each other, 3 is a partition, and cells are partitioned by the glass substrate 1, the glass substrate 2 and the partition 3. 4 is a transparent electrode fixed to 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 to 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, 6 is an address electrode, 9 is the surface of the glass substrate 2 so as to be covered The dielectric layers 10 formed in the above are protective films made of, for example, magnesium oxide.

  In the color FPD, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

As a manufacturing method of such a dielectric, barrier rib, electrode, phosphor, color filter and black matrix of such FPD, for example,
(1) A screen printing method in which a non-photosensitive inorganic powder-containing paste is screen-printed on a substrate to form a pattern, and this is fired (for example, see Patent Document 1),
(2) A photosensitive inorganic powder-containing resin layer is formed on a substrate, and the film is irradiated with ultraviolet rays through a photomask and developed to leave a pattern on the substrate. Lithography method (see, for example, Patent Documents 2 and 3)
However, since the thick film pattern forming process is simple and the pattern shape is excellent, the photolithography method (2) is particularly preferably used.

  In particular, in the above black matrix, for the purpose of increasing the contrast of the image, the performance of low reflectance (preferably the reflectance at a wavelength of 550 nm or all rays is 2% so that the light is reflected off the screen and does not disturb the visibility. The following) and the performance with low transmittance (preferably the transmittance at a wavelength of 550 nm or all light rays is 10% or less).

However, when the transmittance is lowered as described above, when the photolithography method is used, there is a problem that the sensitivity in the film thickness direction is lowered during exposure and the patterning shape is deteriorated. When the sensitivity in the film thickness direction decreases, when the photosensitive resin is a negative type, only the vicinity of the surface is cured, so that undercut occurs during development. For this reason, problems such as deterioration of the pattern shape after development and peeling of the film from the substrate occur. Further, the pattern is warped in the subsequent baking process, and a high-definition black matrix may not be obtained.

  On the other hand, in recent years, there has been an increasing demand for further reducing manufacturing costs while maintaining high performance. Among the manufacturing processes, the baking process, in which each component is baked at a high temperature to eliminate organic components, is a major obstacle to reducing tact time. It was.

  In order to reduce the tact time, in the member forming method of the flat panel display by the photolithography method, a method of forming a laminated pattern composed of a plurality of members and performing baking at once can be considered.

However, in the implementation of this method, there is a problem that the warpage of the pattern does not occur when fired in a single layer, but this warpage occurs when fired by laminating with other member forming materials. .
Japanese Patent Laid-Open No. 6-321619 JP-A-9-102273 Japanese Patent Laid-Open No. 11-162339

  Inorganic powder-containing resin composition capable of forming a black matrix with good sensitivity, a transfer film having an inorganic powder-containing resin layer made of the inorganic powder-containing resin composition, and smooth and warp-free patterning performance It is an object of the present invention to provide a method for manufacturing a flat panel display capable of forming a good black matrix.

The inorganic powder-containing resin composition of the present invention comprises (A) an inorganic powder as a colored pigment (A-1) and a glass powder (A-2),
(B) binder resin,
It is characterized by containing a compound represented by the following formula (1) as (C) a photopolymerizable monomer and (D) a photopolymerization initiator.

〔上記式（１）中、Ｒ¹、Ｒ²及びＲ³は、それぞれ、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲ
Ｒ'、またはＣＮを表し、Ｒ及びＲ'はアルキル基、アリール基、アラルキル基、または複素環基を表し、これらはハロゲン原子もしくは複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ'は一緒に
なって環を形成していてもよい。Ｙは酸素原子、硫黄原子またはセレン原子を表し、Ａは複素環基を表し、ｍは０〜４の整数を表し、ｐは０〜５の整数を表し、ｑは０または１を
表す。〕
前記ガラス粉体（Ａ−２）として、軟化点が４００〜５００℃の無鉛ガラス粉体を含有することが好ましい。

[In the above formula (1), R ¹ , R ² and R ³ are R, OR, COR, SR, CONR, respectively.
R ′ or CN represents R and R ′ each represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom or a heterocyclic group, and among these, an alkyl group And the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ′ may be combined to form a ring. Y represents an oxygen atom, a sulfur atom or a selenium atom, A represents a heterocyclic group, m represents an integer of 0 to 4, p represents an integer of 0 to 5, and q represents 0 or 1. ]
The glass powder (A-2) preferably contains lead-free glass powder having a softening point of 400 to 500 ° C.

The binder resin (B) preferably has a polymerizable unsaturated double bond in the side chain.
The binder resin (B) is preferably a polymer obtained by reacting a hydroxyl group-containing polymer with an isocyanate compound having a (meth) acryloyl group.

  The photopolymerization initiator (D) is preferably a compound represented by the formula (2).

本発明の無機粉体含有樹脂組成物は、有機シラン化合物（Ｅ）をさらに含有することが好ましい。

The inorganic powder-containing resin composition of the present invention preferably further contains an organosilane compound (E).

The transfer film of the present invention has an inorganic powder-containing resin layer obtained from the inorganic powder-containing resin composition on a support film.
The method for producing a flat panel display of the present invention includes a step of transferring an inorganic powder-containing resin layer of the transfer film onto a substrate,
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
A black matrix is formed by a method including a step of baking the pattern.

The method for producing a flat panel display of the present invention includes a step of transferring an inorganic powder-containing resin layer of the transfer film onto a substrate,
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
Forming a pattern on the pattern layer to obtain a laminated pattern layer;
A plurality of members including a black matrix are collectively formed by a method including a step of firing the laminated pattern.

The method for producing a flat panel display of the present invention includes a step of transferring an inorganic powder-containing resin layer of the transfer film onto a substrate,
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
A step of post-baking the obtained pattern layer;
Forming a pattern on the pattern layer to obtain a laminated pattern layer;
A plurality of members including a black matrix are collectively formed by a method including a step of firing the laminated pattern.

  The transfer film having an inorganic powder-containing resin layer made of the inorganic powder-containing resin composition of the present invention obtained by using a specific photopolymerization initiator is a black matrix having excellent patterning performance that is smooth and without warping The flat panel display which can form can be provided.

