JP3958846B2 - Transfer sheet - Google Patents

Description

表１に示されるように、本発明の転写シート（試料１〜３）は、転写層と保護フィルムとの剥離性、および、ガラス基板への転写性も良好であった。また、これらの転写シートを用いて形成した電極パターンは、厚み、線幅が均一であり、高い精度で形成されていることが確認された。
【００６１】
これに対して、ベースフィルムと転写層との剥離強度が０．２ｇ／２５ｍｍ未満、保護フィルムと転写層との剥離強度が０．１ｇ／２５ｍｍ未満である転写シート（試料４）では、スリット時に保護フィルムと転写層間にエアーまたは異物が混入し、一方、ベースフィルムと転写層間では転写層の密着力が低いために、転写層の剥がれやクラックを生じやすかった。このため、この転写シートを用いて形成した電極パターンでは、断線欠陥が多発した。
【００６２】
さらに、ベースフィルムと転写層との剥離強度が３０ｇ／２５ｍｍを超え、保護フィルムと転写層との剥離強度が３０ｇ／２５ｍｍ以上となる転写シート（試料５）では、保護フィルムの剥離時に、転写層に傷や凹みがつき、またベースフィルムの剥離において一部転写層の凝集破壊を生じた。このため、この転写シートを用いて形成した電極パターンでは、断線欠陥を多発した。
【００６３】
【発明の効果】
以上詳述したように、本発明によればベースフィルム上に、ガラスフリットと導電性粉体を含む無機成分と焼成除去可能な有機成分とを少なくとも含有する転写層を剥離強度が０．２ｇ／２５ｍｍ以上で３０ｇ／２５ｍｍ以下の範囲内となるように剥離可能に設けて転写シートとするので、被転写体への転写層の転写において、転写層に凝集破壊が生じることなくベースフィルムと転写層を剥離することができ転写性が良好であり、また、剥離強度を０．１ｇ／２５ｍｍ以上で３０ｇ／２５ｍｍ未満の範囲内で、かつ、上記のベースフィルムと転写層との剥離強度よりも小さく設定して転写層上に保護フィルムを備える場合には、転写層の凝集破壊を生じることなく、また、ベースフィルムと転写層の剥離を生じることなく保護フィルムと転写層とを剥離することができ、さらに、上記のベースフィルムと転写層の剥離、および、保護フィルムと転写層の剥離は、剥離強度が上記範囲内にあることにより、大きなテンション変動を来すことがなく機械的に安定して行うことができ、被転写体への転写層の転写性が良好なものとなり、また、有機成分が感光性を有する場合には、露光・現像によるパターニングの精度が高く、これにより、電極の高精細なパターンを形成することができる。
【図面の簡単な説明】
【図１】本発明の転写シートの一実施形態を示す概略断面図である。
【図２】本発明の転写シートの他の実施形態を示す概略断面図である。
【図３】プラズマディスプレイパネルの一例を示す概略構成図である。
【図４】本発明の転写シートを用いた電極パターン形成の一例を説明するための工程図である。
【符号の説明】
１，１１…転写シート
２，１２…ベースフィルム
３，１３…転写層
１４…保護フィルム
Ｍ…フォトマスク[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transfer sheet for forming an electrode pattern in a plasma display panel with high accuracy.
[0002]
[Prior art]
In recent years, it has been required that fine patterns such as electrodes in a plasma display panel (PDP) can be formed with higher accuracy and at lower manufacturing costs.
[0003]
Conventionally, an electrode pattern in a PDP is formed by forming a predetermined pattern by a printing method such as screen printing or offset printing using a pattern forming paste containing a conductive powder, and baking to form a pattern after drying. It was done by law.
[0004]
[Problems to be solved by the invention]
The above printing method has a simple process and is expected to reduce the manufacturing cost. However, the screen printing method has a limit of printing accuracy due to the elongation of the mesh material constituting the screen printing plate, and the formed pattern has a mesh. There is a problem that eyes are formed or pattern blurring occurs and the edge accuracy of the pattern is low. In the offset printing method, as the number of times of printing proceeds, the pattern forming paste is not completely transferred to the substrate but remains on the blanket, resulting in a decrease in pattern accuracy. Therefore, it is necessary to replace the blanket at any time to prevent the blanket of the paste from remaining, and to maintain the pattern accuracy. Therefore, there is a problem that the operation is extremely complicated.
[0005]
The present invention has been made in view of the above circumstances, and an object thereof is to provide a transfer sheet capable of forming a high-definition electrode pattern.
