KR100680087B1 - Inorganic Particle-Containing Resin Composition, Transfer Film Comprising the Same and Plasma Display Panel Production Process - Google Patents

Abstract

The present invention provides an inorganic particle-containing resin composition excellent in flexibility and transferability and capable of forming an inorganic particle-containing resin layer that does not cause deformation and peeling in a sintered body pattern formed through an etching process and a firing process, and the inorganic particles. It is possible to provide a transfer film having a resin layer containing a resin, and to provide a pattern with high dimensional accuracy, and to provide a method for producing a PDP having excellent workability.

The inorganic particle containing resin composition of this invention contains the compound and solvent containing an inorganic particle, binder resin, a methylol group, and / or an alkoxy methyl group. As for the transfer film of this invention, the inorganic particle containing resin layer obtained from the said inorganic particle containing resin composition is formed on the support film. The PDP manufacturing method of this invention includes the process of forming a PDP component by transferring the inorganic particle containing resin layer which comprises said transfer film on a board | substrate, and etching and baking an inorganic particle containing resin layer.

Inorganic particles, pattern, resin composition, transfer film, plasma display

Description

Inorganic Particle-Containing Resin Composition, Transfer Film Comprising the Same and Plasma Display Panel Production Process

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel.

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

3 is a schematic cross-sectional view showing an example of an electrode formation step (transfer step, resist film formation step, exposure step) in the production method of the present invention.

It is a schematic sectional drawing which shows an example of the formation process (development process, etching process, baking process) of the electrode in the manufacturing method of this invention.

<Explanation of symbols for the main parts of the drawings>

1: glass substrate (front substrate)

2: glass substrate (back substrate)

3: bulkhead

4: transparent electrode

5: bus electrode                 

6: address electrode

7: phosphor

8: Dielectric (Front Board)

9: dielectric (back substrate)

10: shield

1F: support film

2F: inorganic particle-containing resin layer

F3: cover film

11: glass substrate

12: transparent electrode

20: transfer film

21: inorganic particle-containing resin layer

22: support film

25: Pattern of Inorganic Particle-Containing Resin Layer

25A: Resin layer remaining part

25B: Resin Layer Removal Part

31: resist film

35: resist pattern

35A: Resist Residue

35B: resist removal section                 

40: electrode

50: panel material

M: mask for exposure

MA: light transmitting part

MB: Shading part

The present invention relates to an inorganic particle-containing resin composition, a transfer film, and a method for manufacturing a plasma display panel using the same. More particularly, the present invention relates to an electrode, a partition, a resistor, a dielectric, a phosphor, and a color filter constituting each display cell of the plasma display panel. And an inorganic particle-containing resin composition which can be preferably used to form a high precision pattern in forming a black stripe (matrix), a transfer film having an inorganic particle-containing resin layer obtained using the same, and a plasma display performed using the transfer film. It relates to a method for producing a panel.

Plasma display panels (hereinafter referred to as "PDP") are large panels, and are attracting attention among flat panel display technologies for reasons such as easy manufacturing processes, wide viewing angles, and high display quality due to their self-luminous type. PDPs are expected to become mainstream in the future as display devices for wall-mounted televisions of 20 inches or larger.                         

Color PDP can display a color by irradiating a fluorescent substance with the ultraviolet-ray generate | occur | produced by gas discharge. In general, in the color PDP, the red luminescent phosphor portion, the green luminescent phosphor portion and the blue luminescent phosphor portion are formed on the substrate so that the light emitting display cells of each color are uniformly mixed in the whole. Specifically, a partition wall made of an insulating material called a barrier rib is provided on the surface of the substrate made of glass or the like, and a plurality of display cells are partitioned by the partition wall, and the inside of the display cell becomes a plasma working space. A phosphor portion is provided in the plasma working space and an electrode for applying a plasma to the phosphor portion is provided to form a plasma display panel in which each display cell is a display unit.

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel. In the drawings, (1) and (2) are opposed glass substrates, (3) are partition walls, and cells are partitioned by the glass substrate (1), glass substrate (2), and partition walls (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 lowering the resistance of the transparent electrode 4, 6 is a glass substrate 2 An address electrode fixed to the substrate, (7) a phosphor held in the cell, (8) a dielectric formed on the surface of the glass substrate (1) to cover the transparent electrode (4) and the bus electrode (5), (9) an address electrode The dielectric material 10 formed on the surface of the glass substrate 2 so as to cover 6 is a protective film made of, for example, magnesium oxide.

In addition, in order to improve the contrast of the PDP, a red, green, blue color filter or a black matrix having a stripe-like and lattice-shaped shape is interposed between the glass substrate 1 and the dielectric 8 and the dielectric 8 and It may be provided between the protective film 10 and the like.

In the DC-type PDP, a resistor is usually provided between the electrode terminal (anode terminal) and the electrode lead (anode lead) together with the AC-type PDP component.

As a method of manufacturing an electrode, a partition, a resistor, a dielectric, a phosphor, a color filter, a black matrix, and the like constituting such a plasma display panel, (1) a non-photosensitive inorganic particle-containing resin composition is screen printed onto a substrate to obtain a pattern; Screen printing method of baking this, (2) Photosensitive inorganic particle containing resin composition film | membrane is formed on a board | substrate, this pattern is formed by irradiating an ultraviolet-ray through a photomask, and a pattern is formed on a board | substrate, and this photolithographic method of baking this Etc. are known.

However, in the above screen printing method, there is a problem that the demand for positional accuracy of the pattern is very strict due to the increase in size and precision of the panel, and thus it is not possible to cope with the ordinary printing method.

In addition, in the photolithography method, when forming a pattern having a film thickness of 10 to 100 [mu] m in a single exposure and development process, a pattern having a low sensitivity to the depth direction of the inorganic particle-containing resin layer and a high precision with a clear edge are produced. Difficult to obtain Moreover, there exists a problem that a dregs easily generate | occur | produces in a image development process, and the pattern deformation of the sintered compact formed through a baking process and peeling of the said pattern are easy to generate | occur | produce.

An electrode, partition wall, resistor, dielectric, phosphor, color filter, and black matrix with high dimensional accuracy can be obtained, and the forming method has improved workability as compared with the manufacturing methods such as (1) and (2). The inventors form an inorganic particle-containing resin layer obtained from an inorganic particle-containing resin composition on a support film, transfer the inorganic particle-containing resin layer onto a substrate to form a resist film on the inorganic particle-containing resin layer transferred onto the substrate, Exposing the resist film to form a latent image of a resist pattern; developing the resist film to present a resist pattern; etching the inorganic particle-containing resin layer to form an inorganic particle-containing resin layer pattern corresponding to the resist pattern And a method including the step of firing the pattern to form an electrode, a resistor, a dielectric, and a mold. A method of forming at least one of a body, a color filter and a black matrix is proposed (see Japanese Patent Laid-Open No. 11-162339).

According to this manufacturing method, a pattern with high precision and excellent surface uniformity can be formed. Moreover, the composite film (henceforth "transfer film") in which the inorganic particle containing resin layer which consists of an inorganic particle containing resin composition is formed on a support film is also advantageous at the point which can be wound up and preserve | saved in roll shape.

However, the conventional transfer film has a problem that the inorganic particle-containing resin layer formed on the support film does not have sufficient flexibility, and when the transfer film is bent, fine cracks (cracking) occur on the surface of the inorganic particle-containing resin layer. have.

Moreover, there exists a problem that an inorganic particle containing resin layer cannot exhibit sufficient adhesiveness (heat adhesiveness) with respect to a glass substrate, and does not transfer to a glass substrate surface from a support film.                         

Moreover, in the sintered compact pattern formed by baking the pattern of an inorganic particle containing resin layer, there exists a problem that a deformation | transformation and peeling tend to occur easily.

The term "deformation of the pattern" herein refers to a phenomenon in which the pattern edge portion is bent up from the substrate, so-called edge curl.

