KR20020069490A - Transfer Film for Forming Dielectric Layer and Plasma Display Panel - Google Patents

Abstract

PURPOSE: To prepare a dielectric layer forming tranfer film which can form a uniform dielectric layer without being affected by dusts and foreign matters on a substrate, and also it can form the dielectric layer having high light transmission properties, and has excellent flexibility of the film forming material layer and transfer properties (heat-adhesion properties to the substrate). CONSTITUTION: The dielectric layer forming transfer film is characterized by containing 10 to 25 pts.wt. of organic ingredients against 100 pts.wt. of inorganic particules.

Description

Transfer Film for Forming Dielectric Layer and Plasma Display Panel

The present invention relates to a transfer film and a plasma display panel for forming a dielectric layer.

In recent years, a plasma display has attracted attention as a flat fluorescent display. 1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel (hereinafter also referred to as "PDP"). In FIG. 1, (1) and (2) are glass substrates arrange | positioned opposingly, (3) is a partition, and the cell is partitioned and formed by the glass substrate 1, the glass substrate 2, and the partition 3. . 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of lowering the resistance of the transparent electrode 4, 6 is a glass substrate 2 (7) is a fluorescent material held in the cell, (8) a dielectric layer formed on the surface of the glass substrate (1) to cover the transparent electrode (4) and the bus electrode (5), (9) Denotes a dielectric layer formed on the surface of the glass substrate 2 so as to cover the address electrode 6, and P is a protective film containing, for example, magnesium oxide.

Moreover, in a color PDP, in order to obtain an image with high contrast, a color filter (red, green, blue), a black matrix, etc. may be provided between a glass substrate and a dielectric layer.

As a method of forming the dielectric layer 8, a paste-type inorganic particle-containing composition (glass paste composition) containing glass powder, a binder resin and a solvent is produced, and the glass paste composition is subjected to screen printing to The method of forming a film forming material layer by apply | coating to a surface and drying, then baking this film forming material layer, and removing an organic substance and sintering glass powder is known.

By the way, the thickness of the film formation material layer formed on the glass substrate 1 is 1.3-2.0 of the film thickness of the dielectric layer 8 which should be formed in consideration of the reduction of the film thickness accompanying removal of the organic substance in a baking process. It is necessary to make it about double, and for example, in order to make the film thickness of the dielectric layer 8 into 20-50 micrometers, it is necessary to form the film forming material layer about 30-100 micrometers thick.

On the other hand, when apply | coating the said glass paste composition by the screen printing method, the thickness of the coating film formed by one coating process will be about 15-25 micrometers.

Therefore, in order to make a film formation material layer into a predetermined thickness, it is necessary to apply | coat repeatedly (multiprinting) the said glass paste composition several times (for example, 2 to 7 times) to the glass substrate surface.

However, when the film forming material layer is formed by multiple printing using the screen printing method, the dielectric layer formed by firing the film forming material layer does not have a uniform film thickness (for example, the tolerance is within ± 5%). You will not. This is because it is difficult to uniformly apply the glass paste composition to the surface of the glass substrate in the multiple printing by the screen printing method. The larger the coating area (panel size) and the higher the number of coatings, the more uneven the film thickness in the dielectric layer. Becomes large. And in the panel material (glass substrate containing the said dielectric layer) obtained through the application | coating process by multiple printing, a nonuniformity arises in a dielectric characteristic by the film thickness nonuniformity in the surface, and the nonuniformity of a dielectric characteristic is carried out in PDP. It may cause display defects (uneven brightness).

Further, in the screen printing method, the mesh shape of the screen plate may be transferred to the surface of the film forming material layer, so that the dielectric layer formed by firing the film forming material layer is inferior in surface smoothness.

As a means for solving the above problems in forming the film forming material layer by the screen printing method, the present inventors apply the glass paste composition onto the support film, and dry the coating film to form the film forming material layer, A process of forming a dielectric layer on the surface of the glass substrate by transferring the film forming material layer formed on the supporting film to the glass substrate surface on which the electrode is fixed and firing the transferred film forming material layer (hereinafter also referred to as "dry film method"). ) Is proposed a method for producing a PDP (see Japanese Patent Laid-Open No. 9-102273).

According to this manufacturing method, it is possible to form a dielectric layer having excellent film uniformity and surface uniformity.

In addition, the present inventors laminate a support film, a film forming material layer obtained from a glass paste composition, and a cover film easily peeled off the surface of the film forming material layer as a transfer film which can be preferably used to form a dielectric layer of a PDP. Is also proposed for a composite film (hereinafter also referred to as "transfer film") (see JP-A-10-291834).

Such a transfer film is also advantageous in that it can be wound and stored in a roll shape.

However, in the conventional transfer film, there is a problem that pinholes are likely to occur in the dielectric layer formed through the transfer and firing processes under the influence of dust and foreign matter on the substrate, and the pinhole portions are connected to the display defect of the PDP. .

Moreover, in the conventional transfer film, there existed a problem that removal of the organic component at the time of baking becomes difficult, as the film thickness of the dielectric layer to form becomes thick.

