WO2004095495A1

WO2004095495A1 - Inorganic particle containing composition for plasma display panel, transfer film and process for producing plasma display panel

Info

Publication number: WO2004095495A1
Application number: PCT/JP2004/002170
Authority: WO
Inventors: Seiji Kawagishi; Takanori Yamashita; Katsumi Itoh; Yasutake Inoue
Original assignee: Jsr Corporation
Priority date: 2003-04-24
Filing date: 2004-02-25
Publication date: 2004-11-04
Also published as: KR20060005388A; CN100461328C; JP2004323654A; JP4337388B2; KR100859392B1; TWI248425B; TW200502188A; CN1777970A

Abstract

A composition containing inorganic particles for use in a plasma display panel; a transfer film from the composition; and a process for producing a plasma display panel. The composition comprises inorganic particles [A] and polymer [B] having repeating units of the formula (I). The composition may further comprise a plasticizer and/or a silane coupling agent. A transfer film having various excellent properties can be produced from the composition. Plasma display panel constituent elements excelling in various properties can be efficiently formed in a low temperature/short time firing step according to the process for producing a plasma display panel. The process is characterized in, for example, that it includes a step of forming a dielectric layer on a substrate by transferring a film forming material layer obtained from the composition onto the substrate and firing the transferred film forming material layer.

Description

Description Technical Fields for Manufacturing Inorganic Particle-Containing Compositions for Plasma Display Panels, Transfer Films, and Plasma Display Panels>

The present invention relates to an inorganic particle-containing composition for a plasma display panel, a transfer film, and a method for manufacturing a plasma display panel. Background technology>

In recent years, a plasma display has attracted attention as a flat fluorescent display. Figure 1 is a schematic diagram showing the cross-sectional shape of an AC-type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates opposed to each other, and reference numeral 3 denotes a partition. A cell is defined by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of lowering the resistance of the transparent electrode 4, 6 is an address electrode fixed on the glass substrate 2, and 7 is The fluorescent substance held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is the surface of the glass substrate 2 so as to cover the address electrode 6. The dielectric layer 10 formed on the substrate is a protective film made of, for example, magnesium oxide. In the case of color PDP, a color filter (red, green or blue), a black matrix, etc. may be provided between the glass substrate and the dielectric layer in order to obtain a high-contrast image.

As a method of manufacturing such PDP dielectrics, partition walls, electrodes, phosphors, color filters, and black stripes (matrix), a resin layer containing photosensitive inorganic particles is formed on a substrate, and a photomask is formed on the film. A method such as photolithography, in which a pattern is left on a substrate by irradiating with ultraviolet rays through the substrate and then developed, and the pattern is baked, is preferably used. The photolithography method has excellent pattern accuracy in principle, and a method using a transfer film can form a pattern having excellent film thickness uniformity and surface uniformity. However, if the baking conditions for a long time at a high temperature are set in the baking process of the film forming material layer and the film forming material layer is not sufficiently melted, cracks are likely to occur in the film forming material layer, and the high temperature Setting the firing conditions over a long period of time has a problem that the burden on the firing furnace is large and the productivity is reduced. Therefore, a low-temperature, short-time sintering step of the film-forming material layer is desired.

The present invention has been made based on the above circumstances.

A first object of the present invention is to provide a PDP component having excellent surface smoothness (for example, a partition, an electrode, a resistor, a dielectric layer, a phosphor, a color filter, Plaque matrix) can be suitably formed.

A second object of the present invention is to provide an inorganic particle-containing composition capable of producing a transfer film having excellent flexibility of a film-forming material layer.

A third object of the present invention is to provide an inorganic particle-containing composition capable of producing a transfer film excellent in transferability (heat adhesion to a substrate) of a film-forming material layer.

A fourth object of the present invention is to provide a transfer film capable of efficiently forming a component of PDP having excellent surface smoothness in a firing step at a low temperature and in a short time.

A fifth object of the present invention is to provide a transfer film excellent in flexibility of a film forming material layer.

A sixth object of the present invention is to provide a transfer film having excellent transferability (heat adhesion to a substrate) of a film-forming material layer.

A seventh object of the present invention is to provide a low-temperature, short-time firing An object of the present invention is to provide a PDP manufacturing method capable of efficiently forming a component of a PDP having excellent characteristics.

An eighth object of the present invention is to provide a PDP manufacturing method capable of efficiently forming a PDP with high positional accuracy of components in a firing step at a low temperature and in a short time.

A ninth object of the present invention is to provide a method of manufacturing a PDP which can efficiently form a dielectric layer having a large thickness in a firing step at a low temperature and in a short time.

A tenth object of the present invention is to provide a PDP manufacturing method capable of efficiently forming a dielectric layer required for a large panel in a firing step at a low temperature and in a short time.

An eleventh object of the present invention is to provide a method of manufacturing a PDP having a dielectric layer having excellent film thickness uniformity in a firing step at a low temperature and in a short time.

A second object of the present invention is to provide a method for producing a PDP having a dielectric layer having excellent surface smoothness in a firing step at a low temperature and in a short time.

The inorganic particle-containing composition of the present invention comprises [A] inorganic particles, and [B] a polymer having a repeating unit represented by the following formula (1) (hereinafter, also referred to as “polymer [B-1]”): And a binder resin containing: As a result, it is considered that the adsorption of the inorganic particles to the binder resin is strengthened, and the distance between the inorganic particles is reduced during firing, so that the firing can be performed at a low temperature and in a short time.

(I)

(In the formula, X represents a hydrogen atom or a methyl group, R ¹ represents a single bond, a methylene group or an alkylene group having 2 to 5 carbon atoms, and n represents an integer of 1 to 6.)

The inorganic particle-containing composition of the present invention further comprises a composition further comprising (C) a radiation-sensitive component. A composition (hereinafter, also referred to as a “radiation-sensitive inorganic particle-containing composition”) may be used. The transfer film of the present invention has a film-forming material layer obtained from the inorganic particle-containing composition.

In the first method for producing a PDP of the present invention (hereinafter, also referred to as “PDP production method (1)”), a film-forming material layer obtained from the inorganic particle-containing composition of the present invention is transferred to a substrate and transferred. Forming a dielectric layer on the substrate by firing the film forming material layer.

The second method for producing a PDP of the present invention (hereinafter, also referred to as “the method for producing a PDP (2)”) involves transferring a film-forming material layer obtained from the composition containing inorganic particles of the present invention onto a substrate, and transferring the film. Forming a resist film on the formed film forming material layer, exposing the resist film to form a latent image of the resist pattern, developing the resist film to make the resist pattern visible, By forming a pattern layer corresponding to the resist pattern by etching the forming material layer and baking the pattern layer, the partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black are formed. It is characterized by including a step of forming a component selected from Matritus.

Further, the third method for producing a PDP of the present invention (hereinafter, also referred to as “PDP production method (3)”) includes a resist film and a film forming material layer obtained from the inorganic particle-containing composition of the present invention. Is formed on a supporting film, the laminated film formed on the supporting film is transferred to a substrate, and a resist film constituting the laminated film is exposed to light to form a latent image of a resist pattern. The resist film is developed to reveal a resist pattern, the film forming material layer is etched to form a pattern layer corresponding to the resist pattern, and the pattern layer is baked to obtain partition walls, The method includes a step of forming a component selected from an electrode, a resistor, a dielectric layer, a phosphor, a color filter, and a black matrix.

Furthermore, the fourth method for producing a PDP of the present invention (hereinafter, also referred to as “the method for producing a PDP (4)”) comprises a method of forming a film-forming material layer obtained from the composition containing radiation-sensitive inorganic particles of the present invention on a substrate. Transferred to the top, and the film forming material layer is exposed to light to form a latent image of the pattern. Then, the film forming material layer is developed to form a pattern layer, and the pattern layer is baked to obtain a partition, an electrode, a resistor, a dielectric layer, a phosphor, a color filter, and a black matrix. Forming a selected component. Brief description of drawings>

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel. FIG. 2A is a schematic cross-sectional view showing a transfer film of the present invention, and FIG. 2B is a cross-sectional view showing a layer configuration of the transfer film.