In addition, "pattern peeling" means the phenomenon that a pattern falls from a board | substrate as a result of the extreme pattern distortion generate | occur | produced.

This invention is made | formed based on the above circumstances.

The first object of the present invention is excellent in flexibility and transferability (heat adhesion of the inorganic particle-containing resin layer to the glass substrate), and does not cause deformation or peeling of the sintered body pattern formed through the etching process and the firing process. It is providing the inorganic particle containing resin composition which can form an inorganic particle containing resin layer.

The second object of the present invention is excellent in flexibility and transferability (heat adhesion of the inorganic particle-containing resin layer to the glass substrate), and does not cause deformation or peeling of the sintered body pattern formed through the etching process and the firing process. It is to provide a transfer film having an inorganic particle-containing resin layer.

A third object of the present invention is to provide a method of manufacturing a plasma display panel which can form a pattern with high dimensional accuracy and is excellent in workability.

The inorganic particle-containing resin composition of the present invention comprises a compound containing (A) an inorganic particle, (B) a binder resin, (C) a methylol group and / or an alkoxymethyl group (hereinafter simply referred to as a "specific compound") and (D A solvent is contained.

The transfer film of this invention is characterized by the inorganic particle containing resin layer obtained from the said inorganic particle containing resin composition formed on the support film.

In the method of manufacturing a plasma display panel of the present invention, the inorganic particle-containing resin layer constituting the transfer film is transferred onto a substrate, a resist film is formed on the transferred inorganic particle-containing resin layer, and the resist film is exposed to a resist pattern. By forming a latent image of the resist film, developing the resist film to present a resist pattern, etching the inorganic particle-containing resin layer to form an inorganic particle-containing resin layer pattern corresponding to the resist pattern, and firing the pattern And forming at least one of a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix.

Moreover, the manufacturing method of the plasma display panel of this invention forms the laminated film of a resist film and the inorganic particle containing resin layer obtained from said inorganic particle containing resin composition on a support film, and transfers the laminated film on a board | substrate, The resist film constituting the laminated film is exposed to light to form a latent image of the resist pattern, the resist film is developed to present a resist pattern, and the inorganic particle-containing resin layer is etched to contain inorganic particles corresponding to the resist pattern. And forming one or more of a barrier rib, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix by forming a layer pattern and firing the pattern.

<Embodiment of the invention>

EMBODIMENT OF THE INVENTION Hereinafter, the inorganic particle containing resin composition of this invention is demonstrated in detail.

The inorganic particle containing resin composition of this invention contains an inorganic particle, a binder resin, a specific compound, and a solvent as essential components.

<Inorganic particles>

The kind of inorganic particle used for the inorganic particle containing resin composition of this invention is a use of the sintered compact formed with the said composition (for example, PDP components, such as a partition, an electrode, a resistor, a dielectric, fluorescent substance, a color filter, and a black matrix). ), Etc.

Here, as an inorganic particle contained in the partition which comprises a PDP, and the composition for forming a dielectric, the glass frit of a low melting point, etc. are mentioned.

It is preferable that the softening point of this low melting glass frit exists in the range of 400-600 degreeC.

In the case where the softening point of the glass frit is less than 400 ° C, the glass frit melts at a stage in which the organic material such as the binder resin is not completely decomposed and removed in the firing step of the inorganic particle-containing resin layer by the composition. A part of organic substance remains in it, and as a result, a sintered compact will color and the light transmittance will tend to fall. On the other hand, when the softening point of a glass frit exceeds 600 degreeC, since it needs to bake at higher temperature than 600 degreeC, a deformation | transformation etc. are easy to generate | occur | produce in a glass substrate.                     

Specifically, lead oxide, boron oxide, silicon oxide (PbO-B ₂ O ₃ -SiO _{2 type} ), lead oxide, boron oxide, silicon oxide, aluminum oxide type (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ based), zinc oxide, boron oxide, silicon oxide based (ZnO-B ₂ O ₃ -SiO ₂ based), zinc oxide, boron oxide, silicon oxide, aluminum oxide based (ZnO-B ₂ O ₃ -SiO _2- Al ₂ O ₃ based), lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO ₂ based), lead oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide ( PbO-ZnO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ based), bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ based), bismuth oxide, boron oxide, Silicon oxide, aluminum oxide type (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ -Al ₂ O _{3 type} ), bismuth oxide, zinc oxide, boron oxide, silicon oxide type (Bi ₂ O ₃ -ZnO-B ₂ O ₃ -SiO ₂ based), bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide based (Bi ₂ O ₃ -ZnO-B ₂ O ₃ -SiO ₂ And glass frits such as -Al ₂ O ₃ system).

These low melting glass frits may be contained in the composition for forming components other than dielectrics and partitions (eg, electrodes, resistors, phosphors, color filters, black matrices).

As an inorganic particle contained in the composition for forming the electrode which comprises a PDP, particle | grains which consist of Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr, etc. are mentioned.

Examples of the inorganic particles contained in the composition for forming the transparent electrode constituting the PDP include indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), fluorinated indium oxide (FIO), and fluorine addition. Zinc oxide fine particles containing particles consisting of tin oxide (FTO), fluorinated zinc oxide (FZO) and the like, and one or two or more metals selected from Al, Co, Fe, In, Sn and Ti. .

The inorganic particles contained in the composition for forming a resistor constituting a PDP, there may be mentioned particles composed of RuO ₂ and the like.

Examples of the inorganic particles contained in the composition for forming the phosphor constituting the PDP include Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ , YVO ₄ : Eu Red phosphors such as ³⁺ , (Y, Gd) BO ₃ : Eu ^{3 −} , Zn ₃ (PO ₄ ) ₂ : Mn; Green phosphors such as 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 : Tb; _{Y 2 SiO 5: Ce, BaMgAl} 1O O 17: Eu 2+, BaMgAl 14 O 23: Eu 2+, (Ca, Sr, Ba) 10 (PO 4) 6 Cl 2: Eu 2+, (Zn, Cd) And particles made of a blue fluorescent substance such as S: Ag.

Examples of the inorganic particles contained in the composition for forming the black stripe (matrix) constituting the PDP include metals such as Co, Cr, Cu, Fe, Mn, Ni, Ti, and Zn and their oxides, composite oxides, carbides, nitrides, sulfides, and the like. And particles such as silicides, borides and carbon black and graphite.

<Binder Resin>

As the binder resin used in the present invention, a resin containing an alkali-soluble resin in the binder resin in a proportion of 30 to 100% by weight is particularly preferable.

Here, "alkali solubility" means the property which melt | dissolves with the alkaline etching liquid mentioned later and has solubility to the extent that the target etching process is performed.

As a specific example of such alkali-soluble resin, a (meth) acrylic resin, a hydroxy styrene resin, a novolak resin, a polyester resin etc. are mentioned, for example.

Among these alkali-soluble resins, (meth) acrylic resins such as copolymers of the following monomers (a) and monomers (b) or copolymers of monomers (a) and monomers (b) and monomers (c) are particularly preferred. Can be mentioned.

Monomer (A):

Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono Carboxyl group-containing monomers such as (meth) acrylate;

Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; Alkali-soluble functional group containing monomers represented by phenolic hydroxyl group containing monomers, such as o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene.

Monomer (I):

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) (Meth) acrylic acid esters other than monomer (a), such as an acrylate; Aromatic vinyl monomers such as styrene and α-methylstyrene; Monomers copolymerizable with monomers (a) represented by conjugated dienes such as butadiene and isoprene.

Monomer (C):

Macromonomer represented by macromonomer etc. which have polymerizable unsaturated groups, such as a (meth) acryloyl group, in one terminal of a polymer chain, such as polystyrene, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, and benzyl poly (meth) acrylate Liu.

As molecular weight of the said alkali-soluble resin, it is preferable that it is 5,000-500,000 as polystyrene conversion weight average molecular weight (henceforth "Mw") by GPC, and 10,000-300,000 are more preferable.