Hereinafter, the inorganic powder-containing resin composition, transfer film and flat panel display production method of the present invention will be described in detail.
[Inorganic powder-containing resin composition]
The inorganic powder-containing resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”)
(A) As an inorganic powder, a colored pigment (A-1) and a glass powder (A-2),
(B) binder resin,
(C) A photopolymerizable monomer and (D) a photopolymerization initiator are contained. The composition of the present invention may further contain an organosilane compound (E). Hereinafter, each component of the composition of this invention is demonstrated concretely.

<Inorganic powder (A)>
As the inorganic powder (A) used in the composition of the present invention, a colored pigment (A-1) and a glass powder (A-2) are used.

Examples of the colored pigment (A-1) include Mn, Fe, Cr, Ni, Co, Cu, Ti and oxides and composite oxides thereof, specifically, tricobalt tetroxide (Co ₃ O ₄ ) or cobalt Containing complex oxides are preferably used. These colored pigments may be used alone or in combination of two or more.

When using tricobalt tetroxide or a cobalt-containing composite oxide as a colored pigment, the specific surface area is 7.5 m ² / g or more and 20 m ² / g or less, preferably 10 m ² / g or more and 20 m ² / g or less. is there. When the specific surface area is less than 7.5 m ² / g, a black matrix having a low light transmittance cannot be obtained. On the other hand, if it exceeds 20 m ² / g, a black matrix having a good black color may not be obtained, for example, a black matrix having a reddish color may be formed.

Here, the “specific surface area” means an average value of specific surface areas determined by the BET method of tricobalt tetroxide contained in the inorganic powder-containing resin composition.
Moreover, the average particle diameter of tricobalt tetroxide is 0.05-5.0 micrometers normally, Preferably it is 0.1-0.5 micrometer.

  As the glass powder (A-2), glass powder having a softening point of 400 to 500 ° C. is preferably used. When the softening point of the glass powder is less than 400 ° C., the glass powder melts at the stage where the organic substance such as the binder resin is not completely decomposed and removed in the firing step of the inorganic powder-containing resin layer. Therefore, a part of the organic substance may remain in the black matrix to be formed, and as a result of the outgas diffusing in the obtained flat panel display, the lifetime of the phosphor may be reduced. On the other hand, when the softening point of the glass powder exceeds 500 ° C., the inorganic powder-containing resin layer needs to be baked at a temperature higher than 500 ° C. May occur.

As a suitable specific example of the glass powder,
(1) Lead oxide, boron oxide, silicon oxide and calcium oxide system (PbO—B ₂ O ₃ —SiO ₂ —CaO system),
(2) Zinc oxide, boron oxide and silicon oxide type (ZnO—B ₂ O ₃ —SiO ₂ type),
(3) Lead oxide, boron oxide, silicon oxide and aluminum oxide system (PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system),
(4) Lead oxide, zinc oxide, boron oxide and silicon oxide system (PbO—ZnO—B ₂ O ₃ —SiO ₂ system),
(5) Lead oxide, zinc oxide, boron oxide, silicon oxide and titanium oxide system (PbO—ZnO—B ₂ O ₃ —SiO ₂ —TiO ₂ system),
(6) Bismuth oxide, boron oxide and silicon oxide systems (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system)
,
(7) Zinc oxide, phosphorus oxide and silicon oxide system (ZnO—P ₂ O ₅ —SiO ₂ system),
(8) Zinc oxide, boron oxide and potassium oxide systems (ZnO—B ₂ O ₃ —K ₂ O system),
(9) Phosphorus oxide, boron oxide and aluminum oxide systems (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system),
(10) Zinc oxide, phosphorus oxide and titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ ) mixture (11) Bismuth oxide, zinc oxide, boron oxide, barium oxide and silicon oxide (Bi ₂ O ₃ —ZnO) -B ₂ O ₃ -BaO-SiO ₂ type). Among these, lead-free glass, that is, glass powders such as the above (6) to (11) are preferably used from the viewpoint of temporal stability of the composition obtained after kneading.

The average particle size of the glass powder is preferably 0.1 to 3.0 μm.
The content ratio of the colored pigment (A-1) and the glass powder (A-2) in the inorganic powder (A) is preferably 5 for the colored pigment (A-1) with respect to the total amount of the inorganic powder. -30 mass%, and glass powder (A-2) becomes like this. Preferably it is 70-95 mass%. When the ratio of the colored pigment (A-1) is the above ratio, the colored pigment is embedded in the film together with the glass powder without being deposited on the surface even after firing, and has excellent surface smoothness and reflectivity. A black matrix having a low light-shielding property is obtained. Moreover, when the ratio of the glass powder (A-2) is the above ratio, a black matrix having excellent surface smoothness, low reflectance, and excellent light shielding properties can be obtained. An effect of improving the film strength is obtained.

  In particular, in the inorganic powder-containing resin composition of the present invention, since the glass powder content is high, the surface smoothness of the black matrix after firing is improved, and the amount of light that diffuses and reflects upon the screen decreases, It is thought that it has succeeded in obtaining a low reflectance.

  Moreover, the inorganic powder-containing resin composition of the present invention may contain inorganic powder other than (A-1) and (A-2). Specific examples include inorganic oxides such as aluminum oxide, titanium oxide, zirconium oxide, silicon oxide, and cerium oxide. The content of the other inorganic powder is preferably 30% by mass or less of the total amount of the inorganic powder.

<Binder resin (B)>
As the binder resin (B) constituting the composition of the present invention, the binder resin (B) constituting the composition of the present invention is a polymer having a polymerizable unsaturated double bond in the side chain, It is an alkali-soluble resin. Here, “alkali-soluble” refers to the property of being dissolved in an alkaline developer and having solubility to such an extent that the intended development processing is performed.

  The binder resin (B) is preferably contained in an amount of 4 to 67 parts, preferably 10 to 50 parts with respect to 100 parts of the inorganic powder (A). The alkali-soluble resin is preferably contained in an amount of 10 to 100 parts with respect to 100 parts of the binder resin (B).