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

It is a first object of the present invention to provide a transfer film for forming a dielectric layer capable of forming a uniform dielectric layer without being affected by dust, foreign matters, etc. on a substrate.

A second object of the present invention is to provide a transfer film for forming a dielectric layer capable of forming a dielectric layer having a high light transmittance.

A third object of the present invention is to provide a transfer film for forming a dielectric layer having excellent flexibility and transferability (heat adhesion to a substrate) of a film forming material layer.

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

Fig. 2 (a) is a cross sectional view schematically showing a transfer film for forming a dielectric layer of the present invention, and (b) is a cross sectional view showing a layer structure of the transfer film.

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

1: glass substrate 2: glass substrate

3: partition 4: transparent electrode

5: bus electrode 6: address electrode

7: fluorescent substance 8: dielectric layer

9: dielectric layer P: protective layer

F1: support film F2: film-forming material layer

F3: cover film

The transfer film for dielectric layer formation of this invention,

[A] an inorganic particle comprising a glass frit, and

[B] a film-forming material layer containing an organic component containing a binder resin, wherein the content of the organic component [B] in the film-forming material layer is 10 to 25% by mass based on 100 parts by mass of the inorganic particles [A]. It is characterized by the denial.

The plasma display panel of the present invention includes a dielectric layer formed of the transfer film for forming a dielectric layer of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<Transfer Film for Dielectric Layer Formation>

The transfer film for dielectric layer formation of this invention is a transfer film for dielectric layer formation containing the film forming material layer formed on the support film, Comprising: In this film forming material layer, inorganic particle [A] containing a glass frit, and binder resin are included. It contains essential organic component [B], and it is essential that content of organic component [B] is 10-25 mass parts with respect to 100 mass parts of inorganic particle [A].

The transfer film for dielectric layer formation of this invention is a composite film used at the formation process of the dielectric layer which is a component of a PDP, The film forming material layer formed by apply | coating the film forming material composition mentioned later on a support film, and drying a coating film. It is provided with.

(1) Structure of Transfer Film for Dielectric Layer Formation:

Fig. 2 (a) is a cross sectional view schematically showing a transfer film for forming a dielectric layer of the present invention wound in a roll shape, and Fig. 2 (b) is a cross sectional view showing a layer structure of the transfer film [partial detail of (a)]. .

Usually, the transfer film shown in FIG. 2 is easily provided on the support film F1, the film formation material layer F2 formed in the surface of this support film F1 so that exfoliation is possible, and the film formation material layer F2 surface easily. It is comprised by the cover film F3. The cover film F3 may not be used depending on the property of the film formation material layer F2.

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 F1 is flexible, the paste composition (film forming material composition described later) can be applied using a roll coater, a blade coater, or the like, thereby forming a film forming material layer with a uniform film thickness. At the same time, the formed film forming material layer can be stored and supplied in a rolled state.

As resin which forms support film (F1), fluorine-containing resin, such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, nylon And cellulose. The thickness of the support film F1 becomes 20-100 micrometers, for example.

The film formation material layer (F2) which comprises a transfer film is a layer which becomes a glass sintered compact (dielectric layer) by baking, and contains the inorganic particle [A] containing a glass frit, and the organic component [B] containing a binder resin, It is essential that content of the organic component [B] is 10-25 mass parts with respect to 100 mass parts of inorganic particle [A]. Moreover, Preferably content of organic component [B] is 12-20 mass parts with respect to 100 mass parts of inorganic particle [A].

Although the thickness of the film forming material layer F2 changes with the film thickness of the dielectric layer formed, it is 10-150 micrometers normally, Preferably it is 40-120 micrometers.

The cover film F3 which comprises a transfer film is a film for protecting the surface (contact surface with a glass substrate) of the film formation material 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, resin illustrated as forming support film F1 is mentioned. The thickness of cover film F3 becomes 20-100 micrometers, for example.

(2) Manufacturing Method of Transfer Film for Dielectric Layer Formation:

The transfer film for dielectric layer formation of this invention is manufactured by forming a film forming material layer F2 on the support film F1, and providing (pressing) the cover film F3 on the said film forming material layer F2. can do.

As a formation method of a film forming material layer, the method of apply | coating the film forming material composition mentioned later on a support film, drying a coating film, and removing part or all of the said solvent is mentioned.

As a method of apply | coating a film forming material composition on a support film, it apply | coats by a roll coater from a viewpoint which can form efficiently the coating film with a large film thickness (for example, 20 micrometers or more), and excellent in the uniformity of film thickness. The method, the coating method with a blade coater, such as a doctor blade, the coating method with a curtain coater, the coating method with a wire coater, etc. are mentioned as a preferable thing.

Moreover, it is preferable that the mold release process is given to the surface of the support film to which the film forming material composition is apply | coated. Thereby, after transferring a film forming material layer, a support film can be peeled easily from the said film forming material layer.