The content rate of binder resin in an inorganic particle containing resin composition is 1-1,000 weight part normally with respect to 100 weight part of inorganic particles, Preferably it is 5-200 weight part. If the ratio of the binder resin is too small, the inorganic particles can not be reliably bound and held. On the other hand, if the ratio is too large, the firing process takes a long time or the pattern shape formed becomes uneven.

<Specific compound>

By using the composition containing a specific compound, favorable flexibility and transferability can be expressed in the inorganic particle containing resin layer formed. Moreover, the said pattern deformation and pattern peeling do not generate | occur | produce in the sintered compact pattern formed by baking this inorganic particle containing resin layer pattern.

Therefore, according to the transfer film provided with the inorganic particle containing resin layer containing a specific compound, the target sintered compact pattern can be reliably formed by baking the said inorganic particle containing resin layer pattern.

As such a compound, melamine, benzoguanamine, glycoluril, etc. are mentioned.

Of these, compounds containing an average of two or more of alkoxymethyl groups having 6 or less carbon atoms in the repeating unit are used, and more preferably compounds containing two or more of methoxymethyl groups in the repeating unit are used. In particular, preferably, melamine containing two or more methoxymethyl groups in the repeating unit is used.

The weight average degree of polymerization of such a compound is usually 10 or less, preferably 5 or less, particularly preferably 2.5 or less.

As a commercial item of a specific compound, "Cymel 300" (melamine having an average of 5 or more methoxymethyl groups in the repeating unit, polymerization average degree of polymerization 1.35), "Cymel 1170" (having an average of 3 or more methoxybutyl groups in the repeating unit Cymel series (manufactured by Mitsui Cyamide, Inc.) such as glycoluril and polymerization average polymerization degree 1.5), "MW-30" (melamine having an average of 5 or more methoxymethyl groups in a repeating unit, polymerization average polymerization degree 1.5), and "MX- And Nicarac series (manufactured by Sanwa Chemical Co., Ltd.) such as 45 "(melamine having an average of 5 or more in the methoxymethyl group and the methoxybutyl group in a repeating unit, and a polymerization average degree of polymerization of 1.5).

The content rate of the specific compound in an inorganic particle containing resin composition is 0.1-500 weight part normally, Preferably it is 0.5-100 weight part with respect to 100 weight part of inorganic particles, Especially preferably, it is 1-50 weight part. When the specific compound ratio is too small, the flexibility and transferability of the transfer film obtained are insufficient, and edge curl and pattern peeling are likely to occur in the sintered body pattern formed by firing the inorganic particle-containing resin layer pattern. On the other hand, when this ratio is too large, it may take a long time for the firing process or the electrodes, partitions, resistors, dielectrics, phosphors, color filters, and black stripes (matrix) shapes to be formed may become uneven.

<(Meth) acryloyl group containing compound>

The composition of the present invention may contain a compound having one or more (meth) acryloyl groups in the molecule.

As a specific example of the said compound, As a compound which has one (meth) acryloyl group, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylic Latex, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Isostearyl (meth) acrylic Sites of such alkyl (meth) acrylate;

Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth Hydroxyalkyl (meth) acrylates such as) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl ( Alkoxyalkyl (meth) acrylates such as meth) acrylate;

Carboxyl group containing (meth) acryloyl-group containing compounds, such as acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, (omega)-carboxy- polycaprolactone mono (meth) acrylate, etc. are mentioned.

As a compound which has two or more (meth) acryloyl groups, For example, Di (meth) acrylates of alkylene glycols, such as ethylene glycol and propylene glycol;

Polyalkylene glycol adduct poly (meth) acrylates of trivalent or higher polyhydric alcohols;

Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Poly (meth) acrylates of trivalent or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol, and dicarboxyl thereof Acid denaturates;

Poly (meth) acrylates of cyclic polyols such as 4-cyclohexanediol and 1,4-benzenediols;

Oligos, such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiran resin (meth) acrylate ( Meth) acrylates;

Di (meth) acrylates obtained by hydroxylating polymer sock ends such as polybutadiene, polyisoprene and polycaprolactone;

Tris (meth) acryloyloxyethyl phosphate etc. are mentioned, Di (meth) acrylates of alkylene glycol, such as ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols, such as polyethyleneglycol and polypropylene glycol, etc. are mentioned as a preferable thing. These can be used individually or in combination of 2 or more types.

In the composition of this invention, since flexibility and the transferability of the transfer film obtained become favorable, and the adhesiveness of a resist pattern and an inorganic particle containing resin layer pattern becomes excellent, it is especially two or more (meth) acryloyl groups. It is preferable that the compound which has, ie, polyvalent acrylate, is used.

The content ratio of the (meth) acryloyl group-containing compound in the inorganic particle-containing resin composition is usually 0.1 to 500 parts by weight with respect to 100 parts by weight of the inorganic particles in order to give better flexibility and etching properties to the inorganic particle-containing resin layer formed. Preferably, 0.5 to 100 parts by weight is used.

<Solvent>

The solvent which comprises the inorganic particle containing resin composition of this invention is contained in order to provide moderate fluidity | liquidity, plasticity, and favorable film formation property to the said inorganic particle containing resin composition.

The solvent is particularly limited as long as it has a good affinity with inorganic particles, a solubility of organic components such as a binder resin, a specific compound, can impart appropriate viscosity to the inorganic particle-containing resin composition, and can be easily evaporated and removed by drying. For example, ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, sulfoxides, sulfones, hydrocarbons, halogenated hydrocarbons, and the like Etc. can be mentioned.

Specific examples of such solvents include tetrahydrofuran, anisole, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetic acid esters and hydroxy. Acetic acid esters, alkoxyacetic acid esters, propionic acid esters, hydroxypropionic acid esters, alkoxypropionic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxy acetic acid esters, cyclic compounds Ketones, acyclic ketones, acetic acid esters, pyruvic acid esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulls Foxids, dialkyl sulfones, t-pineol, N-methyl-2-pyrrolidone, etc. are mentioned. have. These can be used individually or in combination of 2 or more types.

Although the solvent content ratio in an inorganic particle containing resin composition can be suitably selected from the range which can obtain favorable film formation property (flowability or plasticity), it is usually 1-10000 weight part with respect to 100 weight part of inorganic particles, and it is more preferable. Preferably from 10 to 1,000 parts by weight.

<Plasticizer>

In the composition of this invention, a plasticizer may be contained in order to provide favorable flexibility to the inorganic particle containing resin layer formed. As a particularly preferable plasticizer, a plasticizer (hereinafter, referred to as a "specific plasticizer") consisting of a compound represented by the following general formula (1) or (2) is mentioned. According to the composition of the present invention in which the specific plasticizer is contained, good flexibility and combustibility can also be obtained in the inorganic particle-containing resin layer formed, and since the specific plasticizer is easily decomposed and removed by heat, the inorganic particle-containing resin layer is fired. For example, light transmittance of a dielectric or the like is not lowered.

In the formula, R ¹ and R ³ each represent the same or different alkyl group of 1 to 30 carbon atoms, R ² and R ⁴ each represent the same or different alkylene group of 1 to 30 carbon atoms, m is a number of 0 to 5 , n is a number from 1 to 10.

In formula, R <^5> represents a C1-C30 alkyl group or alkenyl group.

In the above formula (1) representing a specific plasticizer, an alkyl group represented by R ¹ or R ⁴

And the alkylene group represented by R ² or R ³ may be an unsaturated group even if it is a linear, branched or saturated group.

Carbon number of the alkyl group represented by R <^1> or R <^4> is 1-30, Preferably it is 2-20, More preferably, it is 4-10.

N in the said General formula (1) is 1-10, Preferably it is 2-6.

Specific examples of the compound represented by Formula 1 include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl diglycol adipate, and the like. Can be mentioned.