[0006]
[Means for Solving the Problems]
  In order to achieve such an object, the transfer sheet of the present invention is a transfer sheet for forming an electrode of a plasma display panel, and comprises a base film and a transfer layer provided on the base film so as to be peelable. Provided, the transfer layer contains at least an inorganic component containing glass frit and conductive powder, an organic component that can be removed by baking, and when the peel strength between the base film and the transfer layer is measured under the following measurement conditions, It was set as the structure which exists in the range of 0.2 g / 25mm or more and 5.0 g / 25mm or less.
(Peel strength measurement conditions)
  Cut out the sample (25mm width) along the flow direction of the transfer sheet,100 mm of the sampleThe peel strength is measured by peeling 180 ° at a rate of / min.
[0007]
  The transfer sheet of the present invention comprises a protective film that can be peeled off on the transfer layer, and the peel strength between the protective film and the transfer layer.Is measured under the above measurement conditions,0.1g / 25mm or more2.5g / 25mm or lessAnd having a smaller strength than the peel strength between the base film and the transfer layer.
[0008]
And it was set as the structure in which said organic component has photosensitivity.
[0009]
In the present invention as described above, the base film and the transfer layer can be peeled off without causing cohesive failure of the transfer layer in the transfer, and when the protective film is present on the transfer layer, the base film and the transfer layer are separated. The protective film and the transfer layer can be peeled off and transferred to the transfer material without causing peeling and without causing cohesive failure of the transfer layer.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0011]
FIG. 1 is a schematic sectional view showing an embodiment of the transfer sheet of the present invention. In FIG. 1, a transfer sheet 1 includes a base film 2 and a transfer layer 3 provided on the base film 2 so as to be peelable. The transfer layer 3 contains at least an inorganic component containing glass frit and conductive powder and an organic component that can be removed by baking, and the peel strength from the base film 2 is 0.2 g / 25 mm or more and 30 g / 25 mm or less, Preferably, it is set to be in a range of 1.0 g / 25 mm or more and 10 g / 25 mm or less.
[0012]
FIG. 2 is a schematic sectional view showing another embodiment of the transfer sheet of the present invention. In FIG. 2, the transfer sheet 11 includes a base film 12, a transfer layer 13 provided on the base film 12 in a peelable manner, and a protective film 14 provided on the transfer layer 13 in a peelable manner. ing. The transfer layer 13 contains at least an inorganic component containing glass frit and conductive powder and an organic component that can be removed by baking. The transfer layer 13 has a peel strength with respect to the base film 12 of 0.2 g / 25 mm to 30 g / 25 mm, preferably 1.0 g / 25 mm to 10 g / 25 mm. The peel strength with the film 14 is 0.1 g / 25 mm or more and less than 30 g / 25 mm, preferably within the range of 0.2 g / 25 mm or more and 10 g / 25 mm or less, and lower than the peel strength with the base film 12 described above. Is set to
[0013]
In the transfer films 1 and 11 described above, if the peel strength between the base films 2 and 12 and the transfer layers 3 and 13 is less than 0.2 g / 25 mm, the transfer layers 3 and 13 are likely to be undesirably peeled off or dropped off. The handling properties of the transfer sheets 1 and 11 are deteriorated. If the peel strength exceeds 30 g / 25 mm, the transfer layers 3 and 13 may be coherently broken when the base films 2 and 12 and the transfer layers 3 and 13 are peeled off. When peeling with the layers 3 and 13 is performed using an apparatus, the load on the apparatus side for stably and surely peeling the base films 2 and 12 and the transfer layers 3 and 13 with such a high peel strength is large. It is not preferable.
[0014]
On the other hand, if the peel strength between the protective film 14 and the transfer layer 13 is less than 0.1 g / 25 mm in the transfer film 11 described above, the protective film 14 is likely to be undesirably peeled or dropped off, and the transfer sheet 11 is easy to handle. Becomes worse. Further, when the peel strength is 30 g / 25 mm or more, cohesive failure may occur in the transfer layer 13 when the protective film 14 and the transfer layer 13 are peeled, and the apparatus is used to peel the protective film 14 and the transfer layer 13. When it is used, tension fluctuation is large, and stable peeling becomes difficult, which is not preferable. The peel strength between the protective film 14 and the transfer layer 13 is preferably lower than the peel strength between the base film 12 and the transfer layer 13 with a difference of 1.0 g / 25 mm or more.