As a coating film by the film forming material composition formed on the support film is dried, one part or all part of a solvent is removed and it becomes the film forming material layer which comprises a transfer film. As drying conditions of the coating film by a film forming material composition, it becomes about 0.1 to 30 minutes at 40-150 degreeC, for example. The residual ratio (solvent content in the film-forming material layer) of the solvent after drying is usually 5% by weight or less, and preferably 0.1 to 2% by weight.

It is preferable that the mold release process is also performed on the surface of the cover film (usually thermocompression-bonded) provided on the film formation material layer formed as mentioned above. Thereby, the cover film can be easily peeled from the film forming material layer before transferring the film forming material layer.

(3) Transfer of Film Forming Material Layer (Use Method of Transfer Film for Dielectric Layer Formation):

The film forming material layer on the support film is collectively transferred to the substrate surface. According to the transfer film for forming a dielectric layer of the present invention, since the film forming material layer can be reliably formed on the glass substrate by such a simple operation, the process improvement (high efficiency) in the dielectric layer forming step can be achieved. In addition, it is possible to improve the quality of the dielectric layer formed (for example, to express stable dielectric properties).

<Plasma Display Panel (Formation of Dielectric Layer)>

The plasma display panel of the present invention contains the dielectric layer formed on the substrate surface by transferring the film forming material layer constituting the dielectric layer forming transfer film of the present invention to the substrate surface and firing the transferred film forming material layer.

(1) Formation Process of Dielectric Layer:

An example of the transfer process of the film formation material layer by the transfer film for dielectric layer formation of the structure as shown in FIG. 2 is shown below.

(1) Cut the transfer film in the rolled state into a size corresponding to the substrate area.

(2) After peeling the cover film F3 from the surface of the film forming material layer F2 in the cut transfer film, the transfer film is laminated so that the surface of the film forming material layer F2 is in contact with the substrate surface.

(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 film forming material layer F2 fixed to the substrate by thermocompression bonding.

By the above operation, the film forming material 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 step) can be performed by a laminator device. In addition, the board | substrate may be preheated, and as a preheating temperature, it becomes 40-100 degreeC, for example.

The film-forming material layer F2 formed on the substrate surface is fired to become a glass sintered body (dielectric layer). Here, as a baking method, the method of arrange | positioning the board | substrate with which film formation material layer F2 was formed in high temperature atmosphere is mentioned. Thereby, the organic component [B] contained in the film formation material layer F2 is decomposed | disassembled and removed, and the glass frit contained in inorganic particle [A] melts and sinters. Here, as baking temperature, although it changes with the melting temperature of a board | substrate, etc., it becomes 400-700 degreeC, for example, More preferably, it becomes 500-600 degreeC. Moreover, the transfer film for dielectric layer formation of this invention can be used especially suitably when the film thickness of the dielectric layer formed is 25-50 micrometers.

<Film forming material composition>

The film formation material layer which comprises the transfer film for dielectric layer formation of this invention supports the film formation material composition containing the organic component [B] containing the inorganic particle [A] containing a glass frit, a binder resin, and a solvent. It is obtained by apply | coating and drying on a phase.

[A] Inorganic Particles:

The inorganic particles contain glass frit as an essential component. As the composition of the glass frit, for example, ① a mixture of lead oxide, boron oxide, and silicon oxide (PbO-B ₂ O ₃ -SiO _{2 type} ), ② zinc oxide, boron oxide, and silicon oxide (ZnO-B ₂ O ₃ -SiO ₂ )), ③ lead oxide, boron oxide, silicon oxide, a mixture of aluminum oxide (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ based), ④ lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ), and the like. In addition to the above, glass frits having a preferred composition for forming a dielectric layer of a plasma display can be used.

The softening point of the glass frit is usually in the range of 400 to 600 ° C. When the softening point of the glass frit is less than 400 ° C., the glass frit is melted in a step in which the organic material such as the binder resin is not completely decomposed and removed in the firing step of the film forming material layer by the dielectric film forming film of the present invention. As a result, part of the organic material remains in the dielectric layer to be formed, and as a result, the dielectric layer tends to be colored, and its light transmittance tends to be lowered. On the other hand, when the softening point of glass frit exceeds 600 degreeC, since baking needs to be carried out at high temperature rather than 600 degreeC, distortion etc. are easy to generate | occur | produce in a glass substrate. Moreover, in order to form the dielectric layer which has a high light transmittance, it is preferable that the softening point of a glass frit is 450-550 degreeC.

Although the average particle diameter (median diameter) of a glass frit is 0.1-10 micrometers normally, it is 1.0-3.0 micrometers preferably. When the average particle diameter of a glass frit is less than 1.0 micrometer, the plasticity of the film forming material layer in the transfer film for dielectric layer formation of this invention formed using the composition obtained cannot fully be improved. Moreover, when the average particle diameter of a glass frit exceeds 3.0 micrometers, there exists a possibility that the uniformity of the dielectric layer formed may be impaired. Moreover, the average particle diameter of a glass frit becomes like this. More preferably, it is 1.5-3.0 micrometers. Here, "average particle diameter of a glass frit" shall refer to the value calculated | required from the particle diameter measured by the laser diffraction scattering method.