In Formula 2, which represents a specific plasticizer, the alkyl group and alkenyl group represented by R ⁵ may be linear, branched or saturated.

Carbon number of the alkyl group or alkenyl group represented by R <^5> is 1-30, Preferably it is 2-20, More preferably, it is 10-18.

Specific examples of the compound represented by the formula (2) include propylene glycol monolaurate, propylene glycol monooleate, and the like.

Moreover, polypropylene glycol etc. are mentioned as a compound used preferably as a plasticizer other than a specific plasticizer.

As a content rate of the specific sweep in the composition of this invention, it is preferable that it is 100 weight part or less with respect to 100 weight part of inorganic particles, More preferably, it is 0.5-50 weight part.

In addition to the above components, the composition of the present invention includes, as an optional component, a dispersant, a development accelerator, an adhesive preparation, a antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a tackifier, a surface tension regulator, a leveling agent, a crosslinking agent, a polymerization initiator, Various additives, such as an acid generator, can be contained. In addition, the inorganic particle containing resin composition of this invention contains the photoinitiator which comprises the resist composition mentioned later, and may be radiation sensitive.

The inorganic particle containing resin composition of this invention can be manufactured by kneading an inorganic particle binder resin, a specific compound, a solvent, and arbitrary components using kneading machines, such as a roll kneader, a mixer, a homo mixer, a ball mill, and a bead mill.

The inorganic particle containing resin composition of this invention manufactured as mentioned above is a paste-form composition which has the fluidity suitable for application | coating normally, The viscosity is 100-1000,000cp normally, Preferably it is 500-30,000cp.

The composition of this invention can be used especially suitably in order to manufacture the transfer film (transfer film of this invention) mentioned below.

As a viscosity of the inorganic particle containing resin composition of this invention provided here in the application | coating process of a support film, it is preferable that it is 1,000-10Ocp.                     

<Transfer film>

Fig. 2 (a) is a schematic sectional view which shows the transfer film of this invention wound in roll shape, and Fig. (B) is sectional drawing (partial detail view of (a)) which shows the laminated constitution of this transfer film.

As an example of the transfer film of this invention, the transfer film shown in FIG. 2 is a composite film used in order to form the dielectric which comprises a PDP, and can peel normally on the support film F1 and the surface of this support film F1. It is comprised by the inorganic particle containing resin layer (F2) formed in this way, and the cover film (F3) provided in the surface of this inorganic particle containing resin layer (F2) easily peelable. The cover film (F3) may not be used depending on the property of the inorganic particle-containing resin layer (F2) or for the purpose of reducing the weight of the roll wound the transfer film.

It is preferable that the support film (F1) which comprises a transfer film is a resin film which has heat resistance and solvent resistance, and has flexibility. Since the support film has flexibility, the composition of the present invention can be applied by a roll coater or the like, and the formed inorganic particle-containing resin layer can be stored and supplied in a rolled state.

Examples of the resin forming the supporting film (F1) include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, nylon, Cellulose, and the like. As thickness of support film F1, it is 20-100 micrometers, for example.

The inorganic particle containing resin layer (F2) which comprises a transfer film is a layer which becomes a sintered compact by baking, The inorganic particle containing resin composition of this invention is apply | coated on the said support film, and a coating film is dried and a part or all of a solvent is removed. It can form by doing.

As a film thickness of an inorganic particle containing resin layer (F2), it can select suitably according to content rate of an inorganic particle, the kind and size of a member, etc.

Cover film F3 which comprises a transfer film is a film for protecting the surface (contact surface with a glass substrate) of inorganic particle containing resin layer F2. It is preferable that this cover film (F3) is also a resin film which has flexibility. As resin which forms cover film (F3), a polyethylene terephthalate film, a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned. Moreover, as thickness of cover film F3, it is 20-100 micrometers, for example.

The transfer film of the present invention is produced by forming an inorganic particle-containing resin layer (F2) on the support film (F1) and providing a cover film (F3) on the inorganic particle-containing resin layer (F2) (pressing). You can do it.

As a method of apply | coating the composition of this invention on a support film, it is preferable that the coating film of the film thickness (for example, 1 micrometer or more) excellent in the uniformity of film thickness can be formed efficiently, specifically, by gravure Coating methods, coating methods with a die, coating methods with a roll coater, application methods with a doctor blade, application methods with a doctor roll, application methods with a curtain coater, application methods with a wire coater, etc. are preferable. Can be.

As drying conditions of a coating film, it is about 0.5 to 30 minutes at 50-150 degreeC, and the residual ratio (content rate in an inorganic particle containing resin layer) of the solvent after drying is 2 weight% or less normally.

The transfer film of the present invention may be formed by laminating an inorganic particle-containing resin layer made of the inorganic particle-containing resin composition of the present invention after forming a resist film on the support film. In this case, the laminated film of the resist film and inorganic particle containing resin layer formed on the support film can be collectively transferred on a board | substrate, and a process can be simplified and a pattern can be made high definition.

Moreover, it is preferable that the mold release process is given to the surface of the support film used for the transfer film of this invention as needed. Thereby, the peeling operation of a support film can be made easy in the transfer process to a board | substrate.

It is preferable that the mold release process is carried out also on the surface of the cover film (usually thermocompression-bonded) provided on the inorganic particle containing resin layer formed as mentioned above. Thereby, a cover film can be easily peeled from the said inorganic particle containing resin layer before transferring an inorganic particle containing resin layer.

The inorganic particle containing resin layer on a support film is collectively transferred to the surface of a board | substrate. According to the transfer film of the present invention, since the inorganic particle-containing resin layer can be reliably formed on the glass substrate by such a simple operation, it is possible to improve the process (high efficiency) in the process of forming components of the PDP such as dielectrics. At the same time, it is possible to improve the quality of the components formed (for example, the expression of stable electrical properties in the electrode).

The composition of the present invention can be particularly suitably used when forming an inorganic particle-containing resin layer on a support film as described above to produce a transfer film, but the present invention is not limited to the use thereof. It can also be used suitably also for the method of forming an inorganic particle containing resin layer by apply | coating this composition directly to the surface of a glass substrate by a formation method, ie, the screen printing method, and drying a coating film. As a viscosity of the inorganic particle containing resin composition of this invention provided here to the application | coating process to the glass substrate by a screen printing method, it is preferable that it is 10,000-200,000cp.

<Production method of PDP>

The manufacturing method of the present invention transfers the inorganic particle-containing resin layer constituting the transfer film of the present invention onto a substrate, forms a resist film on the transferred inorganic particle-containing resin layer, and exposes the resist film to form a latent image of the resist pattern. By developing the resist film to present the resist pattern, etching the inorganic particle-containing resin layer, forming a pattern layer (pattern of the inorganic particle-containing resin layer) corresponding to the resist pattern, and firing the pattern layer. Forming a component selected from a partition wall, an electrode, a resistor, a dielectric, a phosphor color filter, and a black matrix made of a sintered body.

Or a resist film which forms the laminated film of a resist film and the inorganic particle containing resin layer obtained from the inorganic particle containing resin composition of this invention on a support film, transfers the laminated film formed on the support film, onto a board | substrate, and comprises the resist film which comprises this laminated film. The exposure process forms a latent image of the resist pattern, the resist film is developed and the resist pattern is present to etch the inorganic particle-containing resin layer, a pattern layer corresponding to the resist pattern is formed, and the pattern layer is calcined. Thereby forming a component selected from a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix made of a sintered body.

Through the above process, all of the barrier ribs, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices which are components of the PDP can be formed. Hereinafter, the method of forming a "electrode" in the surface on a front substrate is demonstrated. In this method, the [l] inorganic particle-containing resin layer transfer step, the [2] resist film formation step, the [3] resist film exposure step, the [4] resist film development step [5] the inorganic particle-containing resin layer etching step , [6] An electrode is formed on the surface of the substrate by a pattern firing step of the inorganic particle-containing resin layer.