[0015]
The transfer sheets 1 and 11 according to the present invention can peel the base films 2 and 12 and the transfer layers 3 and 13 without causing the cohesive failure of the transfer layers 3 and 13, and the protective film 14 serves as the transfer layer 13. In the transfer sheet 11 existing above, the protective film 14 and the transfer layer 13 can be peeled without causing the base film 12 and the transfer layer 13 to peel off and without causing the cohesive failure of the transfer layer 13.
[0016]
The peel strength in the present invention is a value obtained by preparing a sample having a width of 25 mm and peeling 180 ° at a rate of 100 mm / min using a large-scale Tensilon universal testing machine UTM-500 of a crystal oscillation digital servo system constant speed strain method. is there.
[0017]
The peel strength of the transfer layers 3 and 13 with respect to the base films 2 and 12 is determined by setting the content of inorganic components, the type and content of organic components, the solvent used, coating conditions, etc. Or it can be in said range (0.2-30 g / 25mm) by the setting of the material, thickness, surface state, film thickness, and surface treatment of the base films 2 and 12. Further, the peel strength of the transfer layer 13 with respect to the protective film 14 is also determined by setting the content of the inorganic component in the transfer layer 13, the type and content of the organic component, the solvent used, the coating conditions, and / or the like. It can be within the above range (0.1 g / 25 mm or more and less than 30 g / 25 mm) by setting the material, thickness, and surface state.
[0018]
Such transfer sheets 1 and 11 may be either a sheet shape or a long shape. In the case of a long shape, the transfer sheets 1 and 11 can be formed into a roll shape wound around a core. The core to be used is preferably a core formed of ABS resin, vinyl chloride resin, bakelite, or a paper tube impregnated with resin in order to prevent generation of dust and paper dust.
[0019]
Next, the configuration of the transfer sheets 1 and 11 will be described.
Base film
The base films 2 and 12 constituting the transfer sheets 1 and 11 of the present invention are stable with respect to the ink composition when the transfer layers 3 and 13 are formed, have flexibility, and have tension or A material that does not cause significant deformation under pressure is selected and used in consideration of the peel strength with respect to the transfer layers 3 and 13.
As a material to be used, a resin film can be mentioned first. Specific examples of the resin film include polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film, polystyrene film, polymethacrylate film, polyvinyl chloride film, polyvinyl alcohol film, polyvinyl Butyral film, nylon film, polyether ketone film, polyphenylene sulfide film, polysulfone film, polyether sulfone film, polytetrafluoroethylene-perfluoroalkyl vinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene -Hexafluoropropylene film, polychlorotrifluoroethylene Film, polyvinylidene fluoride film, polyethylene terephthalate film, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide Films, films obtained by blending these resin materials with fillers, films using these resin materials uniaxially or biaxially stretched, and using these resin materials, the stretch ratio in the width direction was increased from the flow direction. A biaxially stretched film, a biaxially stretched film in which the stretch ratio in the flow direction is increased from the width direction using these resin materials, and a laminate of the same or different types of these films, And include a composite film or the like which is created by co-extruding the same or different resin selected from a raw material resin used for these films. Moreover, what processed the said resin film, for example, a silicon processing polyethylene terephthalate, a corona processing polyethylene terephthalate, a melamine processing polyethylene terephthalate, a silicon processing polypropylene, a corona processing polypropylene etc., may be used.
[0020]
Further, a metal foil or a metal steel strip can be used as the base films 2 and 12. Specific examples of such metal foil and metal steel strip include copper foil, copper steel strip, aluminum foil, aluminum steel strip, stainless steel strip such as SUS430, SUS301, SUS304, SUS420J2 and SUS631, beryllium steel strip, etc. Can do. Furthermore, what stuck the above-mentioned metal foil or the metal steel strip to the above-mentioned resin film can also be used.
[0021]
The thickness of the base films 2 and 12 as described above can be set in the range of 4 to 400 μm, preferably 10 to 150 μm.
Transfer layer
For the transfer layers 3 and 13, an ink composition containing at least an inorganic component containing glass frit and conductive powder and an organic component that can be removed by baking is applied to the base films 2 and 12 by a direct gravure coating method or a gravure reverse coating method. It can be formed by coating and drying by known coating means such as reverse roll coating, slide die coating, slit die coating, comma coating, and slit reverse coating.