FIGS. 3A to 3E are schematic cross-sectional views illustrating an example of a partition forming step (transfer step, resist film forming step and exposure step) in the manufacturing method of the present invention.

FIGS. 4A to 4D are schematic cross-sectional views illustrating an example of a partition forming step (a developing step, an etching step, and a firing step) in the manufacturing method of the present invention.

In the figure, the description of reference numerals is as follows.

1 Glass substrate

2 Glass substrate

3 Partition wall

4 Transparent electrode

5 Bus electrode

6 Address electrode

7 Fluorescent substance

8 Dielectric layer

9 Dielectric layer

1 0 Protective layer

F 1 support film

F 2 film forming material layer

F3 cover film

1 1 Glass substrate

Five

Replacement form (Rule 26) 1 2 electrode

1 3 Dielectric layer

2 0 Transfer film

2 1 Film forming material layer

2 2 Support film

2 5 Partition pattern layer

2 5 A Material layer residual area

2 5 B Material layer removal section

3 1 Resist film

3 5 Register pattern

3 5 A Residual resist

3 5 B Register removal section

4 0 Partition wall

5 0 Panel material

M Exposure mask

MA light transmission section

M B Shading section

Hereinafter, the inorganic particle-containing composition (hereinafter, also simply referred to as “composition”) of the present invention will be described in detail.

The composition of the present invention usually contains inorganic particles, a binder resin and a solvent. The polymer [B_1] is contained in the binder resin.

The inorganic substance constituting the inorganic particles constituting the composition of the present invention is not particularly limited, and may be appropriately selected according to the use of the sintered body formed from the composition (the type of component of the PDP). can do.

Here, a composition for forming the “dielectric layer” or “partition” that constitutes the PDP Examples of the inorganic particles include glass powders having a softening point in the range of 350 to 700 ° C (preferably 400 to 600 ° C). If the softening point of the glass powder is less than 350 ° C., the glass powder is not completely decomposed and removed in the step of firing the film-forming material layer with the composition at a stage where the organic substance such as a binder resin is not completely removed. Because of the melting, a part of the organic substance remains in the formed dielectric layer, and as a result, the dielectric layer tends to be colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 700 ° C., the glass substrate needs to be fired at a temperature higher than 700 ° C., so that the glass substrate is distorted.

Specific examples of suitable glass powder include (1) a mixture of lead oxide, boron oxide and silicon oxide (PbO—B203—Si02), (2) lead oxide, boron oxide, silicon oxide and A mixture of magnesium oxide (PbO-B203-Si02_Mg0), (3) a mixture of lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO-B203-Si02-A1203), (4) a mixture of lead oxide and boron oxide Mixtures of silicon oxide, silicon oxide and calcium oxide (PbO-B203-Si02-CaO), (5) mixtures of lead oxide, zinc oxide, boron oxide and silicon oxide (PbO-Zn0_B20s-Si02) Can be.

These glass powders may be contained (combined) in a composition for forming constituent elements other than the dielectric layer and the partition walls (for example, electrodes, antibodies, phosphors, color filters, or plaque matrices). The content of the glass frit in the inorganic particle-containing resin composition for obtaining these panel materials is usually 90% by weight or less, preferably 50 to 90% by weight, based on the total amount of the inorganic particles. .

Examples of the inorganic particles contained in the composition for forming the “electrode” constituting PDP include metal particles made of Ag, Au, Al, Ni, Ag_Pd alloy, Cu, Cr, and the like.

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

Inorganic particles contained in the composition for forming the "resistor" constituting the PDP; For example, particles made of Ru02 or the like can be used.

Is the inorganic particles contained in the composition for forming a "phosphor" constituting a _{PDP, Y203: Eu 3+, Y2S1O5} : Eu 3+, Y3AI5O12: Eu 3+, YV04: Eu 3+, (Y, Gd) B03: Eu ₃₊ , Zn3 (P04) 2: Red fluorescent substance such as Mn; Zn2Si04: Mn, BaAll20i9: Mn, BaMgAl i4023: Mn, LaP04: (Ce, Tb), Y3 (A1, Ga) 5O12: Tb and other green fluorescent materials; Y ₂ Si05: Ce, BaMgAlloOi7: Eu ₂₊ , BaMgAll4023: Eu _{2 + S} (Ca, Sr, Ba) 10 (PO4) 6CI2: Eu ₂₊ (Zn, Cd ) S: Particles composed of a blue fluorescent substance such as Ag can be cited.

Inorganic particles contained in the composition for forming the `` color filter '' that constitutes the PDP include red substances such as Fe203 and Pb304, green substances such as Cr203, and blue substances such as 2 (Al2Na2Si30io) and Na2S4. Examples include particles made of a substance.

Examples of the inorganic particles contained in the composition for forming “black matrix” constituting PDP include particles composed of Mn, Fe, Cr, and the like. <Binder resin>

The binder resin constituting the composition of the present invention is a resin containing the polymer [B-1]. The binder resin may be the polymer [B-1] alone, or may be a mixture with another polymer. As the other polymer, an acrylic resin other than the polymer [B-1] is preferably used.

The polymer [B_1] is a polymer having a repeating unit represented by the above formula (1), and is preferably an acrylic resin. By containing the acrylic resin as the binder resin, the formed film-forming material layer exhibits excellent (heat) adhesion to the substrate. Therefore, when a transfer film is produced by applying the composition of the present invention on a support film, the transfer film obtained is excellent in transferability of the film-forming material layer (heat adhesion to the substrate). Become.

As the acrylic resin (polymer [B-1] and other polymers) constituting the composition of the present invention, the acrylic resin having appropriate tackiness and capable of binding inorganic particles can be used. It is selected from (co) polymers that are completely oxidized and removed by baking (400 to 600 ° C). The repeating unit represented by the above formula (1) is formed by (co) polymerizing a monomer 'represented by the following formula (i).

(i)

(In the formula, the definitions of X, R ¹ and n are the same as in the above formula (1).)

In the above formula (i), R ¹ is particularly preferably a single bond or a methylene group. Further, n is particularly preferably 1.

Specific examples of the monomer represented by the above formula (i) include glycidyl (meth) acrylate,] 3-methyldaricidyl (meth) atalylate, (meth) atalyloyl methizolecyclohexene oxide, 3,41- Epoxycyclohexynolemethinole (meta) atalylate and the like.

The polymer [: B-1] is preferably a copolymer of the monomer represented by the above formula (i) and another monomer, and the other monomer includes other (meth) acrylates. Compounds are preferred.

Specific examples of such other (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl. (Meth) acrylate, ί-butyl (meta) acrylate, pentyl (meta) acrylate, amyl (meth) acrylate, isoamyl (meta) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate Rate, octyl (meth) acrylate, isococtyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meta) acrylate, pendecyl (Me ) Atari rate, dodecyl (meth) Atarire door, lauryl (meth) Atari rate, steer Lil (meth) Atari rate, isostearyl (meth) Al, such as Atari rate Kill (meta) atarilate;

Hydroxyshetyl (meth) acrylate, 2-hydroxypropyl (meth) phthalate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meta) ) Acrylates, hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate;

Phenoxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate such as 2-pilloxy (meta) phthalate; 2-methoxyxyl (meth) acrylate, 2-methoxyxyl (meth) acrylate Alkoxyalkyl (meth) acrylates, such as acrylates, 2-propoxyshetyl (meth) acrylate, 2-butoxystyl (meth) acrylate, and 2-methoxybutyl (meth) acrylate;

Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycolone (meta) acrylate, phenolic polyethylene glycol Polyalkylenes such as glycol (meth) atalylate, polypropylene glycol (meth) atalylate, methoxy polypropylene glycol (meth) atalylate, ethoxy polypropylene glycol (meth) atalylate, and ultraphenoxy polypropylene glycol (meta) acrylate Glycol (meth) acrylate;

Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, pentaninole (meta) acrylate, dicyclo-pentene; penta (meta) acrylate, dicyclopentagel Cycloalkyl (meth) atalylates such as (meth) atarilate, boluel (meth) atalylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; benzyl (meth) atalylate, tetrahydrofurfuryl (meta) acrylate And the like. These (meth) atalylate compounds can be used alone or in combination of two or more. Of these, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates and alkoxyalkyl (meth) acrylates are preferred, and particularly preferred (meth) acrylate compounds are butyl (meth) acrylate, Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethoxyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate it can.