3 and 4 are schematic cross-sectional views showing a series of processes for forming an electrode. 3 and 4, 11 is a glass substrate, and transparent electrodes 12 for generating plasma are arranged on the glass substrate 11 at equal intervals.

In addition, in this invention, the aspect which "transfers an inorganic particle containing resin layer on a board | substrate" The aspect which transfers to the surface of the said transparent electrode 12 is included in addition to the aspect which transfers to the surface of the said glass substrate 11.

(1) Transfer process of inorganic particle containing resin layer:

An example of the transfer step of the inorganic particle-containing resin layer is as follows.

After peeling the cover film (not shown) of the transfer film, as shown in FIG. 3 (b), the transfer film 20 is brought into contact with the surface of the transparent electrode 12 so that the surface of the inorganic particle-containing resin layer 21 abuts. In addition, after carrying out thermocompression bonding of this transfer film 20 with a heating roller etc., the support film 22 is peeled off from the inorganic particle containing resin layer 21. As a result, as shown in FIG. 3 (c), the inorganic particle-containing resin layer 21 is transferred to and adhered to the surface of the transparent electrode 12. Here, as transfer conditions, the surface temperature of a heating roller can show 80-140 degreeC, the roll pressure by a heating roller is 1-5 kg / cm <2>, and the moving speed of a heating roller may be 0.1-10.0 m / min. . In addition, the glass substrate 11 may be preheated, and preheating temperature may be 40-100 degreeC, for example.

(2) Formation process of resist film

In this step, a resist film 31 is formed on the surface of the transferred inorganic particle-containing resin layer 21 as shown in FIG. 3 (d). The resist constituting the resist film 31 may be either a positive resist or a negative resist.

The resist film 31 can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a rotation coating method, a flexible coating method, and then drying the coating film. Here, the drying temperature of a coating film is about 60-130 degreeC normally.

Moreover, it can form by transferring the resist film formed on the support film to the surface of the inorganic particle containing resin layer 21. FIG. According to this formation method, the number of steps of forming the resist film can be reduced, and the film thickness uniformity of the obtained resist film can be excellent, so that the development process of the resist film and the etching process of the inorganic particle-containing resin layer are performed uniformly. The height and shape of the formed electrode become uniform.

As a film thickness of the resist film 31, it is 0.1-40 micrometers normally, Preferably it is 0.5-20 micrometers.

(3) Exposure process of resist film

In this step, as shown in FIG. 3 (E), the surface of the resist film 31 formed on the inorganic particle-containing resin layer 21 is selectively irradiated (exposed) with radiation such as ultraviolet rays through the exposure mask M. A latent image of the resist pattern is formed. In this figure, MA and MB are light transmitting portions and light blocking portions in the exposure mask M, respectively.

As the radiation irradiation apparatus, an ultraviolet irradiation apparatus used in the photolithography method, an exposure apparatus used when manufacturing a semiconductor and a liquid crystal display device, and the like can be used, but are not particularly limited.

(4) Development process of resist film

In this step, the resist pattern (latent image) is made to present by developing the exposed resist film.

Here, as the development treatment conditions, the type, composition, concentration, development time, development temperature, development method (e.g., immersion method, rocking method, shower method, paddle method, etc.) of the developer depending on the type of resist film 31 and the like. , A developing device and the like can be selected as appropriate.

As a result of this development step, as shown in Fig. 4A, a resist pattern 35 (pattern corresponding to the exposure mask M) composed of the resist remaining portion 35A and the resist removing portion 35B is formed.

The resist pattern 35 acts as an etching mask in the next step (etching step), and the constituent material (photocured resist) of the resist remaining portion 35A is formed more than the constituent material of the inorganic particle-containing resin layer 21. It is necessary that the dissolution rate to the etching solution is small.

(5) etching process of inorganic particle containing resin layer;

In this step, the inorganic particle-containing resin layer is etched to form an electrode pattern layer (pattern of the inorganic particle-containing resin layer) corresponding to the resist pattern.

That is, as shown in FIG.4 (b), the part corresponding to the resist removal part 35B of the resist pattern 35 in the inorganic particle containing resin layer 21 is melt | dissolved in etching liquid, and is selectively removed. 4 (b) shows a state during the etching process.

Further, if the etching process is continued, as shown in Fig. 4C, the predetermined portion in the inorganic particle-containing resin layer 21 is completely removed to expose the transparent electrode 12 or the glass substrate 11. Thereby, the electrode pattern layer (pattern of the inorganic particle containing resin layer) 25 comprised from the resin layer residual part 25A and the resin layer removal part 25B is formed.

Here, the etching treatment conditions may include the type, composition, and concentration of the etching solution, the treatment time, the treatment temperature, the treatment method (for example, the dipping method, the shaking method, the shower method, the spray method, and the like depending on the type of the inorganic particle-containing resin layer 21). Paddle method), a processing apparatus, etc. can be selected suitably.

Here, the resist remaining portion 35A constituting the resist pattern 35 is gradually dissolved during the etching process, so that an electrode pattern layer (pattern of the inorganic particle-containing resin layer) 25 is formed (at the end of the etching process). It is preferred to be removed completely in the.

Moreover, even if part or all of the resist residual part 35A remains after the etching process, the said resist residual part 35A is removed in the next baking process.

(6) Pattern baking process of inorganic particle containing resin layer

In this step, the pattern 25 of the inorganic particle-containing resin layer is baked to form an electrode. Thereby, the organic material in the resin layer remaining part 25A disappears, and an electrode is formed and the panel material 50 by which the electrode 40 is formed in the surface of the transparent electrode 12 as shown in FIG. Can be obtained.

As the temperature of the baking treatment, the temperature at which the organic substance in the resin layer remaining portion 25A disappears is required and is usually 400 to 600 ° C. In addition, baking time is 10 to 90 minutes normally.

Preferred Embodiments Using the Photoresist Method

The formation method of the PDP in this invention is not limited to the method as shown in FIG. 3 and FIG.

Here, the formation method by the process of following (1)-(3) is mentioned as another preferable method for forming the component of a PDP.

(l) After forming a resist film on a support film, the inorganic particle containing resin layer is laminated | stacked by apply | coating and drying the inorganic particle containing resin composition of this invention on this resist film. Here, when forming a resist film and an inorganic particle containing resin layer, a roll coater etc. can be used and a laminated film excellent in the uniformity of a film thickness can be formed on a support film by this.

(2) The laminated film of the resist film formed on the support film and the inorganic particle containing resin layer is transferred onto a substrate. Here, as transfer conditions, what is necessary is just the same as the conditions in "the transfer process of an inorganic particle containing resin layer always."

(3) The same operations as in the "exposure process of resist film", "development process of resist film", "etch process of inorganic particle-containing resin layer" and "pattern baking process of inorganic particle-containing resin layer" are performed. In that case, it is preferable to make the developing solution of a resist film and the etching liquid of an inorganic particle containing resin layer the same solution, and to carry out a "development process of a resist film" and an "etching process of an inorganic particle containing resin layer" continuously.

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

<Resist Composition>

In the manufacturing method of this invention, a resist film is formed on an inorganic particle containing resin layer, and a resist pattern is formed on the said inorganic particle containing resin layer by performing an exposure process and a developing process to this resist film.

As a resist composition used for forming a resist film, although an alkali developing radiation sensitive resist composition, an organic solvent developing radiation sensitive resist composition, an aqueous developing radiation sensitive resist composition, etc. can be illustrated, Preferably it is an alkali developing type A radiation sensitive resist composition is used.

"Radiation" as used in the present invention includes visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like.

An alkali developing radiation sensitive resist composition contains alkali-soluble resin and a radiation sensitive component as an essential component.

As alkali-soluble resin which comprises an alkali-developing radiation sensitive resist composition, the alkali-soluble resin illustrated as what comprises the binder resin of an inorganic particle containing resin composition is mentioned.