The content of the glass frit in the inorganic particles [A] is usually 80 to 100 parts by mass in 100 parts by mass of the inorganic particles, and may contain any inorganic particles such as metals, inorganic pigments, ceramics, etc. in addition to the glass frit.

[B] Organic Ingredients:

The organic component contains the binder resin as an essential component, and the film forming material composition usually contains a solvent.

It is preferable that binder resin is an acrylic resin. By containing acrylic resin as binder resin, the film formation material layer formed will have the outstanding (heating) adhesiveness to a board | substrate. Therefore, in the case of applying the film forming material composition on the support film to produce the transfer film for forming the dielectric layer, the resulting transfer film is excellent in the transferability of the film forming material layer (heat adhesion to the substrate).

The acrylic resin constituting the film forming material composition is selected from (co) polymers which have appropriate adhesiveness and can bind inorganic particles, and which are completely oxidized and removed by firing treatment (400 ° C. to 600 ° C.) of the film forming material.

In such an acrylic resin, the homopolymer of the (meth) acrylate compound represented by following formula (1), the 2 or more types of copolymers of the (meth) acrylate compound represented by following formula (1), and the (meth) represented by following formula (1) Copolymers of acrylate compounds with copolymerizable monomers are included.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group.

As a specific example of the (meth) acrylate compound represented by the said Formula (1), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acryl Latex, 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, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, Alkyl (meth) arcs, such as undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Rate;

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

Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (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;

Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Polyalkylene glycols such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, and nonylphenoxypolypropylene glycol (meth) acrylate ( Meth) acrylates;

Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bor Cycloalkyl (meth) acrylates such as niel (meth) acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate;

Benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Of these, the group represented by R ² in the general formula (1) is preferably a group containing an alkyl group or an oxyalkylene group, and as a particularly preferred (meth) acrylate compound, butyl (meth) acrylate, ethylhexyl (meth) acrylate, Uryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate. The other copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the (meth) acrylate compound. Examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid, vinylbenzoic acid, maleic acid, and vinylphthalic acid; And vinyl group-containing radically polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene and isoprene.

The copolymerization component derived from the (meth) acrylate compound represented by the said Formula (1) in the acrylic resin which comprises a film forming material composition is 70 mass% or more normally, Preferably it is 90 mass% or more.

Here, as a specific example of a preferable acrylic resin, polymethyl methacrylate, polybutyl methacrylate, a methyl methacrylate- butyl methacrylate copolymer, etc. can be illustrated.

As the molecular weight of the acrylic resin constituting the film-forming material composition, the weight average molecular weight (hereinafter referred to simply as "weight average molecular weight") in terms of polystyrene by GPC is preferably 4,000 to 300,000, more preferably 10,000 to 200,000. Do.

It is preferable that it is 5-25 mass parts with respect to 100 weight part of inorganic particles, and, as for the content rate of the binder resin in a film forming material composition, it is more preferable that it is 5-20 weight part. When the ratio of the binder resin is too small, the inorganic particles cannot be reliably bound and maintained. On the other hand, when this ratio is excessive, the removal of the organic component during firing becomes difficult.

As a solvent which comprises a film forming material composition, it is preferable that affinity with a glass frit and the solubility of a binder resin are favorable, it can provide an appropriate viscosity to a film forming material composition, and can be easily evaporated away by drying.

Moreover, ketones, alcohols, and esters (hereinafter, these are referred to as "a specific solvent") whose standard boiling point (boiling point at 1 atmosphere) are 100-200 degreeC as an especially preferable solvent are mentioned.

As a specific example of such a specific solvent, Ketones, such as diethyl ketone, methylbutyl ketone, dipropyl ketone, cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Saturated aliphatic monocarboxylic acid alkyl esters such as acetic acid-n-butyl and amyl acetate; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate; and the like, and methylbutyl ketone and cyclohexanone can be exemplified. And diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, and the like. These specific solvents can be used individually or in combination of 2 or more types.

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

It is preferable that it is 1-50 mass parts with respect to 100 mass parts of glass frits from a viewpoint of keeping the viscosity of a film forming material composition in a preferable range, and it is more preferable that it is 5-40 mass parts in the film forming material composition. Do.

Moreover, it is preferable that it is 50 mass% or more, and, as for the content rate of the specific solvent with respect to all the solvents, it is more preferable that it is 70 mass% or more.

The film forming material composition may contain a silyl group-containing compound for the purpose of improving the dispersion stability of the inorganic particles. As this silyl group containing compound, the silyl group containing compound [saturated alkyl group containing (alkyl) alkoxysilane] represented by following formula (2) is preferable.

In formula, p is an integer of 3-20, m, n, and a are integers of 1-3.

In the said Formula (2), p which shows the carbon number of a saturated alkyl group becomes an integer of 3-20, Preferably it becomes an integer of 4-16.