  As a specific example of the alkali-soluble resin, a polymer obtained by reacting a polymer having a hydroxyl group with an isocyanate compound having a (meth) acryloyl group is preferably used. Specifically, a copolymer obtained by polymerizing a monomer having at least one carboxyl group in the molecule and an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule (hereinafter referred to as “a copolymer”). , “Copolymer b”) and 2- (meth) acryloyloxyalkyl isocyanate are reacted with each other (hereinafter also referred to as “specific copolymer”).

  As a particularly preferred specific example of the specific copolymer, a base polymer of methacrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate is reacted with 2-methacryloyloxyethyl ethyl isocyanate or 2-acryloyloxyethyl isocyanate. What was obtained is mentioned.

  Specific examples of the compound having an isocyanate group and an unsaturated double bond used for the synthesis of the specific copolymer include 2-methacryloyloxyethyl ethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl). ) Ethyl isocyanate. It is 10 mol-60 mol part with respect to 100 mol part of monomer which has a hydroxyl group used as a copolymerization component of the said copolymer b, Preferably it is 20-55 mol part.

  The molecular weight of the binder resin (B) used in the present invention is 3,000 to 300,000 in terms of polystyrene-reduced weight average molecular weight by GPC (hereinafter also simply referred to as “weight average molecular weight” or “Mw”). Preferably it is 10,000-100,000. Further, the polydispersity (Mw / Mn) (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin is 1.0 to 5.0, preferably 1.0 to 3.0.

<Photopolymerizable monomer (C)>
The composition of the present invention is a photosensitive composition containing a photopolymerizable monomer (C) and a photopolymerization initiator (D). The photopolymerizable monomer has a property of being polymerized by exposure to render the exposed portion alkali-insoluble or alkali-insoluble, and a polyfunctional (meth) acrylate is preferable.

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 polybutadiene, hydroxyterminated polyisoprene and hydroxypolycaprolactone at both ends; glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol And poly (meth) acrylates of trihydric or higher polyhydric alcohols such as dipentaerythritol; polyalkylene glycols of trihydric or higher polyhydric alcohols Poly (meth) acrylates of adducts; poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; polyester (meth) acrylate, epoxy (meth) acrylate, urethane Examples include oligo (meth) acrylates such as (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiraline resin (meth) acrylate. These may be used alone or in combination of two or more. Among these, di (meth) acrylates of alkylene glycol, trimethylolpropane triacrylate and its polyalkylene glycol adduct and pentaerythritol triacrylate and its polyalkylene glycol adduct are particularly preferably used. The molecular weight of the polyfunctional (meth) acrylate is preferably 100 to 2,000.

  The photopolymerizable monomer (C) is generally used in an amount in the range of 0.8 to 100.5 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the inorganic powder (A). The photopolymerizable monomer (C) is used in an amount in the range of 20 to 150 parts by mass, preferably 50 to 100 parts by mass with respect to 100 parts by mass of the binder resin (B). If the amount of the binder resin is too small, the inorganic powder may not be securely bound and retained. In some cases, the sintered body does not have sufficient strength and film thickness.

<Photopolymerization initiator (D)>
As the photopolymerization initiator (D) used in the present invention, a compound represented by the following formula (1) is used.

〔上記式（１）中、Ｒ¹、Ｒ²及びＲ³は、それぞれ、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲ
Ｒ'、またはＣＮを表し、Ｒ及びＲ'はアルキル基、アリール基、アラルキル基、または複素環基を表し、これらはハロゲン原子もしくは複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ'は一緒に
なって環を形成していてもよい。Ｙは酸素原子、硫黄原子またはセレン原子を表し、Ａは複素環基を表し、ｍは０〜４の整数を表し、ｐは０〜５の整数を表し、ｑは０または１を表す。〕
このような化合物としては、１−[９−エチル−６−（２−メチルベンゾイル）−９.Ｈ.−カルバゾール−３−イル]−エタン−１−オンオキシム−Ｏ−アセタート、下記式（２）で表される化合物（エタノン−１−［９−エチル−６−［２−メチル−４−（２，２−ジメチル−１，３−ジオキソラニル）メトキシベンゾイル］−９．Ｈ．−カルバゾール−３−イル］−１−（Ｏ−アセチルオキシム））、および（エタノン−１−［９−エチル−６−［２−メチル−４−テトラヒドロフラニルメトキシベンゾイル］−９．Ｈ．−カルバゾール−３−イル］−１−（Ｏ−アセチルオキシム））などのカルボニル化合物などが挙げられる。

[In the above formula (1), R ¹ , R ² and R ³ are R, OR, COR, SR, CONR, respectively.
R ′ or CN represents R and R ′ each represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom or a heterocyclic group, and among these, an alkyl group And the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ′ may be combined to form a ring. Y represents an oxygen atom, a sulfur atom or a selenium atom, A represents a heterocyclic group, m represents an integer of 0 to 4, p represents an integer of 0 to 5, and q represents 0 or 1. ]
Such compounds include 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, the following formula (2) (Etanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9.H.-carbazole-3- Yl] -1- (O-acetyloxime)), and (ethanone-1- [9-ethyl-6- [2-methyl-4-tetrahydrofuranylmethoxybenzoyl] -9.H.-carbazol-3-yl] And carbonyl compounds such as -1- (O-acetyloxime)).

光重合開始剤（Ｄ）として上記式（１）で表される化合物を用いることにより、顔料が分散された透過率の低い無機粉体含有樹脂組成物であっても、高い硬化深度が得られ、アンダーカットを防ぐことができ、高いパターニング性能を有する無機粉体含有樹脂組成物を得ることができる。また、この無機粉体含有樹脂組成物から得られたパターンと他のパターンとを積層して一括焼成してもパターンの反りが発生しない。

By using the compound represented by the above formula (1) as the photopolymerization initiator (D), a high curing depth can be obtained even in the case of an inorganic powder-containing resin composition having a low transmittance and in which a pigment is dispersed. Undercut can be prevented, and an inorganic powder-containing resin composition having high patterning performance can be obtained. Further, even when a pattern obtained from this inorganic powder-containing resin composition and another pattern are laminated and fired at once, the pattern does not warp.