Examples of the radiation-sensitive component constituting the alkali developing radiation-sensitive resist composition include (a) a combination of a polyvalent acrylate and a photopolymerization initiator, and (b) a combination of a melamine resin and a photoacid generator that forms an acid by irradiation. And (c) compounds in which alkali poorly soluble compounds become alkali-soluble due to irradiation, and the negative type of the polyhydric acrylic and the photopolymerization initiator is the combination and the positive type of the (a). Particularly preferred.

As a polyvalent acrylate which comprises a negative radiation sensitive component, the compound which has two or more (meth) acryloyl groups among the (meth) acryloyl-group containing compounds used for the inorganic particle containing resin composition of this invention mentioned above Can be mentioned. These can be used individually or in combination of 2 or more types.

In addition, specific examples of the photopolymerization initiator constituting the negative radiation-sensitive component include benzyl, benzoin, benzophenone, myrrheketone, 4,4'-bisdiethylaminobenzophenone, camphorquinone and 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl]- 2-morpholino-1-propaneone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4-diethyl thioxanthone, isopropyl thi Carbonyl compounds such as oxanthone; Phosphine oxide compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Azo compounds or azide compounds such as azoisobutylonitrile and 4-azide benzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 2,4-bis (trichloromethyl) -6- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-franyl) ethylenyl] -4,6-bis Trihalo methanes such as (trichloromethyl) -1,3,5-triazine; Imidazole dimers such as 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl1,2'-biimidazole, and the like. It can use combining a species or more. Furthermore, a sensitizer, a sensitizer, a hydrogen donor, and a chain transfer agent can be used together.

On the other hand, as a positive type radiation sensitive compound, the 1, 2- benzoquinone diazide- 4-sulfonic acid ester of a polyhydroxy compound, the 1, 2- naphthoquinone diazide- 4-sulfonic acid ester, and 1, 2- naphtho Quinonediazide-5-sulfonic acid ester, 1,2-naphthoquinone diazide-6-sulfonic acid ester, etc. are mentioned, Especially 1,2-naphthoquinone diazide- 4-sulfonic acid ester and 1,2-nap Toquinone diazide-5-sulfonic acid ester is preferable.

A radiation sensitive compound can be obtained by, for example, reacting a polyhydroxy compound with quinonediazidesulfonyl chloride in the presence of a basic catalyst. Usually, the ratio (average esterification rate) of the quinone diazide sulfonic acid ester with respect to the total hydroxyl group of a polyhydroxy compound is 20% or more and 100% or less, Preferably it is 40% or more and 95% or less. If the average esterification rate is too low, pattern formation is difficult, and if too high, it may cause a decrease in sensitivity.

Although it does not specifically limit as a polyhydroxy compound used here, The compound shown by following formula (3)-formula (8) is mentioned as a specific example.

In formula, X <_1> -X <_16> is the same or different, respectively, and is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C6-C10 aryl group, or a hydroxyl group. Provided that X ₁ to X ₂ and X ₆ to X ₁₀ In each combination, at least one is a hydroxyl group. In addition, Y <_1> is a hydrogen atom or a C1-C4 alkyl group.

In formula, X <_16> -X <_30> is the same or different each other, and is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C6-C10 aryl group, or a hydroxyl group. However, X ₁₆ to X _20, X ₂₁ to at least one dog in each combination of X ₂₅ and X ₂₆ to X ₃₀ is a hydroxyl group. In addition, Y <_2> -Y <_4> is the same or different from each other, and is a hydrogen atom or a C1-C4 alkyl group.

Wherein, X ₃₁ to X ₄₄ are each different and each is an aryl group or a hydroxyl group of an alkoxy group, having 6 to 10 carbon atoms in the alkyl group of the hydrogen atoms having from 1 to 4 carbon atoms, 1 to 4 carbon atoms each, provided that in X ₃₃ to X _35, at least One is a hydroxyl group, Y <_5> -Y <_8> is mutually different from each other, and is a hydrogen atom or a C1-C4 alkyl group.

In the formula, X ₄₅ to X ₆₈ are different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a hydroxyl group, except that X ₄₅ At least one in each combination of to X ₄₈ and X ₄₉ to X ₅₃ is a hydroxyl group, and Y ₉ and Y ₁₀ are each different from each other and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms.

Wherein, X ₅₉ to X ₈₀ are, each different from each other, and represents a hydrogen atom, a halogen atom, having from 1 to 4 carbon atoms, an alkoxy group, a cycloalkyl group or a hydroxyl group having 5 to 7 carbon atoms of 1 to 4 carbon atoms, provided that, X ₅₉ To X ₆₃ , X ₆₄ to X ₆₇ , X ₇₂ to X ₇₅ and X ₇₆ to X ₈₀ , at least one is a hydroxyl group, and Y ₁₁ to Y ₁₆ are each different from each other and are hydrogen atoms or 1 to 1 carbon atoms. It is an alkyl group of 4.

Wherein X ₈₁ to X ₉₀ are the same as or different from each other, and each is a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydroxyl group, provided that at least one of the hydroxyl groups in the combination of X ₈₁ to X ₉₀ is to be.

As a content rate of the radiation sensitive component in this alkali developing radiation sensitive resist composition, it is 1-200 weight part normally per 100 weight part of alkali-soluble resin, Preferably it is 5-100 weight part.

In addition, an alkali solvent is suitably contained with respect to alkali developing radiation sensitive resist composition in order to provide favorable film formation. As such an organic solvent, the solvent illustrated as what comprises an inorganic particle containing resin composition is mentioned.

In the resist composition used in the present invention, as an optional component, various additives such as a development accelerator, adhesion preparation, an antihalation agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a surface tension regulator, a leveling agent, a filler, a phosphor, a pigment, and a dye are used. May be contained. Moreover, you may contain the said inorganic particle used for the inorganic particle containing resin composition of this invention.

<Development amount>                     

As a developing solution used at the development process of a resist film, it can select suitably according to the kind of resist film (resist composition). Specifically, an alkaline developer can be used for the resist film of the alkali developing radiation-sensitive resist composition.

Examples of the active component of the alkaline developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, Inorganic alkaline compounds such as lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and ammonia; Tetramethylammonium Hydroxide, Trimethylhydroxyethylammonium Hydroxide, Monomethylamine, Dimethylamine, Trimethylamine, Monoethylamine, Diethylamine, Triethylamine, Monoisopropylamine, Diisopropylamine, Ethanolamine Organic alkaline compounds, such as these, etc. are mentioned.

The alkaline developer used in the development step of the resist film can be produced by dissolving one or two or more kinds of the alkaline compounds in water or the like. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. The alkali developer may contain additives such as nonionic surfactants or organic solvents.

Moreover, after the image development process by alkaline developing solution is performed, the water washing process is normally performed.

<Etching liquid>                     

As an etching liquid used at the etching process of an inorganic particle containing resin layer, it is preferable that it is an alkaline solution. Thereby, alkali-soluble resin contained in an inorganic particle containing resin layer can be easily dissolved and removed.

Moreover, when the inorganic particle contained in an inorganic particle containing resin layer is disperse | distributed uniformly by alkali-soluble resin, an inorganic particle is also removed simultaneously by dissolving and wash | cleaning alkali-soluble resin with alkaline solution.

Here, as an alkaline solution used as an etching solution, it is more preferable that it is a solution of the same composition as a developing solution.

Because the etching solution is the same solution as the alkaline developer used in the developing step, the developing step and the etching step can be performed continuously, and the process can be simplified.

In addition, after the etching process by alkaline solution is performed, the water washing process is performed normally. Moreover, you may include the process of rubbing off the unnecessary part remain | survive on the pattern side surface and board | substrate exposed part of an inorganic particle containing resin layer after an etching process as needed.