The monomer other than the (meth) acrylate compound is not particularly limited as long as it is a compound copolymerizable with the (meth) atalylate compound. Examples thereof include (meth) acrylic acid, bier benzoic acid, and maleic acid. Unsaturated kelevonic acids such as phthalene, butylphthalic acid, etc .; vinylinole group-containing radical polymerizable polymers such as vinylinolebenzizolemethinoleatenole, vinylenoglycidinoleatenoate, styrene, α-methinolestyrene, butadiene, isoprene, etc. Compounds.

In addition, when forming a component of PD II using the photoresist method described below, when the alkali-solubility is required for the etching treatment of the film-forming material layer, the above-mentioned other copolymerizable monomer (copolymerizable monomer) may be used. As the component), a carboxyl group-containing monomer is preferably contained. Specific examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamate, and succinic acid mono (2- ( (Meta) acryloyloxetil), _ω -carboxy-polyproprolatatone mono (meth) acrylate. Of these, methacrylic acid is preferred.

Here, specific examples of preferred alkali-soluble resins include, for example, (meth) acrylic resins, hydroxystyrene resins, nopolak resins, polyester resins and the like.

Of these alkali-soluble resins, preferred are the above-mentioned carboxyl group-containing monomer and alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate or alkoxyalkyl (meth) acrylate. Examples of preferred (meth) acrylate compounds include butyl (meth) acrylate, ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. T) acrylate, isododecyl (meth) acrylate, 2-ethoxyhexyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate can be mentioned.

In the polymer [B-1], the proportion of the monomer represented by the above formula (i) is usually 0.1 to 50 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of all monomers. 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

The molecular weight of the polymer [B-1] is expressed as a weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter, referred to as “GPC”) (hereinafter, also simply referred to as “weight average molecular weight”). It is preferably from 4,000 to 300,000, and more preferably from 10,000 to 200,000. Further, as another polymer which may be used as a mixture with the polymer [B-1], a polymer containing the above-mentioned other (meth) atalylate compound can be preferably mentioned.

The proportion of the repeating unit represented by the above formula (1) in the whole binder resin is usually 0.1 to 50% by weight, preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight. is there. Further, the proportion of the repeating unit derived from (meth) acrylate in the whole binder resin (including the repeating unit represented by the above formula (1)) is preferably 70% by weight or more, and more preferably 90% by weight or more. % Or more.

The content ratio of the binder resin in the composition of the present invention is preferably 5 to 80 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the inorganic particles. . When the proportion of the binder resin is less than 5 parts by weight, the inorganic particles cannot be securely bound and held.On the other hand, when the proportion exceeds 80 parts by weight, a long time is required for the firing step. It may be necessary or the formed sintered body (for example, a dielectric layer) may not have sufficient strength and film thickness.

Solvent>

The composition of the present invention usually contains a solvent. Examples of the solvent include those having good affinity for inorganic particles and good solubility of the binder resin, capable of imparting a suitable viscosity to the obtained composition, and which can be easily evaporated and removed by drying. Is Is preferred.

Specific examples of such a solvent include ketones such as getyl ketone, methyl butyl ketone, di-open pinole ketone and cyclohexanone; /? "Pentanole, 4-methinole-2-pentanole, cyclohexanole, diacetone Noreco noles such as Noreco nore; Ethylene glycol monomethinolate monoethylene, Ethylene glycol monomethinolate monoethylene, Ethylene glycol monoleno Petite / Leatenole, Propylene daryco monomethinele mononoteno, Propylene glycol monolenoethylene Ether alcohols such as lethenole; alkyl esters of unsaturated aliphatic monocarbonates such as butyl acetate and amyl acetate; lactate esters such as ethyl lactate and lactate-butyl-butyl; methinoreserosonolep acetate; Echinoreseroso And ether esters such as levoacetate, propylene glycol monomethinoleate enorea acetate, ethinole-3-ethoxypropionate, etc. These can be used alone or in combination of two or more. Can be used.

The content ratio of the solvent in the composition of the present invention is preferably 40 parts by weight or less based on 100 parts by weight of the inorganic particles from the viewpoint of maintaining the viscosity of the composition in a suitable range. It is more preferably 5 to 30 parts by weight.

Dispersant>

The composition of the present invention preferably contains a dispersant. As the dispersant, a silane coupling agent [saturated alkyl group-containing (alkyl) alkoxysilane] represented by the following formula (2) is preferable.

Η2ρ + ι〇ρ ~~ (-OC _m H _2m + i)

PA, (2)

\ 1 3-a

(Where p is an integer from 3 to 20, m is an integer from 1 to 3, n is an integer from 1 to 3, and a is an integer from 1 to 3.)

In the above formula (2), p indicating the number of carbon atoms of the saturated alkyl group is an integer of 3 to 20 and preferably an integer of 4 to 16.

containing a saturated alkyl group-containing (alkyl) alkoxysilane having p less than 3 However, sufficient flexibility may not be exhibited in the obtained film forming material layer. On the other hand, saturated alkyl group-containing (alkyl) alkoxysilanes having a P value of more than 20 have a high decomposition temperature, and the organic substance (the silane derivative described above) is completely decomposed and removed in the firing step of the obtained film forming material layer. Since the glass powder is melted at a stage where it is not performed, a part of the organic substance remains in the formed dielectric layer, and as a result, the light transmittance of the dielectric layer may decrease.

Specific examples of the silane coupling agent represented by the above formula (2) include n-propyl dimethyl methoxy silane, n-butyl dimethyl methoxy silane, n-decyl dimethyl methoxy silane, n-hexadecyl dimethyl methoxy silane, n-cosa Alkyl dimethyl methoxy silanes such as dimethyl methoxy silane (a = 1, m = l, n = 1);

Saturated anolequinolegers such as _n- propinorejectyl methoxysilane, _n- butinorejetinolemethoxysilane, _n- decinorejetinolemethoxysilane, _n- hexadeci / regetinolemethoxysilane, _n- icosanejetinolemethoxysilane Tilmethoxysilanes (a = 1, m = 1, n = 2);

Saturated alkyl dipropyl methoxy silanes (a = l, such as n-ptynoresylpropyl methoxysilane, n-decinoresolepropinolemethoxysilane, n-hexadecyldipropyl methoxysilane, and n-icosanedipropyl methoxy silane) , M = 1, η = 3);

Saturated alkyl dimethyl ethoxy silas such as η-propyl dimethyl ethoxy silane, η-butyl dimethyl ethoxy silane, η-decyl dimethinoleethoxy silane, _η -hexadecyl dimethyl ethoxy silane, η-icosane dimethyl ethoxy silane Class (a = 1, m = 2, n = 1);

n- professional Pinot Leger Chino Les silane, n- butyl Bruno Leger Chino Les silane, n- decyl Jefferies Chino Les silane, hexadecyl Jefferies chill E Toki silane to n-, _n - I co-San Jefferies chill E Toki silane such as Saturated alkyl ethethylethoxysilanes (a = 1, m = 2, n = 2);

n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, saturated alkyldipropylethoxysilanes (a = 1, m = 2, n = 3) such as n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane;