  Moreover, the said photoinitiator (D) may be used individually by 1 type, and may use together another polymerization initiator. Examples of other polymerization initiators include benzyl, benzoin, benzophenone, camphorquinone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 4,4′-bis (dimethylamino) benzophenone, 4, 4′-bis (diethylamino) benzophenone, 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-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; 2,4,6-trimethylbenzoyl- Diphenylphosphine oxide; azoisobutyronitrile and 4-azidobe Azo or azide compounds such as zaldehyde; organosulfur compounds such as 2-mercaptobenzothiazole and mercaptan disulfide; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and parameterone Organic peroxides such as hydroperoxide; 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -1,3,5-triazine and 2- [2- (2-furanyl) ethylenyl] -4, Trihalomethanes such as 6-bis (trichloromethyl) -1,3,5-triazine; 2,2′-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl1,2′-biimidazole Imidazole dimers such as 2-isopropylthio Sandton, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-based compounds such as 2,4-dichloro thioxanthone, and the like. Among these, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and the like are particularly preferably used.

  By including these photopolymerization initiators, by using them together, a sufficient sensitivity can be achieved even if the amount of photopolymerization initiator used is small, and a flat panel display member with good patterning performance and no warpage is provided. can do. Moreover, since the usage-amount of a photoinitiator may be small, favorable combustibility is expressed in a baking process.

  The photopolymerization initiator (D) is usually 0.1 to 50.0 parts by mass, preferably 1.0 to 30.0 parts by mass with respect to 100 parts by mass of the photopolymerizable monomer (C). Used in quantity. Moreover, another photoinitiator is used in the quantity of 20-100 mass parts with respect to 100 mass parts of photoinitiators (D), Preferably it is the range of 50-80 mass parts.

<Organic Silane Compound (E)>
The composition of the present invention may contain an organosilane compound for the purpose of improving the dispersibility of the inorganic powder (A), particularly glass powder, and improving the plasticization of the transfer film to be formed. Examples of such organic silane compounds include saturated alkylalkoxysilanes represented by the following general formula (3) and silane coupling agents represented by the general formula (4).

（式（３）中、ｐは３〜２０、好ましくは４〜１６の整数、ｍは１〜３の整数、ｎは１〜３の整数、ａは１〜３の整数である。）

(In Formula (3), p is an integer of 3-20, preferably 4-16, m is an integer of 1-3, n is an integer of 1-3, a is an integer of 1-3.)

（式（４）中、Ｒはメチレン基または炭素数２〜１００のアルキレン基を表し、Ｙはビニル基、エポキシ基、アクリロキシ基、メタクリロキシ基、メルカプト基またはアミノ基を表し、Ｘは加水分解性基を表し、ｒは０から３の整数である。）
上記一般式（３）において、ｐの値が３未満の飽和アルキルアルコキシシランを用いる場合は、得られる無機粉体含有樹脂層において十分な可撓性が発現されない場合がある。一方、上記ｐの値が２０を超える飽和アルキルアルコキシシランは分解温度が高いため、無機粉体含有樹脂層の焼成工程において、有機物質（前記シラン誘導体）が完全に分解除去されない段階でガラス粉体が溶融してしまい、形成される誘電体層中に有機物質の一部が残留することにより、誘電体層の光透過率が低下する場合がある。

(In formula (4), R represents a methylene group or an alkylene group having 2 to 100 carbon atoms, Y represents a vinyl group, an epoxy group, an acryloxy group, a methacryloxy group, a mercapto group or an amino group, and X represents a hydrolyzable group. And r is an integer from 0 to 3.)
In the general formula (3), when a saturated alkylalkoxysilane having a p value of less than 3 is used, sufficient flexibility may not be exhibited in the resulting inorganic powder-containing resin layer. On the other hand, since the saturated alkylalkoxysilane having a value of p exceeding 20 has a high decomposition temperature, the glass powder is not completely decomposed and removed in the firing process of the inorganic powder-containing resin layer. As a result of melting, a part of the organic substance remains in the formed dielectric layer, which may reduce the light transmittance of the dielectric layer.

Specific examples of silanes used as the saturated alkylalkoxysilane represented by the general formula (3) are shown below.
Examples of the saturated alkyldimethylmethoxysilane (a = 1, m = 1, n = 1) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, and n-hexadecyldimethyl. Examples include methoxysilane and n-icosanedimethylmethoxysilane.

  Examples of saturated alkyldiethylmethoxysilane (a = 1, m = 1, n = 2) include n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, and n-hexadecyldiethyl. Examples include methoxysilane and n-icosanediethylmethoxysilane.

Saturated alkyldipropylmethoxysilanes (a = 1, m = 1, n = 3) include, for example, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane and Examples include n-icosanedipropylmethoxysilane.

  Examples of saturated alkyldimethylethoxysilanes (a = 1, m = 2, n = 1) include n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, and n-hexadecyldimethyl. Examples include ethoxysilane and n-icosanedimethylethoxysilane.

  Examples of saturated alkyldiethylethoxysilanes (a = 1, m = 2, n = 2) include n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, and n-hexadecyldiethyl. Examples include ethoxysilane and n-icosanediethylethoxysilane.

  Saturated alkyldipropylethoxysilanes (a = 1, m = 2, n = 3) include, for example, n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, and Examples thereof include n-icosanedipropylethoxysilane.

  Examples of saturated alkyldimethylpropoxysilanes (a = 1, m = 3, n = 1) include n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, and n-hexadecyldimethyl. Examples include propoxysilane and n-icosanedimethylpropoxysilane.

  Examples of saturated alkyldiethylpropoxysilanes (a = 1, m = 3, n = 2) include n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, and n-hexadecyldiethyl. Examples include propoxysilane and n-icosanediethylpropoxysilane.