The dielectric constituting the PDP can also be formed by transferring the inorganic particle-containing resin layer constituting the transfer film of the present invention to the surface of the substrate and firing the transferred inorganic particle-containing resin layer.

An example of the transfer process of the inorganic particle containing resin layer by the transfer film of the structure as shown in FIG. 2 is as follows.                     

(1) Cut the transfer film in a rolled shape into a size suitable for the area of the substrate.

(2) After peeling the cover film (F3) from the surface of the inorganic particle-containing resin layer (F2) in the cut transfer film, the transfer film is polymerized so that the surface of the inorganic particle-containing resin layer (F2) is in contact with the surface of the substrate. Let's do it.

(3) Move the heating roller onto the transfer film superimposed on the substrate to perform thermal compression.

(4) The support film F1 is peeled off from the inorganic particle-containing resin layer F2 fixed to the substrate by thermocompression bonding.

By the above operation, the inorganic particle-containing resin layer F2 on the support film F1 is transferred onto the substrate. Here, as transfer conditions, the surface temperature of a heating roller is 60-120 degreeC, the roll pressure by a heating roller is 1-5 kg / cm <2>, and the moving speed of a heating roller is 0.2-10.0 m / min, for example. Such an operation (transfer process) can be performed by a laminator apparatus. Moreover, the board | substrate may be preheated and can be 40-100 degreeC as preheating temperature, for example.

The inorganic particle-containing resin layer F2 formed on the surface of the substrate is fired to form a sintered body (dielectric). Here, as a baking method, the method of arrange | positioning the board | substrate with which the inorganic particle containing resin layer F2 was formed under high temperature conditions is mentioned. Thereby, the organic substance contained in the inorganic particle containing resin layer F2 is decomposed | disassembled and removed, an inorganic particle melts and it sinters.

Hereinafter, although the Example of this invention is described, this invention is not limited by these. In addition, "part" represents a "weight part" below.

<Example 1>

(1) Preparation of Inorganic Particle-Containing Resin Composition (Resin Composition for Electrode Formation):

(A) Low-melting glass flits of Bi ₂ O ₃ -ZnO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ based 100 parts Ag particles having an average particle diameter of 1 μm and inorganic particles having an average particle diameter of 1 μm , Softening point 520 ° C.), 10 parts, (B) methacrylic acid n-butyl / methacrylic acid 3-hydroxypropyl / methacrylic acid = 60/20/20 (wt%) copolymer (Mw-100,000) 30 parts, (C) 10 parts of "Cymel 300" (made by Mitsui Saiamide) as a specific compound, 100 parts of propylene glycol monomethyl ether acetate as a solvent (D), and 10 parts of trimethylol propane triacrylate as an optional component And 1 part of stearic acid (dispersant) were kneaded with a bead mill and then filtered with a stainless mesh (500 mesh, 25 µm diameter) to prepare an inorganic particle-containing resin composition of the present invention.

(2) Preparation of alkali developing radiation sensitive resist composition

60 parts of methyl methacrylate / methacrylic acid = 70/30 (weight%) copolymer (Mw = 60,000) as alkali-soluble resin, 40 parts of pentaerythritol tetraacrylate as a polyvalent acrylate (radiation sensitive component), a photoinitiator After mixing and dissolving 5 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as a (radiation sensitive component) and 100 parts of propylene glycol monomethyl ether acetate as a solvent, The alkali developing radiation sensitive resist composition (hereinafter referred to as "resist composition 1") was produced by filtering with a cartridge filter (1 탆 diameter).                     

(3) Preparation of Transfer Film

By the operation of following (a) and (b), the transfer film of this invention in which the laminated film of a resist film and an inorganic particle containing resin layer was formed on the support film was produced.

(A) The resist composition 1 prepared in the above (2) was coated on a supporting film made of a PET film (400 mm wide, 30 m long, 38 μm thick) previously released by using a die coater, and the coating film was 100 It dried at 5 degreeC for 5 minutes, and the solvent was removed completely and the resist film of thickness 5micrometer was formed on the support film.

(B) The inorganic particle-containing resin composition prepared in (1) was applied onto the resist film using a die coater, the coating film was dried at 100 ° C. for 5 minutes to completely remove the solvent, and the inorganic particle-containing water having a thickness of 20 μm. The ground layer was formed on the resist film.

(4) evaluation of flexibility of transfer film

When the flexibility of the transfer film was evaluated by bending the transfer film prepared in the above (3) and visually confirming the occurrence of cracks on the surface of the inorganic particle-containing resin layer, the crack on the surface of the inorganic particle-containing resin layer It was not recognized and the said inorganic particle containing resin layer had the outstanding flexibility.

(5) Transfer of Inorganic Particle-Containing Resin Layer (Evaluation of Transferability of Transfer Film):

The transfer film produced in said (4) was polymerized so that the surface of an inorganic particle containing resin layer might contact the glass substrate surface previously heated at 80 degreeC on the hotplate, and this transfer film was thermocompression-bonded with the heating roller.

Here, as crimping conditions, the surface temperature of the heating roller is 120 deg. C, the roll pressure is 4 kg / cm, and the moving speed of the heating roller is 0.5 m / min (condition (1)) and 0.1 m / min (condition (2)). It was. After completion of the thermocompression bonding under each condition, the support film was peeled off and removed from the transfer film (the surface of the resist film), and the transferability evaluation of the transfer film was performed by visually confirming the state where the laminated film was transferred to the surface of the glass substrate. As a result, the transferred laminated film was in close contact with the surface of the glass substrate, and transferability was good.

(6) Firing of Inorganic Particle-Containing Resin Layer (Evaluation of Patterning Characteristics)

I-line (ultraviolet light having a wavelength of 365 nm) is irradiated from ultra-high pressure mercury or the like to the resist film of the laminated film formed on the glass substrate in the above (5) through an exposure mask (100 m wide stripe pattern). 200 mJ / cm 2), and then to the exposed resist film, a development process of the resist film by a shower method using 0.1 wt% tetramethylammonium hydroxide aqueous solution (30 ° C.) as a developer is carried out. Subsequent to the treatment, an etching treatment of the inorganic particle-containing resin layer by a shower method using 0.1 wt% tetramethylammonium hydroxide aqueous solution (30 ° C.) as an etching solution was performed. The total processing time was 90 seconds.

Subsequently, the water washing process and the drying process by ultrapure water were performed, and the glass substrate in which the pattern of the inorganic particle containing resin layer was formed was baked for 30 minutes in air | atmosphere under the temperature condition of 600 degreeC in the baking furnace. Thereby, the panel material in which the electrode pattern which consists of sintered compacts was formed in the surface of a glass substrate was obtained.

When the patterning characteristic evaluation was performed by observing the deformation | transformation of a pattern and the presence or absence of the peeling with the optical microscope with respect to the electrode pattern in the obtained panel material, the deformation and peeling of the pattern did not generate | occur | produce.

<Example 2>

(1) Preparation of Inorganic Particle-Containing Resin Composition (Resin Composition for Black Electrode Formation):

(A) 50 parts of Ag particles having an average particle diameter of 1 μm, 50 parts of Ni particles (spherical) having an average particle diameter of 0.2 μm, and Bi ₂ O ₃ -ZnO-B ₂ O ₃ -SiO having an average particle diameter of 3 μm. 10 parts of ₂ -Al ₂ O ₃ system low melting glass fleece (an amorphous form, softening point 520 ° C.), (B) n-butyl / methacrylic acid 3-hydroxypropyl / methacrylic acid as a binder resin = 60 / 20 parts by weight of 20/20 (% by weight) copolymer (Mw = 100,000), (C) 20 parts of `` Synol 300 '' (manufactured by Mitsui Cyamide) as a specific compound, and (D) propylene glycol monomethyl ether acetate The inorganic particle-containing resin composition of the present invention was prepared by kneading 100 parts of trimethylolpropanetriacrylate and 1 part of oleic acid (dispersant) as a bead mill, followed by filtering with a stainless mesh (500 mesh, 25 μm diameter) as 100 parts and optional components. Prepared.