(1) Inorganic component
Examples of the glass frit include a softening temperature of 350 to 650 ° C. and a thermal expansion coefficient α.₃₀₀ Is 60 × 10^-7~ 100 × 10^-7A glass frit that is / ° C can be used. When the softening temperature of the glass frit exceeds 650 ° C., it is necessary to increase the firing temperature. For example, if the heat resistance of the pattern forming body is low, thermal deformation occurs in the firing step, which is not preferable. Further, when the softening temperature of the glass frit is less than 350 ° C., the glass frit is fused before the organic components are completely decomposed, volatilized and removed by firing, and thus voids are likely to be generated. Furthermore, the thermal expansion coefficient α of the glass frit₃₀₀ Is 60 × 10^-7/ ° C or 100 x 10^-7If it exceeds / ° C., the difference from the coefficient of thermal expansion of the pattern-formed body may be too large, resulting in distortion and the like. The average particle size of such a glass frit is preferably in the range of 0.1 to 10 μm. As these glass frit, for example, Bi₂ O_Three Or the glass frit which has PbO as a main component can be used.
[0022]
When an alkali development type photosensitive resin composition as described later is used as the organic component that can be removed by baking, it is preferable to use a bismuth-based glass frit from the standpoint of resistance to polymers.
[0023]
The transfer layers 3 and 13 are inorganic powders such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, calcium carbonate, and the like in 100 parts by weight of the glass frit. On the other hand, it can contain in 30 weight part or less. Such an inorganic powder preferably has an average particle size in the range of 0.1 to 20 μm, and serves as an aggregate to prevent pattern casting during firing. In order to improve contrast, the transfer layers 3 and 13 may contain a refractory black pigment as an inorganic powder. Examples of black pigments include Co-Cr-Fe, Co-Mn-Fe, Co-Fe-Mn-Al, Co-Ni-Cr-Fe, Co-Ni-Mn-Cr-Fe, and Co-Ni-Al-Cr. -Fe, Co-Mn-Al-Cr-Fe-Si, etc. can be mentioned.
[0024]
As said electroconductive powder, 1 type (s) or 2 or more types, such as Au powder, Ag powder, Cu powder, Ni powder, Al powder, Ag-Pd powder, can be used. The shape of the conductive powder may be various shapes such as a spherical shape, a plate shape, a lump shape, a conical shape, a rod shape, etc., but a spherical conductive powder having no cohesiveness and good dispersibility is preferable. The average particle size is preferably in the range of 0.05 to 10 μm. The content ratio of the conductive powder and the glass frit in the transfer layers 3 and 13 is in the range of 2 to 20 parts by weight, preferably 2 to 15 parts by weight of the glass frit with respect to 100 parts by weight of the conductive powder. be able to.
(2) Organic components
A thermoplastic resin can be used as the organic component contained in the transfer layers 3 and 13 which can be removed by firing.
[0025]
The thermoplastic resin is contained as a binder for the above-mentioned inorganic components and for the purpose of improving transferability. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl Methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n -Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate Chryrate, n-decyl acrylate, n-decyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone Examples thereof include polymers or copolymers comprising at least one of the above, cellulose derivatives such as ethyl cellulose, and the like.
[0026]
In particular, among the above, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Preferred is a polymer or copolymer comprising at least one of tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and ethyl cellulose.
[0027]
The molecular weight of the thermoplastic resin is preferably in the range of 10,000 to 500,000.
[0028]
A photosensitive resin composition can be used as the organic component contained in the transfer layers 3 and 13 that can be removed by firing.
[0029]
The photosensitive resin composition contains at least a polymer, a monomer, and an initiator, and is volatilized and decomposed by firing so that no carbides remain in the fired film.
[0030]
Examples of the polymer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert- Butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n- Decyl acrylate, n-decyl methacrylate, 2-hydroxyethyl acrylate Of at least one of a salt, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, acrylic acid, methacrylic acid, acrylic acid Dimer (for example, M-5600 manufactured by Toa Gosei Co., Ltd.), 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate, hexa A polymer or copolymer comprising one or more of 2-methacryloyloxyethyl hydrophthalate, 2-acryloyloxyethyl hexahydrophthalate, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof; Carboxyl group included Cellulose derivatives and the like.
[0031]
Moreover, although the polymer etc. which added the ethylenically unsaturated compound which has a glycidyl group or a hydroxyl group to said copolymer are mentioned, it is not limited to these.
[0032]
The molecular weight of the polymer is in the range of 5,000 to 300,000, preferably 30,000 to 150,000. Further, other polymers such as methacrylic acid ester polymer, acrylic acid ester polymer, cellulose derivative, N-vinylpyrrolidone polymer, polyvinyl alcohol, polyvinyl alcohol derivative and the like may be mixed.