Even if p contains a saturated alkyl group-containing (alkyl) alkoxysilane having less than 3, sufficient flexibility may not be expressed in the resulting film forming material layer. On the other hand, a saturated alkyl group-containing (alkyl) alkoxysilane having a p value of more than 20 has a high decomposition temperature and is free at the stage where the organic material (the silane derivative) is not completely decomposed and removed in the firing process of the film forming material layer obtained. Since the frit melts, part of the organic material remains in the dielectric layer to be formed, and as a result, the light transmittance of the dielectric layer may decrease.

Specific examples of the silyl group-containing compound represented by the formula (2) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, and n-eco Saturated alkyldimethylmethoxysilanes such as sildimethylmethoxysilane (a = 1, m = 1, n = 1);

saturated alkyl di such as n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-ecosyldiethylmethoxysilane Ethyl methoxysilanes (a = 1, m = 1, n = 2);

saturated alkyldipropyl methoxysilanes such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane and n-ecosyldipropylmethoxysilane (a = 1 , m = 1, n = 3);

Saturated alkyl dimethyl ethoxy silanes, such as n-propyl dimethyl ethoxysilane, n-butyl dimethyl ethoxy silane, n-decyl dimethyl ethoxy silane, n-hexadecyl dimethyl ethoxy silane, n-eicosyl dimethyl ethoxy silane, etc. (a = 1, m = 2, n = 1);

Saturated alkyl di, such as n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, and n-eicosyldiethylethoxysilane Ethyl ethoxysilanes (a = 1, m = 2, n = 2);

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

Saturated alkyl dimethyl propoxy silanes, such as n-propyl dimethyl propoxy silane, n-butyl dimethyl propoxy silane, n-decyl dimethyl propoxy silane, n-hexadecyl dimethyl propoxy silane, n-eicosyl dimethyl propoxy silane, etc. (a = 1, m = 3, n = 1);

Saturated alkyl di, such as n-propyl diethyl propoxy silane, n-butyl diethyl propoxy silane, n-decyl diethyl propoxy silane, n-hexadecyl diethyl propoxy silane, and n-ecosyl diethyl propoxy silane Ethyl propoxysilanes (a = 1, m = 3, n = 2);

Saturated alkyl dipropyl propoxy silanes, such as n-butyl dipropyl propoxy silane, n-decyl dipropyl propoxy silane, n-hexadecyl dipropyl propoxy silane, and n-eicosyl dipropyl propoxy silane (a = 1 , m = 3, n = 3);

Saturated alkyl methyl dimethoxy silanes, such as n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, and n-eicosylmethyldimethoxysilane (a = 2, m = 1, n = 1);

Saturated alkyl ethyl dimethoxy silanes, such as n-propyl ethyl dimethoxy silane, n-butyl ethyl dimethoxy silane, n-decyl ethyl dimethoxy silane, n-hexadecyl ethyl dimethoxy silane, and n-eicosyl ethyl dimethoxy silane (a = 2, m = 1, n = 2);

Saturated alkyl propyl dimethoxy silanes, such as n-butyl propyl dimethoxy silane, n-decyl propyl dimethoxy silane, n-hexadecyl propyl dimethoxy silane, and n-eicosyl propyl dimethoxy silane (a = 2, m = 1). , n = 3);

Saturated alkylmethyl diethoxysilanes, such as n-propylmethyl diethoxysilane, n-butylmethyl diethoxysilane, n-decylmethyl diethoxysilane, n-hexadecylmethyl diethoxysilane, and n-eicosylmethyl diethoxysilane (a = 2, m = 2, n = 1);

Saturated alkyl ethyl diethoxysilanes, such as n-propyl ethyl diethoxy silane, n-butyl ethyl diethoxy silane, n-decyl ethyl diethoxy silane, n-hexadecyl ethyl diethoxy silane, and n-eicosyl ethyl diethoxy silane. (a = 2, m = 2, n = 2);

Saturated alkyl propyl diethoxysilanes, such as n-butyl propyl diethoxysilane, n-decyl propyl diethoxy silane, n-hexadecyl propyl diethoxy silane, and n- ethoxy propyl diethoxy silane (a = 2, m = 2) , n = 3);

saturated alkyls such as n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-ecosylmethyldipropoxysilane Methyldipropoxysilanes (a = 2, m = 3, n = 1);

saturated alkyls such as n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-ecosylethyldipropoxysilane Ethyldipropoxysilanes (a = 2, m = 3, n = 2);

Saturated alkyl propyl dipropoxy silanes, such as n-butyl propyl dipropoxy silane, n-decyl propyl dipropoxy silane, n-hexadecyl propyl dipropoxy silane, and n- ecoxy propyl dipropoxy silane (a = 2, m = 3, n = 3);

Saturated alkyl trimethoxysilanes, such as n-propyl trimethoxysilane, n-butyl trimethoxysilane, n-decyl trimethoxysilane, n-hexadecyl trimethoxysilane, and n-eicosyl trimethoxysilane (a = 3, m = 1);

Saturated alkyl triethoxysilanes, such as n-propyl triethoxysilane, n-butyl triethoxysilane, n-decyl triethoxysilane, n-hexadecyl triethoxysilane, and n-eicosyl triethoxysilane (a = 3, m = 2);

Saturated alkyl tripropoxy silanes, such as n-propyl tripropoxy silane, n-butyl tripropoxy silane, n-decyl tripropoxy silane, n-hexadecyl tripropoxy silane, and n-eicosyl tripropoxy silane (a = 3, m = 3), etc. These can be used individually or in combination of 2 or more types.