  Saturated alkyldipropylpropoxysilanes (a = 1, m = 3, n = 3) include, for example, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, and Examples include n-icosanedipropylpropoxysilane.

  Examples of the saturated alkylmethyldimethoxysilane (a = 2, m = 1, n = 1) include n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, and n-hexadecylmethyl. Examples include dimethoxysilane and n-icosanemethyldimethoxysilane.

  Examples of the saturated alkylethyldimethoxysilane (a = 2, m = 1, n = 2) include n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, and n-hexadecylethyl. Examples include dimethoxysilane and n-icosaneethyldimethoxysilane.

  Examples of the saturated alkylpropyldimethoxysilane (a = 2, m = 1, n = 3) include n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane and n-icosane. Examples thereof include propyldimethoxysilane.

Examples of the saturated alkylmethyldiethoxysilane (a = 2, m = 2, n = 1) include, for example, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n -Hexadecylmethyldiethoxysilane, n-icosanemethyldiethoxysilane, etc. are mentioned.

  Examples of the saturated alkylethyldiethoxysilane (a = 2, m = 2, n = 2) include n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n -Hexadecylethyldiethoxysilane, n-icosaneethyldiethoxysilane, etc. are mentioned.

  Saturated alkylpropyldiethoxysilanes (a = 2, m = 2, n = 3) include, for example, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, and Examples thereof include n-icosanepropyldiethoxysilane.

  Examples of the saturated alkylmethyldipropoxysilane (a = 2, m = 3, n = 1) include, for example, n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n -Hexadecylmethyl dipropoxysilane, n-icosanemethyldipropoxysilane, etc. are mentioned.

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

  Examples of saturated alkylpropyl dipropoxysilanes (a = 2, m = 3, n = 3) include, for example, n-butylpropyl dipropoxysilane, n-decylpropyl dipropoxysilane, n-hexadecylpropyl dipropoxysilane, and n-Icosanpropyl dipropoxysilane and the like can be mentioned.

  Saturated alkyltrimethoxysilanes (a = 3, m = 1) include, for example, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane and n -Icosan trimethoxysilane and the like.

  Saturated alkyltriethoxysilanes (a = 3, m = 2) include, for example, n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane and n -Icosan triethoxysilane and the like.

  Examples of saturated alkyltripropoxysilanes (a = 3, m = 3) include n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane and n -Icosan tripropoxysilane and the like.

Examples of the silane coupling agent represented by the general formula (4) include vinyl group-containing silane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane;
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3- (2-aminoethyl) aminopropylmethyldimethoxy Amino group-containing silane compounds such as silane;
(Meth) such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane An acryloxy group-containing silane compound;
Epoxy group-containing silane compounds such as 3-glycidoxypropyltrimeethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
Examples include mercapto group-containing silane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

  The said organosilane compound may be used individually by 1 type, or may be used in combination of 2 or more type. Among the above silanes, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-butyltriethoxysilane N-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexa Particularly preferred are decyltripropoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane and 3-methacryloxypropyltrimethoxysilane.

  The organic silane compound is usually used in an amount of 10 parts by mass or less, preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the inorganic powder. When the amount of the organosilane compound is excessive, the viscosity increases with time when the inorganic powder-containing resin composition is stored, or the reaction between the organosilane compounds occurs, and after the panel member to be formed is baked It may cause a decrease in light transmittance.

<Other ingredients>
The composition of the present invention may contain a plasticizer as an auxiliary agent for the binder resin (B) in order to give the transfer film good flexibility. Since the inorganic powder-containing resin layer formed from the composition containing the plasticizer has sufficient flexibility, the transfer film having the resin layer is fine on the surface of the resin layer even when it is bent. No cracks (cracks) are generated, and it can be easily wound up into a roll.

  Examples of the plasticizer include polypropylene glycol, copolymerizable monomers such as the (meth) acrylate compounds described above and solvents described later, dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2 -Ethylhexyl azelate, dibutyl sebacate, dibutyl diglycol adipate, propylene glycol monolaurate and propylene glycol monooleate. Among these, those having a boiling point of 150 ° C. or more are preferable. Such plasticizers may be used alone or in combination of two or more.

  Further, the composition of the present invention includes, as optional components, a dispersant, a development accelerator, an adhesion assistant, an antihalation agent, a leveling agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a sensitizer. And various additives such as a chain transfer agent. As the dispersant, organic fatty acids such as stearic acid and oleic acid are preferably used.

<Solvent>
The composition of the present invention usually contains a solvent. As such a solvent, the affinity with the inorganic powder and the solubility of the binder resin are good, an appropriate viscosity can be imparted to the inorganic powder-containing resin composition, and it can be easily performed by a drying treatment. Preferably, it can be removed by evaporation.

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

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

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

  The said solvent is 5-50 mass parts with respect to 100 mass parts of inorganic powder (A) from a viewpoint of maintaining the viscosity of a composition in a suitable range, Preferably it is used in 10-40 mass parts. Moreover, the ratio of the specific solvent with respect to all the solvents is 50 mass% or more, Preferably it is 70 mass% or more.

  The inorganic powder-containing resin composition of the present invention includes the inorganic powder (A), the binder resin (B), the photopolymerizable monomer (C), the photopolymerization initiator (D), and others used as necessary. These components and the solvent can be prepared by kneading using a kneader and a disperser such as a roll kneader, a mixer, a homomixer, and a sand mill.

In addition, it is preferable that the viscosity of the composition of this invention is 0.1-10 Pa.s.
[Transfer film]
The transfer film of the present invention has an inorganic powder-containing resin layer obtained from the composition of the present invention on a support film, and may have a cover film on the surface of the resin layer as necessary. .

Hereinafter, each component of the transfer film will be specifically described.
<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 has flexibility, the inorganic powder-containing resin composition can be applied to the surface of the support film by a roll coater or a blade coater, and the resulting transfer film is wound in a roll shape. Can be stored or supplied.