Saturated anolequinoresimetinos such as n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethinolepropoxysilane, n-icosanedimethizolepropoxysilane Le propoxysilanes (a = 1, m = 3, η = 1);

η-Propyl ethynolepropoxy silane, η-butynole ethynolepropoxy silane, η-decyl ethynolepropoxy silane, η-hexadeci / regetinole propoxy silane, η-ycosan getinolepropoxy silane Saturated anolequinolegetyl propoxysilanes such as silane (a = 1, m = 3, η = 2);

Saturated alkyldipropylpropoxysilanes such as η-butinoresylpropylpropoxysilane, η-decyldipropylpropoxysilane, η-hexadesinoresolepropinolepropoxysilane, η-icosanedipropynolepropoxysilane (a = 1, m = 3, n = 3);

n- propyl-methylol Roh regime Tokishishiran, n- Petit Honoré methylate Roh regime Tokishishiran, n- Deshirumechirujime Tokishishiran, hexadecyl methyl dimethyl Tokishishiran to n-, _n - I co San saturated alkyl methyl dimethyl Tokishishira emissions such as methyl dimethyl Tokishishiran (a = 2, m = 1, η = 1);

η- professional Pinot milled by wet Chino regime Tokishishiran, η- butyrate Norre ethyl Roh regime Tokishishiran, η- Deshiruechirujime Tokishishiran, hexadecyl E chill dimethyl Tokishishiran to _η-, η - concentrated acid E saturated alkyl E chill dimethyl Tokishishira emissions such as Chino regimen Tokishishiran ( a = 2, m = 1, η = 2);

Saturated alkyl pyrumethoxysilanes such as η-ptinolepropyldimethoxysilane, η-decylpropyldimethoxysilane, η-hexadecylpropyldimethoxysilane, η-icosanpropyldimethoxysilane (a = 2, m = 1, η = 3)

η-Propyl methino rejetoxy silane, η-Peptinole methino reethoxy silane, Saturated alkyl methyl ethoxy silanes such as _n -decyl methino reethoxy silane, _n -hexadecyl methyl ethoxy silane, _n- icosane methyl ethoxy silane (a = 2, m = 2, n = 1) ;

n- propyl E chill jet silane, n- butyl E chill jet silane, n one deci / Les ethyl Honoré jet silane, n to single hexa Desi Roh Ree Chino Leger butoxy silane, _n - I co San E chill jet silanes such as Saturated alkyl ethyl ethoxy silanes (a = 2, m = 2, η = 2);

Saturated alkyl propyl ethoxy silanes such as η-butyl propyl ethoxy silane, η-decyl propyl ethoxy silane, η-hexadecinole propyl ethoxy silane, η- icosan propyl ethoxy silane (a = 2, m = 2, η = 3);

η-propynolemethinoresipropoxysilane, η-butinoremethinoresipropoxysilane, η-decinolemethinoresipropoxysilane, η-hexadecinolemethinoresipropoxysilane, η-icosanemethyldipropoxysilane Saturated alkylmethinoresipropoxysilanes (a = 2, m = 3, η = 1) such as;

η-propynoleethinoresolepropoxysilane, η-butynolethinoresolepropoxysilane, η-decylethyldipropoxysilane, η-hexadecylethyldipropoxysilane, η-icosaneethyldipropoxysilane, etc. Saturated anolequinolethienoresipropoxysilanes (a = 2, m = 3, η = 2);

Saturated alkyl pill dipropoxy silanes such as η-butyl propyl dipropoxy silane, η-decyl propyl dipropoxy silane, η _ hexadecyl propyl dipropoxy silane, η- icosan propyl dipropoxy silane (a = 2, m = 3, n = 3);

Saturated alkyltrimethoxysilanes such as n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosantrimethoxysilane (a = 3, m = 1); n-propyltriethoxysilane N-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosant Saturated alkyltriethoxysilanes such as riethoxysilane ( _a = 3, m = 2); n-propyltripropoxysilane, n-butyltripropoxysilane, n_decyltripropoxysilane, n-hexadecyltrip Saturated alkyl tripropoxy silanes (a = 3, m = 3) such as roboxy silane and n-icosane tripropoxy silane can be exemplified. These can be used alone or in combination of two or more.

Of these, n- Buchirutorime Tokishishiran, n- Deshirutorime Tokishishira emissions, n - to Kisadeshirutorime Tokishishiran, n- decyl dimethyl main Tokishishiran, _n - the hexadecyl dimethyl main Tokishishiran, _n - heptyl triethoxysilane, n - decyl triethoxysilane , n - the hexadecyl triethoxysilane, n- deci Rue chill jet silane, _n - the hexadecyl E chill jet silane, _n - Bed tilt Li propoxysilane, n- decyl triple Lobo silane, Kisadeshi to n- Lutripropoxysilane and the like are preferred.

The content ratio of the silane coupling agent in the film forming material layer of the transfer film of the present invention is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the glass powder. Preferably it is 0.001 to 5 parts by weight. When the ratio of the silane coupling agent is less than 0.01 part by weight, the effect of improving the dispersion stability of the glass powder and the effect of improving the flexibility of the formed film-forming material layer are sufficiently exhibited. I can't. On the other hand, when this ratio exceeds 10 parts by weight, the viscosity of the obtained glass paste composition increases with time when stored, or a reaction occurs between the silane coupling agents, and the light after baking is reduced. This may cause the transmittance to decrease.

Plasticizer>

The composition of the present invention preferably contains a plasticizer in order to exhibit good flexibility and combustibility in the formed film-forming material layer. As the plasticizer, a plasticizer comprising a compound represented by the following formula (3) is preferable. (3)

(Wherein, R ₂ and R ₅ each represent the same or different alkyl groups having 1 to 30 carbon atoms, and R ₃ and R ₄ each represent the same or different methylene groups or 2 to 30 carbon atoms. Wherein s is a number from 0 to 5, and t is a number from 1 to 10.)

According to the transfer film provided with the film forming material layer containing the plasticizer, even if the transfer film is bent, minute cracks (cracks) do not occur on the surface of the film forming material layer. The transfer film becomes excellent in flexibility, and can be easily wound up in a roll shape.

In particular, the plasticizer made of the compound represented by the above formula (3) is easily decomposed and removed by heat, so that the light transmittance of the dielectric layer obtained by firing the film forming material layer is reduced. Never.

In the above formula (3), the alkyl group represented by R ₂ or R ₅ , and the alkylene group represented by R ₃ or R ₄ may be linear or branched; It may be a saturated group or an unsaturated group.

The alkyl group represented by R ₂ or R ₅ has 1 to 30 carbon atoms, preferably 2 to 20 and more preferably 4 to L;

If the number of carbon atoms in the alkyl group exceeds 30, the solubility of the plasticizer in the solvent constituting the present invention may decrease, and good flexibility may not be obtained.

Specific examples of the compound represented by the above formula (3) include dibutyl adipate, disobutyl adipate, di-2-ethylhexyl adipate, di-12-ethylhexyl azelylate, dibutyl sebacate, and dibutyl diglycol adipate. And the like. Preferably, n is a compound represented by 2 to 6.

The content ratio of the plasticizer in the film-forming material layer of the transfer film of the present invention is preferably 1 to 20 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the glass powder. 5 to 10 parts by weight. When the ratio of plasticizer is less than 0.1 part by weight In some cases, the plasticity of the film-forming material layer may not be sufficiently improved. On the other hand, if this ratio exceeds 20 parts by weight, the tackiness of the film-forming material layer formed using the obtained composition becomes excessive, and thus the film-forming material layer is provided. The transferability of the transfer film may be poor.