Of these, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-butyltriethoxy Silane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n-decyltripropoxy Silane, n-hexadecyl tripropoxysilane, and the like are particularly preferable.

It is preferable that it is 5 mass parts or less with respect to 100 mass parts of glass frits, and, as for the content rate of the silyl group containing compound in a film forming material composition, it is more preferable that it is 3 mass parts or less. When the proportion of the silyl group-containing compound is excessive, the viscosity may increase over time when preserving the resulting film-forming material composition, or the silyl group-containing compounds may cause a reaction to lower the light transmittance after firing.

In addition, in a film forming material composition, a plasticizer may be contained in order to express favorable flexibility and combustibility in the film forming material layer formed. As a plasticizer, the plasticizer containing the compound represented by following formula (3) or 4, or polypropylene glycol is preferable.

Wherein R ³ and R ⁶ each represent the same or different alkyl group having 1 to 30 carbon atoms, R ⁴ and R ⁵ each represent the same or different methylene group or an alkylene group having 2 to 30 carbon atoms, and s is 0 To 5 and t is a number from 1 to 10.

In formula, R <^7> represents a C1-C30 alkyl group or alkenyl group.

According to the transfer film provided with the film forming material layer containing a plasticizer, even if this is bent, a small crack (cracking) does not generate | occur | produce on the surface of this film forming material layer, and this transfer film becomes excellent in flexibility It can also be easily wound up in roll shape.

In particular, since the plasticizer containing the compound represented by the above formula (3) or (4) is easily decomposed and removed by heat, the light transmittance of the dielectric layer obtained by firing the film forming material layer is not reduced.

In the general formula (3), the alkyl group represented by R ³ or R ⁶ and the alkylene group represented by R ⁴ or R ⁵ may be linear, branched, or may be saturated or unsaturated.

Carbon number of the alkyl group represented by R <^3> or R <^6> becomes 1-30, Preferably it is 2-20, More preferably, it is 4-10.

When carbon number of the said alkyl group exceeds 30, solubility of the plasticizer with respect to the solvent which comprises this invention may fall, and favorable flexibility may not be obtained.

Specific examples of the compound represented by Formula 3 include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl diglycol adipate Etc. can be mentioned. Preferably, n is a compound represented by 2-6.

In Formula 4, R ⁷ represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and the alkyl group and alkenyl group represented by R ⁷ may be linear, branched, or may be saturated or unsaturated. .

Carbon number of the alkyl group or alkenyl group represented by R <^7> becomes 1-30, Preferably it is 2-20, More preferably, it is 10-18.

Specific examples of the compound represented by the formula (4) include propylene glycol monolaurate, propylene glycol monooleate, and the like.

Moreover, when using polypropylene glycol as a plasticizer, it is preferable that the weight average molecular weight (Mw) of such polypropylene glycol exists in the range of 200-3,000, and it is especially preferable to exist in the range of 300-2,000. When Mw of polypropylene glycol is less than 200, it may become difficult to form a film forming material layer with a large film strength on a support film, and the transfer performed using the transfer film comprised with the said film forming material layer. In a process, when it is going to peel a support film from the film forming material layer heat-bonded to the glass substrate, the said film forming material layer may cause cohesive failure. On the other hand, when Mw exceeds 3,000, the film formation material layer with favorable heat adhesiveness with a glass substrate may not be obtained.

As content of the plasticizer in a film forming material composition, 0.5-10 mass parts is preferable with respect to 100 mass parts of inorganic powder, and 2-7 mass parts is more preferable. When the addition amount of a plasticizer increases, there exists a possibility that it may become impossible to maintain the intensity | strength of the transfer film for dielectric layer formation of this invention obtained.

The film forming material composition may contain, in addition to the above components, various additives such as a tackifier, a surface tension regulator, a stabilizer, an antifoaming agent, and a dispersant as optional components. As the dispersant, fatty acids are preferably used. In particular, fatty acids having 8 to 30 carbon atoms are preferred. Preferable specific examples of the fatty acid include saturated fatty acids such as octanoic acid, undecyl acid, lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid and arachnic acid; Unsaturated fatty acids, such as elic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, and carboxypolycaprolactone (n = 2) monoacrylate, are mentioned, These can be used individually or in combination of 2 or more types.

5 mass parts or less are preferable with respect to 100 mass parts of inorganic particles, and, as for the content rate of the dispersing agent in a film formation material composition, 3 mass parts or less are more preferable.