[0033]
As the reactive monomer constituting the photosensitive resin composition, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butane Diol diacrylate, , 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propylene oxide modified pentaerythritol triacrylate, Lopylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,3 -Pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and the above acrylate replaced with methacrylate, gamma-methacryloxypropyltrimethoxysilane, 1-vinyl-2 -Pyrrolidone etc. are mentioned. In the present invention, the above reactive monomers can be used as one or a mixture of two or more or as a mixture with other compounds.
[0034]
Photopolymerization initiators constituting the photosensitive resin composition include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetate , Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p -Azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione- 2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) Oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, naphthalenesulfonyl Chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyldisulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, tetrabrominated carbon, tribromophenylsulfone, peroxidation A combination of a photoreducible pigment such as benzoin, eosin, methylene blue and a reducing agent such as ascorbic acid or triethanolamine can be used. In the present invention, one or more of these photopolymerization initiators can be used.
[0035]
The content of the thermoplastic resin or photosensitive resin composition in the transfer layers 3 and 13 takes into consideration the type of material used, the material and surface properties of the base film, the material and surface properties of the protective film described later, and the like. The peel strength between the base film and the transfer layer is in the range of 0.2 g / 25 mm to 30 g / 25 mm, and the peel strength of the protective film and the transfer layer is in the range of 0.1 g / 25 mm to less than 30 g / 25 mm. For example, it can be set in the range of 3 to 50 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight of the inorganic component. If the content of the thermoplastic resin or the photosensitive resin composition is less than 3 parts by weight, the shape retaining properties of the transfer layers 3 and 13 are low, and in particular, problems arise in storage stability and handling properties in a roll state. When the transfer sheets 1 and 11 are cut (slit) into a desired shape, inorganic components are generated as dust, which may hinder the production of the plasma display panel. On the other hand, when the content of the thermoplastic resin or the photosensitive resin composition exceeds 50 parts by weight, the organic components cannot be completely removed by baking, and the carbide remains in the electrode pattern after baking, resulting in a deterioration in quality. Therefore, it is not preferable.
[0036]
Furthermore, in the above-mentioned thermoplastic resin and photosensitive resin composition, as additives, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a dispersant, a transferability imparting agent, a stabilizer, an antifoaming agent, A thickener, a suspending agent, a release agent and the like can be contained as necessary.
[0037]
The transferability-imparting agent is added for the purpose of improving transferability and fluidity of the ink composition. For example, normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate and di-n-octyl phthalate, di-2- Phthalic acid esters such as ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tri-2-ethylhexyl trimellitate, tri-n-alkyl trimellitate , Trimellitonate such as triisononyl trimellitate, triisodecyl trimellitate, dimethyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol Dipetate, di-2-ethylhexyl azate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n -Aliphatic dibasic acid esters such as butyl citrate and acetyl tributyl citrate, polyethylene glycol benzoate, triethylene glycol di- (2-ethylhexoate), glycol derivatives such as polyglycol ether, glycerol triacetate, glycerol Glycerin derivatives such as diacetyl monolaurate, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., low molecular weight polyethers having a molecular weight of 300 to 3000, the same low molecular weight poly-α-styrene, Low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate , Orthophosphoric acid esters such as 2-ethylhexyl diphenyl phosphate, ricinoleic acid esters such as methylacetyl ricinolate, poly-1,3-butanediol adipate, polyester epoxidized esters such as epoxidized soybean oil, glycerin triacetate And acetic acid esters such as 2-ethylhexyl acetate.
[0038]
Further, the dispersant and the anti-settling agent are intended to improve the dispersibility and anti-settling property of the above inorganic powder. For example, phosphate ester type, silicone type, castor oil ester type, various surfactants Examples of the antifoaming agent include silicone-based, acrylic-based, various surfactants, etc., and examples of the release agent include silicone-based, fluorine oil-based, paraffin-based, fatty acid-based, fatty acid ester. Type, castor oil type, wax type, compound type and the like, and as the leveling agent, for example, fluorine type, silicone type, various surfactants and the like can be mentioned, and appropriate amounts can be added respectively.
[0039]
Examples of the solvent used together with the thermoplastic resin or the photosensitive resin composition for forming the transfer layers 3 and 13 include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, α- Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, and aromatics such as toluene, xylene, tetramethylbenzene Hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol Acetates such as acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, dipropylene Recall dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, N-dimethylformamide and the like. Two or more of these may be mixed.