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

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

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

  The method of applying the composition of the present invention on a support film is a method that can form a coating film with high film thickness uniformity and high film thickness (for example, 10 μm or more) with high efficiency. Specific examples include a coating method using a roll coater, a coating method using a blade coater, a coating method using a curtain coater, and a coating method using a wire coater. The film thickness of the inorganic powder-containing resin layer is usually 1 to 20 μm.

  As drying conditions of a coating film, it is about 0.5 to 30 minutes at 50-150 degreeC, for example, The residual ratio (content rate in an inorganic powder containing resin layer) of the solvent after drying is 2 mass normally. %.

<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 flexible resin film, whereby the obtained transfer film can be stored or supplied in a rolled state.

Examples of the resin constituting the cover film include a polyethylene terephthalate film, a polyethylene film, and a polyvinyl alcohol film.
[Manufacturing method of flat panel display]
Preferred embodiments of the method for producing the flat panel display of the present invention are as follows.

  [1] A step (1) of transferring the inorganic powder-containing resin layer of the transfer film onto the substrate, and a step (2) of exposing the inorganic powder-containing resin layer to form a latent image of the pattern. A method for producing a flat panel display, wherein a black matrix is formed by a method comprising a step (3) of developing the inorganic powder-containing resin layer to form a pattern and a step (6) of baking the pattern (6). FPD production method (I)).

  [2] Step (1) of transferring the inorganic powder-containing resin layer of the transfer film onto the substrate, and Step (2) of exposing the inorganic powder-containing resin layer to form a latent image of the pattern. The step of developing the inorganic powder-containing resin layer to form a pattern (3), the step of forming a pattern on the pattern layer to obtain a laminated pattern layer (5), and the laminated pattern A flat panel display manufacturing method (FPD manufacturing method (II)) in which a plurality of members including a black matrix are collectively formed by a method including a firing process (6).

[3] A step (1) of transferring the inorganic powder-containing resin layer of the transfer film onto the substrate, and a step (2) of exposing the inorganic powder-containing resin layer to form a latent image of the pattern. The inorganic powder-containing resin layer is developed to form a pattern (3), the resulting pattern layer is post-baked (4), and a pattern is further formed on the pattern layer. A flat panel display manufacturing method (FPD manufacturing method) in which a plurality of members including a black matrix are collectively formed by a method including a step (5) of obtaining a laminated pattern layer and a step (6) of firing the laminated pattern (III)).

Hereinafter, each process of the said manufacturing method (I)-(III) is demonstrated.
(1) Transfer process of inorganic powder-containing resin layer After peeling the cover film of the transfer film, the transfer film is overlaid on the surface of the glass substrate so that the surface of the inorganic powder-containing resin layer is in contact with this surface. The transfer film is thermocompression bonded with a heating roller or the like. As a result, the inorganic powder-containing resin layer is transferred and adhered to the surface of the glass substrate. 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 0.90 to 0.50 MPa, and the moving speed of the heating roller is 0.1 to 10.0 m / min. Is preferred. Moreover, the glass substrate may be preheated and can be 40-100 degreeC as preheat temperature, for example.

(2) Exposure step of inorganic powder-containing resin layer In this step, the surface of the inorganic powder-containing resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a resist. A latent image of the pattern is formed.

  The ultraviolet irradiation apparatus used in the exposure is not particularly limited, and an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used in manufacturing a semiconductor and a liquid crystal display device, and the like. Can be mentioned.

In addition, it is preferable to perform an exposure process in the state which does not peel the support film coat | covered on the inorganic powder containing resin layer, and to peel after exposure.
(3) Development step of inorganic powder-containing resin layer In this step, the exposed inorganic powder-containing resin layer is developed to reveal a resist pattern (latent image).

  The development processing conditions include the type / composition / concentration of the developer, the development time, the development temperature, the development method (eg, dipping method, rocking method, shower, etc.) depending on the type of components of the inorganic powder-containing resin layer. Method, spray method and paddle method), developing device, and the like can be appropriately selected.

By this development process, an inorganic powder-containing resin pattern (pattern corresponding to an exposure mask) is formed.
(4) Post-baking step of inorganic powder-containing resin pattern layer In this step, the substrate on which the inorganic powder resin pattern was formed was post-baked for 15 minutes in an oven at 200 ° C.

(5) Laminating step of inorganic powder-containing resin pattern In this step, a paste is further laminated by screen printing on the upper layer of the inorganic powder-containing pattern formed on the glass substrate, followed by patterning. At this time, once the above-mentioned inorganic powder-containing resin pattern is post-baked in an oven at 190 ° C. to 220 ° C., the inorganic powder-containing resin pattern can be laminated without being destroyed by the solvent contained in the paste to be laminated. it can. As a result, two layers can be fired at the same time, so that the firing process can be shortened.

(6) Inorganic powder-containing resin pattern firing step In this step, the inorganic powder-containing resin pattern is fired to form a black matrix. As a result, the organic material in the resin layer residual portion is burned off, and a black matrix is formed.

The temperature for the baking treatment needs 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.
<Black matrix>
The warp when laminated and fired is caused by a difference in thermal expansion coefficient between other member forming materials formed on the underlying pattern. In particular, in such a case, if an undercut is generated in the underlying pattern, the problem of warpage becomes more prominent. In addition, since another member forming material is laminated on the pattern formed for one member and pattern formation is performed, there is a problem in that the underlying pattern is broken by the organic solvent contained in the newly laminated material. . Therefore, high solvent resistance is also required for the pattern after development.

  However, if the transfer film of the present invention is used, a black matrix having a low reflectance and transmittance and a good patterning shape can be effectively formed. In addition, since no warping occurs in patterning after firing, bending cracks (cracks) hardly occur on the surface, and a stable material can be provided when a laminated structure is constructed. Furthermore, it has a margin for the thermal expansion coefficient of the member formed above.