The composition of the present invention may contain, as optional components, various additives such as a tackifier, a surface tension adjuster, a stabilizer, and an antifoaming agent, in addition to the above essential components. <Radiation sensitive component>

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

Specific examples of the polyfunctional (meth) acrylate constituting the radiation-sensitive component include di (meth) acrylates of anolexylene glycolone such as ethylene glycolone and propylene glycolone; polyethylene glycol and polypropylene glycol. Di (meth) acrylates of polyalkylene glycols such as hydroxyl; hydroxy-terminated polybutadiene at both ends, hydroxy-terminated polyisoprene at both ends, hydroxy-terminated polyhydroxylates at both ends, etc. (Meta) Atarile

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4_butanetriol, trimethylolalkane, tetramethylironolenolecan, pentaerythritol tonole and dipentaerythritol tonole; Poly (meth) acrylates of polyalkylene glycol adducts of polyhydric alcohols; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; Polyester (meth) Atarilate, Epoxy (meta) Atarilate, Urethane (meth) acrylate, Alkyd resin (meta) Atarilet, Silicone resin (meta) Atarilate, Spirane Oligo (meth) atalylates such as fatty (meth) acrylates; and the like. These can be used alone or in combination of two or more.

Specific examples of the radiation polymerization initiator that constitutes the radiation-sensitive component include benzoinole, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methylenolone, phenylenepropane, and one-one. Hydroxycyclene hexinolephenyl ketone, 2,2-dimethoxy-12-phenyl-acetophenone, 2-methyl-1- [4 '-(methinorethio) phen-nore] 1-2-Monolereforinol 1-propanone, 2-benzyl-1 2 —Diolamino compounds such as dimethylamino-1- (4-morpholinophenyl) -butane-1-one; azo compounds or azides such as azoisobutyronitrile, 4-azidobenzaldehyde Compounds; Organosulfur compounds such as mercaptan disulfide; Benzoyl peroxide, di-tert-butyl peroxide, tert-ptino Lehigh Doroha ⁰ - Okishido, Kumenhai Doroha ⁰ Okishido, organic such as Bruno lame Tanhai Doropaokishido Paokishido; 1, 3- bis (trichloro port methyl) Single 5- (2, - black port phenyl) - 1, 3, 5-Toriajin, 2- [2- (2-furaninole) ethyleninole]-4,6, -bis (trichloromethinole) trihalomethanes such as 1,1,3,5-triazine; 2,2,1-bis (2-chloromouth phenol) ) 4,5,4,5, -tetraphenylinole 1,2, -imidazolone dimer such as biimidazonole; and the like. These can be used alone or in combination of two or more.

As an example of a composition for forming a dielectric layer, as an example of an inorganic particle-containing composition, lead oxide, boron oxide, silicon oxide, and calcium oxide (PbO—B203—Si02) can be used as inorganic particles (glass powder). — CaO-based mixture: 100 to 100 parts by weight, butyl methacrylate ethylhexyl methacrylate hydroxypropyl methacrylate glycidyl methacrylate copolymer 5 to 30 parts by weight as a binder resin, and n-decyl trime as a dispersant Essential components are 0.1 to 5 parts by weight of toxicoxysilane, 0.1 to 10 parts by weight of di-2-ethylhexylazelate as a plasticizer, and 5 to 30 parts by weight of propylene daricol monomethyl ether as a solvent. Can be included.

The composition of the present invention can be prepared by mixing the inorganic particles, the binder resin, the specific compound and the solvent, and optional components using a mixer such as a roll mixer, a mixer, and a homomixer. .

The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for application, and its viscosity is usually from 1,000 to 300,000. O mPa ■ s, and preferably 3,000 to 100,000 mPa's.

The composition of the present invention can be particularly suitably used for producing a transfer film (transfer film of the present invention) described in detail below.

Further, the composition of the present invention is obtained by directly applying the composition to the surface of a substrate by a conventionally known method for forming a film-forming material layer, that is, a screen printing method, and drying the coating film. It can also be suitably used for a method of forming a film forming material layer. '

Transfer Transcription>

The transfer film of the present invention is a composite film suitably used in the step of forming a PDP component, particularly in the step of forming a dielectric layer, wherein the composition of the present invention is applied on a support film, and the coating film is formed. It comprises a film-forming material layer formed by drying.

That is, the transfer film of the present invention is formed by forming a film-forming material layer containing inorganic particles, a binder resin and a specific compound on a support film.

In addition, the transfer film of the present invention may be a film obtained by forming a resist film described later on a support film, coating the composition of the present invention thereon, and drying (a laminated film).

Further, the transfer film of the present invention may be a radiation-sensitive transfer film constituted by using a composition containing radiation-sensitive inorganic particles.

(1) Composition of transfer film:

2A is a schematic cross-sectional view showing a transfer film of the present invention wound in a roll shape, and FIG. 2B is a cross-sectional view showing a layer configuration of the transfer film [partial detail of FIG. 2A. Figure].

The transfer film shown in FIG. 2 is, as an example of the transfer film of the present invention, a composite film used for forming a dielectric layer constituting a PDP, and usually includes a support film F1 and a support film F1. The film forming material layer F2 formed on the surface of the film forming material layer 1 so as to be peelable, and a cover film F3 easily provided on the surface of the film forming material layer F2. The cover film F3 may not be used depending on the properties of the film-forming material layer F2.

The support film F1 constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and having flexibility. Since the support film F1 has flexibility, the paste-like composition (the composition of the present invention) can be applied using a roll coater, a blade coater, or the like, and thus, the uniform film thickness can be obtained. The film forming material layer can be formed, and the formed film forming material layer can be stored and supplied in a state of being wound into a roll. Examples of the resin constituting the support film F1 include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. And the like. The thickness of the support film F1 is, for example, 20 to 10Ομιη.

The film-forming material layer F2 constituting the transfer film is a layer that becomes a glass sintered body (dielectric layer) by being baked, and contains glass powder (inorganic particles), a binder resin, and a specific compound. It is contained as an essential component.

The thickness of the film-forming material layer F2 varies depending on the glass powder content, the type of panel and the size of the panel, but is, for example, 5 to 20 μμιι, preferably 10 to 10 μμιι. Is done. If the thickness is less than 5 μηι, the thickness of the finally formed dielectric layer will be too small, and the desired dielectric properties may not be secured. Normally, when the thickness is 5 to 20 μμπι, the thickness of the dielectric layer required for a large panel can be sufficiently secured.

The cover film F3 constituting the transfer film is formed on the surface (film) of the film forming material layer F2. This is a film for protecting the contact surface with the glass substrate. This cover film

Preferably, F 3 is also a flexible resin film. Examples of the resin forming the cover film F3 include the resins exemplified as those forming the support film F1. The thickness of the cover film F3 is, for example, 20 to 10Ομπι.

(1) Production method of transfer film:-The transfer film of the present invention comprises: forming a film forming material layer (F 2) on a support film (F 1); and forming a cover film on the film forming material layer (F 2). It can be manufactured by providing (press bonding) (F 3).

As a method for forming the film-forming material layer, a composition of the present invention containing inorganic particles, a binder resin, a dispersant, a plasticizer, and a solvent is applied to a support film, and the coated film is dried to remove the solvent. A method of removing part or all can be mentioned.

As a method of applying the composition of the present invention onto a support film, a coating film having a large thickness (for example, 20 μπι or more) and excellent uniformity of the film thickness can be efficiently formed. From the viewpoint, a coating method using a roll coater, a coating method using a blade coater such as a doctor blade, a coating method using a curtain coater, a coating method using a wire coater, and the like can be preferably mentioned.

The surface of the support film to which the composition of the present invention is applied is preferably subjected to a release treatment. Thus, after transferring the film forming material layer, the support film can be easily peeled from the film forming material layer.

The coating film of the composition of the present invention formed on the supporting film is dried to remove a part or all of the solvent, and becomes a film-forming material layer constituting the transfer film. The drying condition of the coating film of the composition of the present invention is, for example, about 40 to 150 ° C. for about 0.1 to 30 minutes. The residual ratio of the solvent after drying (the content of the solvent in the film-forming material layer) is usually 10% by weight or less, and the film-forming material layer exhibits adhesiveness to the substrate and moderate shape retention. From the viewpoint, it is preferably 0.1 to 5% by weight.