Protective film
The protective film 14 constituting the transfer sheet 11 of the present invention has surface characteristics such that the peel strength with the transfer layer 13 is in the range of 0.1 g / 25 mm or more and less than 30 g / 25 mm, and is flexible, tension or Materials that do not undergo significant deformation under pressure can be used. Specifically, polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film, polystyrene film, polymethacrylic acid film, polyvinyl chloride film, polyvinyl alcohol film, polyvinyl butyral film, Nylon film, polyether ether ketone film, polysulfone film, polyether sulfone film, polytetrafluoroethylene-perfluoroalkyl vinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene-hexafluoropropylene film, Polychlorotrifluoroethylene film, polyvinylidene fluoride film, poly Tylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide film, film in which filler is added to these resin materials, film using these resin materials Uniaxially stretched or biaxially stretched, biaxially stretched film using these resin materials to increase the stretch ratio in the width direction from the flow direction, and using these resin materials, the stretch ratio in the flow direction from the width direction. It is produced by co-extrusion of the same type or different type of resin selected from the biaxially stretched film, the same type or different type of these films, and the raw resin used for these films. Double Mention may be made of the film, and the like. Among these films, it is particularly preferable to use a biaxially stretched polyester film. Moreover, you may use what processed said resin film, for example, a silicon processing polyethylene terephthalate, a corona processing polyethylene terephthalate, a melamine processing polyethylene terephthalate, a corona processing polyethylene, a corona processing polypropylene, a silicon processing polypropylene, etc.
[0040]
The thickness of the protective film 14 as described above can be set in the range of 4 to 400 μm, preferably 6 to 150 μm.
[0041]
Next, an example of forming an electrode pattern of a plasma display panel (PDP) using the transfer sheet of the present invention as described above will be described.
[0042]
Here, an AC type PDP will be described before describing electrode pattern formation.
[0043]
FIG. 3 is a schematic configuration diagram showing an AC type PDP, in which a front plate and a rear plate are separated from each other. In FIG. 3, the PDP 51 has a front plate 61 and a back plate 71 arranged in parallel with each other and facing each other, and a barrier 76 is formed on the front side of the back plate 71 so as to stand upright. The front plate 61 and the back plate 71 are held at regular intervals by the barrier 76. The front plate 61 has a front glass substrate 62. On the back side of the front glass substrate 62, composite electrodes including a sustain electrode 63 that is a transparent electrode and a bus electrode 64 that is a metal electrode are formed in parallel to each other. A dielectric layer 65 is formed so as to cover it, and an MgO layer 66 is further formed thereon. Further, the back plate 71 has a back glass substrate 72, and on the front side of the back glass substrate 72, an address electrode 74 is located between the barriers 76 so as to be orthogonal to the composite electrode via a base layer 73. Are formed in parallel to each other, and a dielectric layer 75 is formed so as to cover this, and a phosphor layer 77 is provided so as to cover the wall surface of the barrier 76 and the bottom surface of the cell. In this AC type PDP, an electric field is formed by applying a predetermined voltage from an AC power source between the composite electrodes on the front glass substrate 62, so that the front glass substrate 62, the rear glass substrate 72, and the barrier 76 are partitioned. Discharge is performed in each cell as a display element. Then, the phosphor layer 77 is caused to emit light by the ultraviolet rays generated by this discharge, and an observer can visually recognize this light transmitted through the front glass substrate 62.
[0044]
Next, the formation of the address electrode 74 in the back plate 71 of the PDP will be described.
[0045]
FIG. 4 is a process diagram for explaining pattern formation of the address electrode 74 using the transfer sheet 1 of the present invention. In this case, the transfer layer 3 of the transfer sheet 1 contains a negative photosensitive resin composition as an organic component that can be removed by baking.
[0046]
In FIG. 4, first, the transfer layer side of the transfer sheet 1 is pressure-bonded to the back glass substrate 72 provided with the base layer 73, and then the base film 2 is peeled off to transfer the transfer layer 3 (FIG. 4A). ). In this transfer step, the peel strength between the base film 2 and the transfer layer 3 of the transfer sheet 1 is preferably in the range of 1.0 to 10 g / 25 mm, so that the transfer layer 3 is good without causing cohesive failure. Transcription is possible. In addition, when heating is required for the transfer of the transfer layer 3, heating may be performed by heating the back glass substrate 72, a pressure bonding roll, or the like.
[0047]
Next, the transfer layer 3 is exposed through the photomask M (FIG. 4B). In addition, when using the film which has a light transmittance as the base film 2, you may expose before peeling the base film 2. FIG.
[0048]
Next, by developing the transfer layer 3, a pattern 3 ′ composed of a conductive photosensitive resin layer is formed on the base layer 73 (FIG. 4C), and then baked to form an organic component of the pattern 3 ′. The address electrode pattern 74 is formed by removing (FIG. 4D).