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

<Synthesis Example 1>
60 g of benzyl methacrylate (BzMA), 20 g of methacrylic acid (MA) and 20 g of 2-hydroxyethyl methacrylate (HEMA) were mixed in a four-necked flask, and after adding 212.5 g of methoxypropyl acetate, the temperature was raised to 70 ° C. 1.0 g of 2,2′-azobisisobutyronitrile (AIBN) is added. Furthermore, the temperature is raised to 80 ° C., and the reaction is performed for 3 hours under nitrogen. After reacting for 3 hours, 0.5 g of AIBN is added and reacted for another 1 hour. Thereafter, the temperature was raised to 100 ° C. and reacted for 1 hour, and benzyl methacrylate (BzMA) / methacrylic acid (MA) / 2-hydroxyethyl methacrylate (HEMA) = 60/20/20 (mass%) copolymer (Mw = 35000) (hereinafter simply referred to as “binder resin 1”).

<Synthesis Example 2>
Binder resin 2 was obtained by adding 5 mol% of 2-methacryloyloxyethyl isocyanate (MOI) to the number of moles of 2-hydroxyethyl methacrylate in binder resin 1.

<Synthesis Examples 3-5>
In the same manner as in Synthesis Example 2, except that 2-methacryloyloxyethyl isocyanate (MOI) was added in an amount shown in Table 1 with respect to the number of moles of 2-hydroxyethyl methacrylate (HEMA) in binder resin 1, Binder resins 3 to 5 were obtained.

<Evaluation by single layer>
(1) Preparation of resin composition containing inorganic powder:
As the inorganic powder (A), MnCo ₂ O ₄ —CoMn ₂ O ₄ —CuMn ₂ O ₄ —Cu ₃ Mn ₃ O ₈
System colored pigment (A-1) (specific surface area 18.9 m ² / g; average particle diameter (D50) 0.3 μm) (
Hereinafter, it is also simply referred to as “Pigment 1”. ) And 20 parts of Bi ₂ O ₃ —ZnO—B ₂ O ₃ —BaO—SiO ₂ -based glass frit (A-2) (indefinite shape; average particle diameter (D50) 0.6 μm; softening point 4)
56 ° C .; linear expansion coefficient 8.6 × 10 ⁻⁶ / K) (hereinafter also simply referred to as “glass 1”) 90 parts, binder resin 1 24 parts, and photopolymerizable monomer (C) 16 parts trimethylolpropane EO-modified (n≈2) triacrylate (trade name: M360, manufactured by Toagosei Co., Ltd.) as a photopolymerization initiator (D), ethanone-1- [9-ethyl-6- [ 2-Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) (compound represented by formula (2)) (hereinafter also simply referred to as “photopolymerization initiator d-1”), 5 parts, As a photopolymerization initiator, 3.3 parts of 2,4-diethylthioxanthone (DETX-S) (hereinafter, also simply referred to as “photopolymerization initiator d-2”) and 3-organosilane compound (E) as 3- Inorganic powder-containing resin by kneading 0.22 parts of methacryloxypropylmethoxysilane and 20 parts of propylene glycol monomethyl ether as a solvent with a bead mill and filtering with a stainless mesh (500 mesh; 25 μm diameter) Composition (I) was prepared.

(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 μm, 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 for 1 minute 30 seconds to remove the solvent, and forming an inorganic powder-containing resin layer having a thickness of 6 μm on the support film.

(3) Transfer film transfer process:
Using the transfer film prepared 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 90 ° C., the roll pressure was 0.25 MPa, and the moving speed of the heating roller was 0.5 m / min. As a result, the transfer film was transferred to and closely adhered to the surface of the glass substrate.

(4) Exposure step and development step of the inorganic powder-containing resin layer:
The inorganic powder-containing resin layer formed on the glass substrate is irradiated with i-rays (ultraviolet light having a wavelength of 365 nm) with an ultra-high pressure mercury lamp through an exposure mask (5 cm × 5 cm) after peeling the support film. Then, a latent image of the pattern was formed on the inorganic powder-containing resin layer. Here, the irradiation amount was 800 mJ / cm ² . After the exposure, development treatment was performed for 20 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developing solution, followed by washing with ultrapure water.

Thereby, the inorganic powder containing resin of the part which was not irradiated with an ultraviolet-ray was removed, and the inorganic powder containing resin pattern was formed.
(5) Firing step:
The glass substrate on which the inorganic powder-containing resin pattern was formed was baked for 30 minutes in a temperature atmosphere of 520 ° C. As a result, a black matrix having a thickness of 2.0 μm was formed on the surface of the glass substrate.

(6) Black matrix curing depth evaluation:
The inorganic powder-containing resin layer formed on the glass substrate was irradiated with i-line (ultraviolet light having a wavelength of 365 nm) from the glass substrate with an ultra-high pressure mercury lamp to cure the inorganic powder-containing resin layer. Here, the irradiation amount was 800 mJ / cm ² . After the exposure, the support film is peeled off and then developed for 30 seconds by a shower method using a 0.5 mass% sodium carbonate aqueous solution at a liquid temperature of 25 ° C. as a developer, followed by washing with ultrapure water. Went. Thereby, the ultraviolet-ray was irradiated and the inorganic powder containing resin which was not hardened | cured was removed. As a result of measuring the residual film thickness of the obtained black matrix of 5 cm × 5 cm using a fine column height measuring device P-10 (manufactured by KLA-TENCOR), it was 4.5 μm. It was confirmed to have sensitivity. In order to express the goodness of the curing depth by x, o, and し た, it was defined in the following range of remaining film values.
×: <4 μm, ○: 4-6 μm, ◎:> 6 μm
(7) Black matrix patterning evaluation:
After firing, when the patterning shape was confirmed with a scanning electron microscope (manufactured by Hitachi High-Technologies) using the obtained 5 cm × 5 cm-shaped black matrix, the pattern was smooth and no warping phenomenon was observed. Excellent patterning performance was demonstrated.

<Evaluation by lamination>
(8) Preparation of post-baking step / laminated pattern An inorganic powder-containing resin pattern (linear expansion coefficient: 8.6 × 10 ⁻⁶ / K) was formed by the steps described in (1) to (4) above. The glass substrate was post-baked in an oven at 200 ° C. for 15 minutes. A pattern is further formed on the upper layer of the inorganic powder-containing resin pattern by a printing method using an inorganic powder-containing resin composition containing glass having a linear expansion coefficient of 9.2 × 10 ⁻⁶ / K, and a laminated pattern is formed. Obtained.