(2) Preparation of alkali developing radiation sensitive resist composition (resin composition for electrode formation):

Methacrylic acid n-butyl / methacrylic acid 3-hydroxypropyl / methacrylic acid = 60/20/20 (wt%) copolymer (Mw = 100,000) as alkali-soluble resin, polyvalent acrylate (radiation-sensitive) 40 parts of trimethylolpropane triacrylate as a component), 5 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as a photoinitiator (radiation sensitive component), inorganic 250 parts of Ag particles having an average particle diameter of 1 μm and Bi ₂ O ₃ -ZnO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ based low-melting glass flits (negative, softening point of 540 ° C.) as particles. ) 30 parts, and 100 parts of propylene glycol monomethyl ether acetate as a solvent, and 1 part of stearic acid (dispersant) as an optional component by kneading with a bead mill, and then filtered with a stainless mesh (500 mesh, 25 ㎛ diameter), alkali A radioactive resist composition (hereinafter referred to as "resist composition 2") was prepared.

(3) Preparation of Transfer Film

By the operation of (a) and (b), the transfer film of this invention in which the laminated film of a resist film and an inorganic particle containing layer was formed on the support film was produced.

(A) Applying a resist plate on the support film which consists of PET film (width: 400 mm, length: 30 m, thickness 38 micrometers) previously mold-released the resist composition 2 manufactured by said (2), The coating film was dried at 100 ° C. for 5 minutes, and the solvent was completely removed to form a resist film having a thickness of 20 μm on the supporting film.

(B) Applying the inorganic particle-containing resin composition prepared in (1) above using a doctor plate on a resist film, drying the coating film at 100 ° C. for 5 minutes to completely remove the solvent to contain inorganic particles having a thickness of 10 μm. The resin layer was formed on the resist film.

(4) evaluation of flexibility of transfer film

By flexing the transfer film prepared in the above (3) and visually confirming the occurrence of cracks (bending cracks) on the surface of the inorganic particle-containing resin layer, the flexibility of the transfer film was evaluated. No crack was found on the surface, and the inorganic particle-containing resin layer had excellent flexibility.

(5) Transfer of Inorganic Particle-Containing Resin Layer (Evaluation of Transferability of Transfer Film):

The transfer film produced in said (4) was superposed | polymerized so that the surface of an inorganic particle containing resin layer might contact the surface of the glass substrate previously heated at 80 degreeC on the hotplate, and this transfer film was thermocompression-bonded with the heating roller.

Here, as crimping | compression-bonding conditions, the surface temperature of a heating roller is 120 degreeC, a roll pressure is 4 kg / cm, the moving speed of a heating roller is 0.5 m / min (condition (1)), and 0.1 m / min (condition (2)) It was made. After completion of the thermocompression bonding under each condition, the support film was peeled off and removed from the transfer film (the surface of the resist film), and the transferability evaluation of the transfer film was performed by visually confirming the state where the laminated film was transferred to the surface of the glass substrate. As a result, the transferred laminated film was in close contact with the surface of the glass substrate and the transferability was good.

(6) evaluation of patterning characteristics

The resist film in the laminated film formed on the glass substrate in (5) above is irradiated with i-line (ultraviolet light having a wavelength of 365 nm) from an ultra-high pressure mercury lamp through an exposure mask (100 m wide stripe pattern). mJ / cm 2), and then, the exposed resist film is subjected to the development of the resist film by a shower method using 0.5% by weight of a sodium carbonate aqueous solution (30 ° C.) as a developing solution, followed by 0.5% by weight of the development process. The inorganic particle containing resin layer was etched by the shower method which uses the sodium carbonate aqueous solution (30 degreeC) as an etching liquid. The processing time of the sum was 90 seconds.                     

Subsequently, the water washing process and the drying process by ultrapure water were performed, and the glass substrate in which the pattern of the inorganic particle containing resin layer was formed was baked in air in the kiln for 30 minutes under the temperature condition of 600 degreeC. This obtained the panel material in which the electrode pattern which consists of a sintered compact is formed in the surface of a glass substrate.

When the patterning characteristic evaluation was performed by observing the deformation | transformation of a pattern and the presence or absence of peeling with the optical microscope with respect to the electrode pattern in the obtained panel material, the deformation and peeling of the pattern did not generate | occur | produce.

Comparative Example 1

A comparative composition was produced in the same manner as in Example 1 (1) except that no specific compound was used, and a comparative transfer film was prepared in the same manner as in Example 1 (3) except that the composition was used. It was.

When the transfer film thus obtained was subjected to the flexibility evaluation in the same manner as in Example 1 (4), when the transfer film was bent, cracks were remarkably recognized on the surface of the inorganic particle-containing resin layer to contain the inorganic particles. The resin layer was inferior in flexibility.

Moreover, except having used the obtained transfer film, it carried out similarly to Example 1 (5), and performed transferability evaluation by carrying out the transfer film | membrane, but it did not have favorable transferability with respect to the surface of a glass substrate.

In addition, except that the glass substrate which transferred and formed the inorganic particle containing resin layer was carried out similarly to Example 1 (6), by etching and baking, the electrode which consists of a sintered compact is formed in the surface of a glass substrate, and patterning characteristic evaluation is carried out. It was confirmed that deformation of the pattern and peeling occurred.

The evaluation results regarding the flexibility, the transferability, and the patterning characteristics of the electrode pattern of the transfer film according to the above Examples 1 to 2 and Comparative Example 1 were collectively shown in Table 1 below.

Flexibility Transcription Patterning properties Condition ① Condition ② Example 1 Good Good Good Good Example 2 Good Good Good Good Comparative Example 1 Bad Bad Bad Bad

According to the inorganic particle containing resin composition of this invention, the inorganic particle containing resin layer which is excellent in flexibility and a transferability, and does not produce distortion and peeling in the pattern of the sintered compact formed through an etching process and a baking process can be formed.

According to the transfer film of the present invention, the pattern of the target sintered body can be reliably formed from the inorganic particle-containing resin layer constituting this, so that the electrode, the partition, the resistor, the dielectric, the phosphor, the color filter and the black of the plasma display panel can be formed. It can be used suitably for matrix formation.

Moreover, according to the manufacturing method of the plasma display panel of this invention, the pattern with high dimensional precision can be formed and the outstanding workability can be obtained.

Claims (4)

(A) inorganic particles, (B) binder resin, (C) melamines, benzoguanamines or glycolurils containing 0.1 to 500 parts by weight of methylol group, alkoxymethyl group or both with respect to 100 parts by weight of inorganic particles, and (D) solvent Inorganic particle containing resin composition characterized by including the. The inorganic particle containing resin layer obtained from the inorganic particle containing resin composition of Claim 1 is formed on the support film, The transfer film characterized by the above-mentioned. The inorganic particle-containing resin layer constituting the transfer film according to claim 2 is transferred onto a substrate, a resist film is formed on the transferred inorganic particle-containing resin layer, and the resist film is exposed to light to form a resist pattern latent image, The resist film is developed to present a resist pattern, the inorganic particle-containing resin layer is etched to form an inorganic particle-containing resin layer pattern corresponding to the resist pattern, and the pattern is fired to form a partition, an electrode, a resistor, a dielectric And forming at least one of a phosphor, a color filter, and a black matrix. The laminated film of the resist film and the inorganic particle containing resin layer obtained from the inorganic particle containing resin composition of Claim 1 is formed on a support film, the said laminated film is transferred on a board | substrate, and the resist film which comprises the said laminated film is exposed-processed. By forming a resist pattern latent image, developing the resist film to present a resist pattern, etching the inorganic particle-containing resin layer to form an inorganic particle-containing resin layer pattern corresponding to the resist pattern, and firing the pattern And forming at least one of a partition wall, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix by treating the plasma display panel.

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