Provided on the film forming material layer formed as described above (usually thermocompression bonding It is preferable that the surface of the cover film is also subjected to a release treatment. Thus, the cover film can be easily peeled off from the film forming material layer before transferring the film forming material layer.

(1) Transfer of the film forming material layer (how to use the transfer film);

The film-forming material layer on the support film is transferred onto the surface of the substrate at once. According to the transfer film of the present invention, the film forming material layer can be reliably formed on the glass substrate by such a simple operation, so that the steps in the process of forming the PDP components such as the dielectric layer can be achieved. Improvement (high efficiency) can be achieved, and the quality of the constituent elements formed can be improved (for example, stable dielectric characteristics in the dielectric layer can be exhibited).

In the method (1) for producing a PDP of the present invention, the film forming material layer constituting the transfer film of the present invention is transferred to the surface of a substrate, and the transferred film forming material layer is fired. Forming a dielectric layer on the surface of the substrate.

An example of the step of transferring the film-forming material layer using the transfer film having the configuration shown in FIG. 2 is as follows.

1. Cut the transfer film wound on a roll into a size corresponding to the area of the substrate.

2. After peeling off the cover film (F3) from the surface of the film-forming material layer (F2) in the cut transfer film, place the transfer film so that the surface of the film-forming material layer (F2) contacts the surface of the substrate. Overlap.

3. The heating roller is moved on the transfer film superimposed on the substrate and thermocompression-bonded.

4. The support film (F1) is peeled off from the film-forming material layer (F2) fixed to the substrate by thermocompression bonding.

By the above operation, the film-forming material layer (F 2) on the support film (F 1) is transferred onto the substrate. The transfer conditions include, for example, the surface temperature of the heating roller is 60 to 120 ° C, the roll pressure by the heating roller is 1 to 5 kg m ² , Is set to 0.2 to 10 Om / min. Such an operation (transfer step) can be performed by a laminator device. The substrate may be preheated, and the preheating temperature may be, for example, 40 to 100 ° C.

The film-forming material layer (F 2) formed and transferred on the surface of the substrate is baked to become an inorganic sintered body (dielectric layer). Here, as a firing method, a method in which the substrate on which the film-forming material layer (F ² ) is transferred and formed is placed in a high-temperature atmosphere can be cited. As a result, the organic substances (eg, binder resin, residual solvent, dispersant, plasticizer, and various additives) contained in the film-forming material layer (F 2) are decomposed and removed, and the inorganic particles are melted. And sinter. Here, the firing temperature varies depending on the melting temperature of the substrate, the constituent material in the film-forming material layer, and the like. 0 ° C.

<Method of Manufacturing PDP (2) (Formation of Components Using Photoresist Method)> The method of manufacturing PDP (2) of the present invention is a method of forming a film forming material layer constituting a transfer film of the present invention on a substrate. A resist film is formed on the transferred film forming material layer, the resist film is exposed to light to form a latent image of the resist pattern, and the resist film is developed to develop the resist pattern. The film forming material layer is subjected to an etching treatment to form a pattern layer corresponding to the resist pattern, and the pattern layer is subjected to a baking treatment, whereby partition walls, electrodes, resistors, dielectric layers, phosphors, and color filters are formed. Forming a component selected from a filter and a black matrix.

Alternatively, a laminated film of a resist film and a film-forming material layer obtained from the inorganic particle-containing composition of the present invention is formed on a support film, and the laminated film formed on the support film is transferred onto a substrate. The resist film forming the laminated film is exposed to light to form a latent image of a resist pattern, and the resist film is developed to reveal the resist pattern, and the film forming material layer is etched. By forming a pattern layer corresponding to the resist pattern and subjecting the pattern layer to a baking treatment 1 ", the constituent elements selected from partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black matrix Is formed. Hereinafter, a method of forming a “partition wall” as a component of the PDP on the surface of the rear substrate will be described. In this method, [1] a film forming material layer transferring step, [2] a resist film forming step, [3] a resist film exposing step, [4] a resist film developing step, and [5] a film A partition is formed on the surface of the substrate by the step of etching the material layer and the step of baking the partition pattern.

3 and 4 are schematic cross-sectional views showing a series of steps for forming a partition. In FIGS. 3 and 4, reference numeral 11 denotes a glass substrate. Electrodes 12 for generating plasma are arranged at regular intervals on the glass substrate, and the glass substrate is covered with the electrodes 12 so as to cover the electrodes 12. A dielectric layer 13 is formed on the surface of 11.

In the present invention, as the “transferring the film-forming material layer onto the substrate”, in addition to the mode of transferring the film-forming material layer onto the surface of the glass substrate 11, the transfer onto the surface of the dielectric layer 13 Such aspects shall be included.

(1) Transfer process of the film forming material layer:

An example of the step of transferring the film forming material layer is as follows.

After peeling off the cover film (not shown) of the transfer film, as shown in FIG. 3B, the transfer film 2 is brought into contact with the surface of the dielectric layer 13 with the surface of the film forming material layer 21. After the transfer film 20 is thermocompressed with a heating roller or the like, the support film 22 is peeled off from the film forming material layer 21. As a result, as shown in FIG. 3C, the film-forming material layer 21 is transferred to the surface of the dielectric layer 13 and is brought into close contact therewith. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 80 to 140 ° C., the roller pressure by the heating roller is 1 to 5 kg m ² , and the moving speed of the heating roller is 0.1 to 10. O mZ can be shown. Further, the glass substrate 11 may be preheated, and the preheating temperature may be, for example, 40 to 100 ° C.

(1) Step of forming resist film:

In this step, as shown in FIG. 3D, a resist film 31 is formed on the surface of the transferred film forming material layer 21. 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 spin coating method, a casting coating method, and then drying the coating film. it can. Here, the drying temperature of the coating film is usually about 60 to 130 ° C.

Further, it may be formed by transferring a resist film formed on the support film to the surface of the film forming material layer 21. According to such a formation method, the number of steps for forming the resist film can be reduced, and the uniformity of the thickness of the obtained resist can be improved. The etching process of the layer is performed uniformly, and the height and shape of the partition walls formed are uniform.

The thickness of the resist film 31 is usually 0.1 to 4 μπη, preferably 0.5 to 20 μπι.

(1) Resist film exposure process:

In this step, as shown in FIG. 3A, the surface of the resist film 31 formed on the film forming material layer 21 is selectively irradiated with radiation such as ultraviolet rays through an exposure mask マスク ( Exposure) to form a resist pattern latent image. In the figure, ΜΑ and MB are a light transmitting part and a light shielding part in the exposure mask M, respectively.

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

In the case where the resist film is formed by transfer, it is preferable to perform the exposure step in a state where the supporting film coated on the resist film is not peeled off.

(1) Development process of resist film

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

Here, the developing conditions include the type, composition and concentration of the developing solution, the developing time, the developing temperature, the developing method (for example, the immersion method, the oscillating method, etc.) according to the type of the resist film 31 and the like. Method, shower method, spray method, paddle method), a developing device, and the like can be appropriately selected.

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

The resist pattern 35 acts as an etching mask in the next step (etching step), and the constituent material (the photo-hardened resist) of the resist remaining portion 35 A is the same as that of the film forming material layer 21. It is necessary that the dissolution rate in the etching liquid is lower than that of the constituent materials.

(1) Etching process of the film forming material layer:

In this step, the film forming material layer is etched to form a partition pattern layer corresponding to the resist pattern.

That is, as shown in FIG. 4B, a portion of the film forming material layer 21 corresponding to the resist removal portion 35B of the resist pattern 35 is dissolved in the etching solution and selectively removed. Here, FIG. 4B shows a state during the etching process. Then, when the etching process is further continued, as shown in FIG. 4C, a predetermined portion of the film forming material layer 21 is completely removed, and the dielectric layer 13 is exposed. As a result, a partition pattern layer 25 composed of the material layer remaining portion 25A and the material layer removed portion 25B is formed.