(9) Firing step The glass substrate on which the laminated pattern was formed by the step described in (8) above was baked for 30 minutes in a temperature atmosphere of 520 ° C. Thereby, the laminated structure was formed on the surface of the glass substrate.

(10) Evaluation of solvent resistance of black matrix:
The glass substrate on which the laminated pattern is formed by the process described in (8) above is dried in an oven at 100 ° C. for 10 minutes, and then taken out, and the pattern of the black matrix is observed with an optical microscope. The surface was visually checked for wrinkles.

Pattern collapse or wrinkle occurrence: ×
No pattern collapse / wrinkle generation: ○
(11) Confirmation of warpage generation The substrate obtained after firing was observed with a scanning electron microscope to visually check whether warpage had occurred. When there is no warpage, it is indicated by ○, and when it is generated, it is indicated by ×.

  Except that the binder resin 2 was used, the inorganic powder-containing resin composition, the transfer film, and the black matrix were formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  Except that the binder resin 3 was used, the inorganic powder-containing resin composition, the transfer film, and the black matrix were formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  Preparation of inorganic powder-containing resin composition, production of transfer film, and formation of black matrix in the same manner as in Example 1 except that 15 parts of pigment 1 and 95 parts of glass 1 were used and binder resin 4 was used. And evaluated. The evaluation results are shown in Table 2.

  Except for changing the pigment 1 to 20 parts and the glass 1 to 90 parts, the inorganic powder-containing resin composition, the transfer film, and the black matrix were formed and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 2.

  Except for changing the pigment 1 to 25 parts and the glass 1 to 85 parts, an inorganic powder-containing resin composition, a transfer film, and a black matrix were formed and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 2.

  Except not performing the post-baking process, it carried out similarly to Example 5, and prepared the inorganic powder containing resin composition, preparation of the transfer film, and formation and evaluation of the black matrix. The evaluation results are shown in Table 2.

[Comparative Example 1]
20 parts of pigment 1, 90 parts of glass 1, 24 parts of binder resin 1, 16 parts of trimethylolpropane EO-modified (n≈2) triacrylate as photopolymerizable monomer (C), photopolymerization initiator (D ) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name: IRG.369, manufactured by Ciba Special Chemicals) (hereinafter simply referred to as “photopolymerization initiation”) 2.5 parts of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRG.651, manufactured by Ciba Special Chemicals) (hereinafter referred to as “agent d-3”) (Also simply referred to as “photopolymerization initiator d-4”), 1.1 parts of organic silane compound (E), 0.22 parts of 3-methacryloxypropylmethoxysilane, and propylene glycol monomer as solvent. Except for using 20 parts of the methyl ether, the same procedure as in Example 1, preparation of inorganic powder-containing resin composition, it has been fabricated and the formation and evaluation of the black matrix of the transfer film. The evaluation results are shown in Table 2.

[Comparative Examples 2 to 5]
Except that the inorganic powder-containing resin composition having the composition shown in Table 2 was used, the preparation of the inorganic powder-containing resin composition, the production of the transfer film, and the black matrix were performed in the same manner as in Example 1. Formation and evaluation were performed. The evaluation results are shown in Table 2.

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

Explanation of symbols

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

Claims (10)

(A) As an inorganic powder, a colored pigment (A-1) and a glass powder (A-2),
(B) binder resin,
(C) An inorganic powder-containing resin composition containing a photopolymerizable monomer and (D) a compound represented by the following formula (1) as a photopolymerization initiator.

(1)
[In the above formula (1), R ¹ , R ² and R ³ are R, OR, COR, SR, CONR, respectively.
R ′ or CN represents R and R ′ each represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom or a heterocyclic group, and among these, an alkyl group And the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ′ may be combined to form a ring. Y represents an oxygen atom, a sulfur atom or a selenium atom, A represents a heterocyclic group, m represents an integer of 0 to 4, p represents an integer of 0 to 5, and q represents 0 or 1. ]   The inorganic powder-containing resin composition according to claim 1, wherein the glass powder (A-2) contains a lead-free glass powder having a softening point of 400 to 500 ° C.   The inorganic powder-containing resin composition according to claim 1 or 2, wherein the binder resin (B) has a polymerizable unsaturated double bond in a side chain.   The inorganic powder-containing product according to any one of claims 1 to 3, wherein the binder resin (B) is a polymer obtained by reacting an isocyanate compound having a (meth) acryloyl group with a polymer having a hydroxyl group. Resin composition. The inorganic powder-containing resin composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (D) is a compound represented by the formula (2).

  The inorganic powder-containing resin composition according to any one of claims 1 to 5, further comprising an organosilane compound (E).   The transfer film which has an inorganic powder containing resin layer obtained from the inorganic powder containing resin composition in any one of Claims 1-6 on a support film. Transferring the inorganic powder-containing resin layer of the transfer film according to claim 7 onto a substrate;
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
A method for producing a flat panel display, wherein a black matrix is formed by a method comprising a step of firing the pattern. Transferring the inorganic powder-containing resin layer of the transfer film according to claim 7 onto a substrate;
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
Forming a pattern on the pattern layer to obtain a laminated pattern layer;
A method of manufacturing a flat panel display, wherein a plurality of members including a black matrix are collectively formed by a method including a step of firing the laminated pattern. Transferring the inorganic powder-containing resin layer of the transfer film according to claim 7 onto a substrate;
A step of exposing the inorganic powder-containing resin layer to form a latent image of a pattern;
Developing the inorganic powder-containing resin layer to form a pattern;
A step of post-baking the obtained pattern layer;
Forming a pattern on the pattern layer to obtain a laminated pattern layer;
A method of manufacturing a flat panel display, wherein a plurality of members including a black matrix are collectively formed by a method including a step of firing the laminated pattern.

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