The film-forming material composition usually uses inorganic kneaders [A] containing the glass frit and organic ingredients [B] containing the binder resin and the solvent, using kneading and dispersing machines such as a roll kneader, a mixer, a homo mixer, and a sand mill. It can manufacture by kneading. As a viscosity of the said film forming material composition, it is preferable that it is 100-10000 mPa * s- ¹ .

<Example>

EMBODIMENT OF THE INVENTION Hereinafter, although the Example of this invention is described, this invention is not limited by these. In addition, "part" shows a "mass part" below.

<Example 1>

(1) Preparation of Film Forming Material Composition:

PbO-B ₂ O ₃ -SiO ₂ -based glass frit (softening point 480 ° C., average particle diameter 2.0 μm) as the inorganic particles (component [A]), 2-ethylhexyl methacrylate as binder resin (component [B]) / Hydroxyethyl methacrylate = 90% by mass / 10% by mass copolymer (weight average molecular weight: 50,000) 8 parts, a plasticizer (component [B]) represented by the following formula (a) (propylene glycol monooleate) 4 In addition, 20 parts of propylene glycol monomethyl ethers were knead | mixed using a dispersing machine as a solvent (component [B]), and the film forming material composition which has a viscosity of 4,000 mPa * s- ¹ was manufactured.

(2) Preparation and Evaluation of Transfer Film for Dielectric Layer Formation (Flexibility):

Applying the film-forming material composition prepared in the above (1) using a blade coater on a support film (400 mm wide, 30 m long, 38 μm thick) containing polyethylene terephthalate (PET) pre-release treated, The solvent was removed by drying the formed coating film at 100 degreeC for 5 minutes, and the 50-micrometer-thick film forming material layer was formed on the support film by this (film thickness 1). Subsequently, by adhering a cover film (400 mm wide, 30 m long, 25 μm thick) containing PET previously released on the film forming material layer, the dielectric layer of the present invention comprising the structure as shown in FIG. 2. A transfer film for formation was produced.

After the obtained transfer film was bent at 135 ° and held for 10 seconds, the original film was returned to its original state, and the cover film was peeled off to evaluate the presence or absence of (bending cracking) of cracking on the surface of the film forming material layer (flexibility evaluation; evaluation 1 ). The results are shown in Table 1.

(3) Transfer and Evaluation of Film Forming Material Layer (Transferability):

After spraying 0.5 mg (about 50) of the resin powder of 200 micrometers (about 50) as a foreign material on the glass substrate surface (fixed surface of a bus electrode) for 20-inch panels, peeling a cover film from the transfer film obtained by said (2) The transfer film (lamination body of a support film and a film formation material layer) was superposed so that the surface of a film formation material layer might contact the said glass substrate surface, and this transfer film was thermocompression-bonded with the heating roll. Here, as crimping | compression-bonding conditions, the surface temperature of the heating roll was 100 degreeC, the roll pressure was 3 kg / cm, and the moving speed of the heating roll was 1 m / min.

After the thermocompression bonding was completed, the support film was peeled off from the film forming material layer fixed (heat-bonded) to the glass substrate surface, and evaluation of transfer of the film forming material layer was carried out (transferability evaluation; evaluation 2). The results are shown in Table 1.

(4) Firing and evaluation of the film forming material layer (content of component [B], pinhole and light transmittance of the dielectric layer):

The glass substrate which transfer-formed the film formation material layer by said (3) is arrange | positioned in a baking furnace, and the temperature in a furnace is heated up to 580 degreeC with the temperature increase rate of 10 degree-C / min from normal temperature, and it is air | atmosphere in the atmosphere of 580 degreeC temperature atmosphere. By baking over 30 minutes, the dielectric layer with a film thickness of 30 micrometers containing a glass sintered compact was formed on the glass substrate surface (film thickness 2).

By measuring the mass before and after baking in this dielectric layer, content of component [B] with respect to 100 mass parts of component [A] was measured (evaluation 3). Here, it calculated as (content of component [B] with respect to 100 mass parts of component [A]) = 100x (mass of the mass-dielectric layer of a film forming material layer) / (mass of a dielectric layer).

In addition, the number of occurrence of pinholes in the dielectric layer corresponding to ten positions of the resin powder dispersed in the step (3) was evaluated (evaluation 4). The results are shown in Table 1.

Moreover, the light transmittance (measurement wavelength 600 nm) was measured about this dielectric layer. The results are shown in Table 1 (evaluation 5).

<Example 2>

Except having changed the quantity of the binder resin in Example 1 into 11 parts, it carried out similarly to Example 1, manufacturing a film forming material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer, The same evaluation was performed. The results are shown in Table 1.

<Example 3>

Except having changed the quantity of the binder resin in Example 1 into 14 parts, it carried out similarly to Example 1, manufacturing a film forming material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer, The same evaluation was performed. The results are shown in Table 1.

<Example 4>

Except having changed the quantity of the binder resin in Example 1 into 17 parts, it carried out similarly to Example 1, manufacturing a film forming material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer, The same evaluation was performed. The results are shown in Table 1.