Here, the etching process conditions include the type, composition, and concentration of the etchant, the processing time, the processing temperature, and the processing method (for example, the dipping method, the oscillating method, Method, spray method, paddle method), processing equipment, and the like can be appropriately selected.

In addition, by selecting the type of the resist film 31 and the film forming material layer 21 so that the same solution as the developing solution used in the developing step can be used as the etching solution, the developing step and the etching step can be performed. Can be continuously performed, and the manufacturing efficiency can be improved by simplifying the process.

Here, the resist remaining portion 35 A constituting the resist pattern 35 is formed by etching.

28 Replacement Paper (Rule 26) Preferably, it is gradually dissolved during the etching treatment and completely removed at the stage when the partition pattern layer 25 is formed (at the end of the etching treatment).

Even if a part or all of the remaining resist portion 35 A remains after the etching process, the remaining resist portion 35 A is removed in the next baking step.

(1) Baking process of partition pattern layer:

In this step, the partition wall pattern layer 25 is baked to form partition walls. As a result, the organic substance in the material layer residual portion 25 A is burned off to form a partition, and as shown in FIG. 4D, a panel material in which the partition 40 is formed on the surface of the dielectric layer 13. In 50, a space defined by the partition wall 40 (a space derived from the material layer removing portion 25B) is a plasma working space.

Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the material layer residual portion 25A is burned out, and is usually 400 to 600 ° C. The baking time is usually set to 10 to 90 minutes.

PDP Production Method (3) (Preferred Embodiment Utilizing Photoresist Method)> The PDP production method of the present invention is not limited to the method shown in FIGS.

Here, as another preferable method for forming the PDP component (the method for manufacturing PDP ③), the following method (1) to (3) can be mentioned.

(1) After forming a resist film on a support film, the composition containing inorganic particles of the present invention is applied on the resist film and dried to form a film-forming material layer. Here, when forming the resist film and the film forming material layer, a roll coater or the like can be used, whereby a laminated film having excellent uniformity of the film thickness can be formed on the supporting film. it can.

(2) The laminated film of the resist film and the film forming material layer formed on the supporting film is transferred onto the substrate. Here, the transfer conditions may be the same as the conditions in the above “transfer step of film forming material layer”.

(3) The “exposure step of the resist film”, the “development step of the resist film”, the “film forming material”

29

Replacement form (Rule 26) The same operation as in the “layer etching step” and the “sintering step of the partition pattern layer” is performed. At that time, as described above, the resist film developing solution and the film forming material layer etching solution are made the same solution, and the “resist film developing step” and the “film forming material layer etching step” are performed. Is preferably performed continuously.

According to the method as described above, the film forming material layer and the resist film are collectively transferred onto the substrate, so that the manufacturing efficiency can be further improved by simplifying the steps. Production method of PDP (4) (Formation of components using radiation-sensitive transfer film)>

In the method (4) for producing a PDP of the present invention, the film-forming material layer constituting the radiation-sensitive transfer film of the present invention is transferred onto a substrate, and the film-forming material layer is subjected to an exposure treatment so that the latent image of the resist pattern is formed. An image is formed, the film forming material layer is developed to form a pattern layer, and the pattern layer is baked to form a partition, an electrode, a resistor, a dielectric layer, a phosphor, a color filter, and a black. And forming a component selected from a matrix.

In this method, for example, taking a method of forming a partition wall as an example, the above-described “film forming material layer transferring step” is followed by a “resist film exposing step” and a “resist film developing step”. A pattern layer is formed under the conditions, and thereafter, a partition wall is formed on the surface of the substrate by a “step of firing a partition wall pattern”.

The method of forming the “partition” as a PDP constituent element has been described above in the description of each step of the PDP manufacturing method (1) to (4). According to this method, the electrodes, resistors, and dielectrics constituting the PDP are formed. Body layers, phosphors, color filters and black matrices can also be formed.

Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. In the following, “parts” means “parts by weight”.

Example 1

(1) Preparation of glass paste composition (inorganic particle-containing composition): 100 parts of a mixture of glass powder (inorganic particles) consisting of lead oxide, boron oxide, silicon oxide, and oxidizing power (Pb0_B20s—Si02—CaO) (softening point 560 ° C) 100 parts, butylmetallic binder resin Rate (BMA) / 2-Ethylhexylmethacrylate (EHMA) / 2-Hydroxypropyl methacrylate (HPM A) / Dalicidyl methacrylate (GMA) copolymer (weight ratio 30 60 5/5 , Weight average molecular weight: 105,000) 17 parts, n-decyl trimethoxysilane 1.◦ part as dispersant, 2.5 parts di-2-ethylhexyl azelate as plasticizer, and propylene glycol as solvent By mixing 7.3 parts of monomethyl ether and 1.5 parts of ethyl 3-ethoxypropionate using a dispersing machine, the viscosity becomes 1,60 OmPa · s (2 Orpm, manufactured by Toki Sangyo, TV-30 type viscometer) Was prepared.

(2) Production and evaluation of transfer film (flexibility and handleability):

The composition of the present invention prepared in (1) above is coated on a support film (width: 400 mm, length: 30 m, thickness: 38 πι) made of polyethylene terephthalate (PET) which has been pre-released by using a ply coater. Then, the formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, whereby a film forming material layer having a thickness of 9 was formed on the support film. Next, a cover film (400 mm in width, 30 m in length, and 38 μm in thickness) made of PET, which has been pre-released, is pasted on the film forming material layer to obtain the configuration shown in Fig. 2. The transfer film of the present invention having the following was produced.

The resulting transfer film had flexibility and could be easily wound into a roll. Even when this transfer film was bent, no cracks (bending cracks) occurred on the surface of the film-forming material layer, and the film-forming material layer had excellent flexibility.

Further, the cover film is peeled off from the transfer film, and the transfer film (the laminate of the support film and the film-forming material layer) is pressed so that the surface of the film-forming material layer comes into contact with the surface of the glass substrate. When the transfer film was peeled off from the surface of the glass substrate, the film forming material layer was Demonstrates moderate adhesiveness to glass substrates, and allows the transfer film to be peeled off without causing cohesive destruction in the film forming material layer, making it easy to handle as a transfer film. Was good.

(3) Transfer of film forming material layer:

After peeling off the cover film from the transfer film obtained in the above (2), the surface of the film-forming material layer is brought into contact with the surface of the glass substrate for a 21-inch panel (the fixed surface of the bus electrode). The transfer film (the laminate of the support film and the film-forming material layer) was overlapped, and the transfer film was thermocompression-bonded with a heating roll. Here, the pressing conditions were as follows: the surface temperature of the heating roll was 90 ° C, the roll pressure was 2 kg m ² , and the moving speed of the heating roll was 0.8 mZ.

After the completion of the thermocompression bonding, the support film was peeled off from the film forming material layer fixed (heat bonded) to the surface of the glass substrate, and the transfer of the film forming material layer was completed.

In this transfer step, when the support film was peeled off, the film-forming material layer did not cause cohesion and breakage, and the film-forming material layer had a sufficiently large film strength. Furthermore, the transferred film-forming material layer had good adhesion to the surface of the glass substrate.

(4) Firing the film forming material layer (forming the dielectric layer):

The glass substrate on which the film-forming material layer was transferred and formed according to (3) above was placed in a firing furnace, and the temperature in the furnace was raised to 570 ° C at a rate of 10 ° C per minute, and then 570 ° C. By baking for 10 minutes at C, a dielectric layer composed of a glass sintered body was formed on the surface of the glass substrate.

When the film thickness (average film thickness and tolerance) of this dielectric layer was measured, it was in the range of 44 μιη ± 0.4 m, and the film had excellent uniformity in film thickness.

In addition, the surface of the obtained dielectric layer was subjected to three-dimensional measurement using a non-contact film thickness meter (manufactured by Ryoko Co., NH-3), and the surface roughness was measured in accordance with JIS standard (B0601). When (Ra, Ry, Rz) was determined, it was Ra = 0.06 μιη, Ry = 0.43 μπι, and Rz = 0.21 μιη, which were excellent in surface smoothness.

Examples 2 to 6 In Example 1, a glass paste composition was prepared in the same manner as in Example 1 (1) except that each of the copolymers shown in Table 1 was used as the binder resin, and each of the obtained glass pastes was used. A transfer film was formed in the same manner as in Example 1 (2). Each of the obtained transfer films had flexibility, and the operation of winding in a roll shape could be easily performed. Even when this transfer film was bent, no cracks (bending cracks) occurred on the surface of the film forming material layer, and the film forming material layer had excellent flexibility.

When the transfer was performed in the same manner as in Example 1 (3) using each of the obtained transfer films, no matter which transfer film was used, when the support film was peeled off, the film-forming material layer was agglomerated and broken. The film forming material layer had a sufficiently large film strength. Furthermore, the transferred film-forming material layer had good adhesion to the surface of the glass substrate.

Further, a dielectric layer was formed in the same manner as in Example 1 (4), and the surface roughness (Ra, Ry, Rz) of the obtained dielectric layer was determined in the same manner as in Example 1. The values of Ra, Ry, and Rz are shown in Table 1 together with Example 1.

Copolymerization ratio of binder resin (weight ratio) Surface roughness

Example

BMA EHMA HPMA GMA Ra Ry Rz

1 30 60 5 5 0.06 0.43 0.21

2 30 57.5 10 2.5 0.06 0.42 0.23

3 30 55 10 5 0.06 0.43 0.21

4 30 52.5 10 7.5 0.07 0.44 0.25

5 30 50 10 10 0.12 1.12 0.65

6 30 40 10 20 0.10 0.62 0.34

Comparative example

The number of binder resin was 17 parts, and butyl methacrylate 2-ethylhexyl methacrylate Z 2-hydroxypropyl methacrylate Z glycidyl methacrylate copolymer (weight ratio 30/60/5 / 5, weight average molecular weight 1 0 5,00

0) instead of butyl methacrylate Z2-ethylhexyl methacrylate Z

Except that a 2-hydroxypropyl methacrylate copolymer (weight ratio 30Z60 / 10, weight average molecular weight 150,000) was used, the viscosity was 1,200 mPa · s (2 Orpra, manufactured by Toki Sangyo Co., Ltd., TV-30 type viscometer) was prepared. Using the obtained composition, a transfer film was manufactured and evaluated in the same manner as in the example, and the flexibility and handleability were good. However, the dielectric layer was formed in the same manner as in the example. The surface roughness (Ra, Ry, Rz) was calculated as follows: Ra = 0.31 μηι, Ry = 2.61 μιη, Rz = 1.10 μιη, which is inferior in surface smoothness. there were. Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a patent application No. 2003-119490 filed on April 24, 2003, the contents of which are incorporated herein by reference. <Industrial applicability>

According to the composition of the present invention, the following effects are exerted.

(1) PDP components with excellent surface smoothness (for example, partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black matrix) are suitable for the low-temperature, short-time baking process. Can be formed.

(2) A transfer film excellent in flexibility of the film forming material layer can be manufactured. (3) It is possible to manufacture a transfer film having excellent transferability (heat adhesion to a substrate) of the film forming material layer.

According to the transfer film of the present invention, the following effects can be obtained.

(1) The components (particularly, the dielectric layer) of the PDP having excellent surface smoothness can be efficiently formed in a firing process at a low temperature and in a short time.

(2) The film-forming material layer is excellent in flexibility, and the surface of the film-forming material layer does not have bending cracks.

(3) It has excellent flexibility and can be easily rolled.

(4) The film-forming material layer exhibits suitable adhesiveness, and has good handling properties (handling properties).

(5) Excellent transferability (heat adhesion to substrate) of the film forming material layer.

According to the manufacturing method of the present invention, the following effects can be obtained.

(1) Efficient components of PDP with excellent surface smoothness (for example, partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black matrix) in a low-temperature, short-time baking process Can be formed.

(2) Low-temperature, short-time firing process enables efficient formation of PDPs with high positional accuracy of components.

(3) A dielectric layer having a large thickness can be efficiently formed in a firing process at a low temperature and in a short time.

(4) The dielectric layer required for large panels can be efficiently formed in a firing process at a low temperature and in a short time. (5) In a baking process at a low temperature in a short time, a PDP having a dielectric layer with excellent film thickness uniformity and surface smoothness can be efficiently formed.

Claims

The scope of the claims

1. [A] inorganic particles, and

[B] a binder resin containing a polymer (B-1) having a repeating unit represented by the following formula (1):

An inorganic particle-containing composition for a plasma display panel, comprising:

H C (I)

(In the formula, X represents a hydrogen atom or a methyl group, R ¹ represents a single bond, a methylene group or an alkylene group having 2 to 5 carbon atoms, and η represents an integer of 1 to 6.)

2. The inorganic particle-containing composition according to claim 1, further comprising [C] a radiation-sensitive component.

3. The inorganic particle-containing composition according to claim 1, further comprising a plasticizer.

4. The inorganic particle-containing composition according to claim 1, further comprising a silane coupling agent.

5. [B-1] The polymer is a monomer represented by the following formula (i) and at least one selected from an alkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate and an alkoxyalkyl (meth) acrylate. 2. The inorganic particle-containing composition according to claim 1, which is a polymer obtained by copolymerizing one kind with another. (i)

6. The inorganic particle-containing composition according to claim 1, comprising [A] glass powder having a softening point of 350 to 700 ° C as inorganic particles.

7. A transfer film, comprising a film-forming material layer obtained from the composition containing inorganic particles according to claim 1.

8. A transfer, characterized by having a laminate of a resist film and a film-forming material layer obtained from the inorganic particle-containing composition according to claim 1.

9. A film-forming material layer obtained from the inorganic particle-containing composition according to claim 1 is transferred onto a substrate, and the transferred film-forming material layer is baked, whereby a dielectric material is formed on the substrate. A method for manufacturing a plasma display panel, comprising a step of forming a layer.

10. Transferring a film-forming material layer obtained from the composition containing inorganic particles according to claim 1 onto a substrate, forming a resist film on the transferred film-forming material layer, The resist film is exposed to light to form a latent image of the resist pattern, the resist film is developed to reveal the resist pattern, and the film forming material layer is etched to form a pattern layer corresponding to the resist pattern. By forming and firing the pattern layer, partition walls, electrodes, resistors, dielectric layers, phosphors, A method for manufacturing a plasma display panel, comprising a step of forming a component selected from one of a filter and a black matrix.

11. A laminated film of a resist film and a film-forming material layer obtained from the inorganic particle-containing composition according to claim 1 is formed on a support film, and the laminated film formed on the support film is formed. The resist film constituting the laminated film is transferred to a substrate and exposed to a resist film to form a latent image of the resist pattern, and the resist film is developed to reveal a resist pattern. A pattern layer corresponding to the resist pattern is formed by etching, and the pattern layer is baked to be selected from partition walls, electrodes, resistors, dielectric layers, phosphors, color filters, and black matrices. A method for manufacturing a plasma display panel, comprising a step of forming a component.

12. A film-forming material layer obtained from the inorganic particle-containing composition according to claim 2 is transferred onto a substrate, and the film-forming material layer is exposed to light to form a latent image of a pattern. By developing the film forming material layer to form a pattern layer and baking the pattern layer, the pattern layer is selected from a partition, an electrode, a resistor, a dielectric layer, a phosphor, a color filter, and a black matrix. A method for manufacturing a plasma display panel, comprising a step of forming a component.