Example 5

Except having changed the average particle diameter of the glass frit in Example 2 into 0.5 micrometer, it carried out similarly to Example 1, manufacturing a film formation material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer, Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 6>

Except having changed the average particle diameter of the glass frit in Example 2 to 1.5 micrometers, it carried out similarly to Example 1, manufacture of a film formation material composition, preparation of the transfer film for dielectric layer formation, and formation of a dielectric layer, Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 7>

Except having changed the average particle diameter of the glass frit in Example 2 into 3.5 micrometers, it carried out similarly to Example 1, manufacturing a film formation material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer, Evaluation similar to 1 was performed. The results are shown in Table 1.

Comparative Example 1

Except having changed the quantity of the binder resin in Example 1 into 23 parts, it carried out similarly to Example 1, manufacturing a film forming material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer. The same evaluation was performed. The results are shown in Table 1.

Comparative Example 2

Except having changed the quantity of the binder resin in Example 1 into 5 parts, it carried out similarly to Example 1, manufacturing a film forming material composition, preparing the transfer film for dielectric layer formation, and forming a dielectric layer. The same evaluation was performed. The results are shown in Table 1.

Film thickness 1 (㎛) Rating 1 Evaluation 2 Film thickness 2 (㎛) Evaluation 3 (part) Evaluation 4 Evaluation 5 (%) Example 1 50 Good Good 30 12.5 0 85 Example 2 54 Good Good 30 15.5 0 85 Example 3 58 Good Good 30 18.5 0 85 Example 4 64 Good Good 30 21.5 2 85 Example 5 54 Good Good 30 15.5 0 85 Example 6 54 Good Good 30 15.5 0 85 Example 7 54 Good Good 30 15.5 0 80 Comparative Example 1 73 Good Good 30 27.5 8 70 Comparative Example 2 46 Bad Bad - - - - Film thickness 1; Film thickness evaluation 1 of the film-forming material layer; Flexibility assessment (no cracks → good, cracked → bad) evaluation 2; Transferability evaluation (transfer possible → good, transfer impossible → bad) film thickness 2; Film thickness evaluation of the dielectric layer 3; Evaluation of the ratio of component [B] to 100 parts by mass of component [A] in the film-forming material layer 4; Evaluation of the number of pinholes in the dielectric layer (out of 10 locations corresponding to foreign matters) 5; Light transmittance of dielectric layer (600 nm)

According to the transfer film for dielectric layer formation of this invention, it has the following effects.

(1) A uniform dielectric layer can be formed without being affected by dust and foreign matter on the substrate.

(2) A dielectric layer having a high light transmittance can be formed.

(3) A transfer film for forming a dielectric layer having excellent flexibility and transferability (heat adhesion to a substrate) of a film forming material layer can be produced.

(4) The dielectric layer can be formed efficiently.

(5) A dielectric layer having a large film thickness can be efficiently formed.

According to the plasma display panel of the present invention, the following effects are obtained.

(6) By providing a dielectric layer excellent in uniformity, a plasma display panel with high display quality can be provided.

Claims (11)

[A] an inorganic particle comprising a glass frit, and [B] Organic Component Containing Binder Resin A film-forming material layer containing a film, wherein the content of the organic component [B] in the film-forming material layer is 10 to 25 parts by mass with respect to 100 parts by mass of the inorganic particles [A]. . The transfer film for forming a dielectric layer according to claim 1, wherein the content of the organic component [B] in the film forming material layer is 12 to 20 parts by mass with respect to 100 parts by mass of the inorganic particles [A]. The transfer film for forming a dielectric layer according to claim 1, wherein the average particle diameter of the glass frit in the inorganic particles [A] in the film forming material layer is 1.0 to 3.0 µm. The transfer film for forming a dielectric layer according to claim 1, wherein the thickness of the dielectric layer obtained is 25 to 50 µm. The transfer film for forming a dielectric layer according to claim 1, wherein the content of the binder resin in the organic component [B] in the film forming material layer is 5 to 25 parts by mass with respect to 100 parts by mass of the inorganic particles [A]. The transfer film for forming a dielectric layer according to claim 1, comprising a plasticizer as an organic component [B] in the film forming material layer. The transfer film for forming a dielectric layer according to claim 1, wherein the silyl group-containing compound is contained as the organic component [B] in the film forming material layer. The transfer film for forming a dielectric layer according to claim 1, wherein the content of components other than the binder resin in the organic component [B] in the film forming material layer is 2 to 7 parts by mass with respect to 100 parts by mass of the inorganic particles [A]. The transfer film for forming a dielectric layer according to claim 8, wherein components other than the binder resin in the organic component [B] in the film forming material layer are plasticizers. The transfer film for forming a dielectric layer according to claim 1, wherein the softening point of the glass frit in the inorganic particles [A] in the film forming material layer is 450 to 550 ° C. A plasma display panel comprising a dielectric layer formed of the transfer film for forming a dielectric layer according to claim 1.