[0049]
In the above example, the transfer sheet of the present invention as shown in FIG. 1 is used. However, when the transfer sheet 11 having the protective film 14 as shown in FIG. 2 is used, the protective film 14 is peeled off. After the removal, the electrode pattern can be formed by the same operation as in FIG. In the peeling of the protective film 14, the peeling strength between the protective film 14 and the transfer layer 13 is preferably in the range of 0.2 to 10 g / 25 mm, which is higher than the peeling strength between the base film 12 and the transfer layer 13. Since it is low, the protective film 14 can be satisfactorily peeled without causing cohesive failure in the transfer layer 13 and without causing peeling between the transfer layer 13 and the base film 12.
[0050]
【Example】
Next, an Example is shown and this invention is demonstrated further in detail.
[0051]
First, a photosensitive resin composition A having the following composition was prepared as an ink composition.
[0052]
Composition A of photosensitive resin composition
Silver powder (spherical shape, average particle size 1 μm) ... 96 parts by weight
・ Glass frit: 4 parts by weight
(Main component: Bi₂ O_Three , SiO₂ , B₂ O_Three (No alkali)
Softening point = 500 ° C., thermal expansion coefficient α₃₀₀ = 80 × 10^-7/ ℃)
・ N-Butyl methacrylate / 2-hydroxyethyl methacrylate
/ Methacrylic acid copolymer with 5 mol% glycidyl methacrylate
Added 14 parts by weight
(Molecular weight = 70,000, acid value = 110 mgKOH / g)
・ Pentaerythritol tri / tetraacrylate: 11 parts by weight
(M-305 manufactured by Toa Gosei Co., Ltd.)
-Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Gaigi) ... 1 part by weight
・ 3-methoxybutyl acetate: 20 parts by weight
Next, a polyethylene terephthalate film (T-60 manufactured by Toray Industries, Inc.) is prepared as a base film, and the ink composition is applied onto the base film by a blade coating method and dried (100 ° C., 2 minutes). A transfer layer having a thickness of 17 μm was formed.
[0053]
Next, a silicon-treated polyethylene terephthalate film (03-25-C (25 μm thickness) manufactured by Tosero Co., Ltd.) as a protective film is laminated on this transfer layer, and a transfer sheet (sample 1) as shown in FIG. Formed.
[0054]
Also, photosensitive resin compositions B to E having the following compositions were prepared, and transfer sheets (samples 2 to 5) were prepared in the same manner as described above using these photosensitive resin compositions. Sample 5 (Composition E) has the same composition as Sample 2 (Composition B), but the base film is corona-treated PET (E5101 (25 μm thickness) manufactured by Toyobo Co., Ltd.), and the protective film is stretched. A polypropylene film (E-600 (25 μm thickness) manufactured by Oji Paper Co., Ltd.) was used.
[0055]
Composition B of photosensitive resin composition
Silver powder (spherical shape, average particle size 1 μm) ... 96 parts by weight
・ Glass frit: 4 parts by weight
(Main component: Bi₂ O_Three , SiO₂ , B₂ O_Three (No alkali)
Softening point = 500 ° C., thermal expansion coefficient α₃₀₀ = 80 × 10^-7/ ℃)
・ N-Butyl methacrylate / 2-hydroxyethyl methacrylate
/ Methacrylic acid copolymer: 14 parts by weight
(Molecular weight = 70,000, acid value = 140 mgKOH / g)
・ Pentaerythritol tri / tetraacrylate: 12 parts by weight
(M-305 manufactured by Toa Gosei Co., Ltd.)
・ Dibutyl phthalate: 2 parts by weight
-Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Gaigi) ... 1 part by weight
・ 3-methoxybutyl acetate: 20 parts by weight
Composition C of photosensitive resin composition
Silver powder (spherical shape, average particle size 1 μm) ... 96 parts by weight
・ Glass frit: 4 parts by weight
(Main component: Bi₂ O_Three , SiO₂ , B₂ O_Three (No alkali)
Softening point = 500 ° C., thermal expansion coefficient α₃₀₀ = 80 × 10^-7/ ℃)
・ N-Butyl methacrylate / 2-hydroxyethyl methacrylate
/ Methacrylic acid copolymer: 14 parts by weight
(Molecular weight = 70,000, acid value = 140 mgKOH / g)
・ Pentaerythritol tri / tetraacrylate: 8 parts by weight
(M-305 manufactured by Toa Gosei Co., Ltd.)
-Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Gaigi) ... 1 part by weight
・ 3-methoxybutyl acetate: 20 parts by weight
Composition D of photosensitive resin composition
Silver powder (spherical shape, average particle size 1 μm) ... 96 parts by weight
・ Glass frit: 4 parts by weight
(Main component: Bi₂ O_Three , SiO₂ , B₂ O_Three (No alkali)
Softening point = 500 ° C., thermal expansion coefficient α₃₀₀ = 80 × 10^-7/ ℃)
・ N-Butyl methacrylate / 2-hydroxyethyl methacrylate
/ Methacrylic acid copolymer: 14 parts by weight
(Molecular weight = 70,000, acid value = 140 mgKOH / g)
・ Pentaerythritol tri / tetraacrylate: 8 parts by weight
(M-305 manufactured by Toa Gosei Co., Ltd.)
-Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Gaigi) ... 1 part by weight
・ N-methyl-2-pyrrolidone: 20 parts by weight
Composition E of photosensitive resin composition
Silver powder (spherical shape, average particle size 1 μm) ... 96 parts by weight
・ Glass frit: 4 parts by weight
(Main component: Bi₂ O_Three , SiO₂ , B₂ O_Three (No alkali)
Softening point = 500 ° C., thermal expansion coefficient α₃₀₀ = 80 × 10^-7/ ℃)
・ N-Butyl methacrylate / 2-hydroxyethyl methacrylate
/ Methacrylic acid copolymer: 14 parts by weight
(Molecular weight = 70,000, acid value = 140 mgKOH / g)
・ Pentaerythritol tri / tetraacrylate: 14 parts by weight
(M-305 manufactured by Toa Gosei Co., Ltd.)
-Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Gaigi) ... 1 part by weight
・ 3-methoxybutyl acetate: 20 parts by weight
Next, the transfer sheet (Samples 1 to 5) was slit to a predetermined width, wound around an ABS resin core, and stored in a roll state at 25 ° C. for 7 days. Thereafter, for each transfer sheet (Samples 1 to 5), the peel strength between the base film and the transfer layer and the peel strength between the protective film and the transfer layer were measured under the following conditions, and the results are shown in Table 1 below.
[0056]
(Peel strength measurement conditions)
A sample (25 mm in width) is cut along the flow direction of each transfer sheet, and this is peeled 180 ° at a rate of 100 mm / min using a large-scale Tensilon universal testing machine UTM-500 manufactured by Orientec Co., Ltd. It was measured.
[0057]
Next, the protective film of the transfer sheet after the storage was peeled off and pressure-bonded with a hot roll at 40 ° C. using an auto-cut laminator on a glass substrate at room temperature. Subsequently, after cooling to room temperature, the base film was peeled off and the transfer layer was transferred to a glass substrate. The transfer film (samples 1 to 5) in this transfer step was observed for the peelability of the protective film and the transferability of the transfer layer (including the peelability of the base film), and the results are shown in Table 1 below.
[0058]
Next, ultraviolet rays (light source: ultra-high pressure mercury lamp) are irradiated (800 mJ / cm through a negative pattern mask (opening line width 70 μm) of the electrode of the plasma display panel.² ) To expose the transfer layer. Thereafter, development was performed using a 0.5% aqueous sodium carbonate solution, washing with pure water and drying were performed to obtain a predetermined pattern. Next, the glass substrate was baked at 600 ° C. to form an electrode pattern.
[0059]
The thickness and line width of the electrode pattern thus formed were measured and shown in Table 1 below.
[0060]
[Table 1]

As shown in Table 1, the transfer sheets (Samples 1 to 3) of the present invention also had good peelability between the transfer layer and the protective film and transferability to the glass substrate. Moreover, it was confirmed that the electrode pattern formed using these transfer sheets has a uniform thickness and line width, and is formed with high accuracy.
[0061]
On the other hand, in the transfer sheet (sample 4) in which the peel strength between the base film and the transfer layer is less than 0.2 g / 25 mm and the peel strength between the protective film and the transfer layer is less than 0.1 g / 25 mm, Air or foreign matter was mixed between the protective film and the transfer layer. On the other hand, the adhesion of the transfer layer was low between the base film and the transfer layer, so that the transfer layer was easily peeled off or cracked. For this reason, in the electrode pattern formed using this transfer sheet, disconnection defects frequently occurred.
[0062]
Furthermore, in the transfer sheet (sample 5) in which the peel strength between the base film and the transfer layer exceeds 30 g / 25 mm and the peel strength between the protective film and the transfer layer is 30 g / 25 mm or more, the transfer layer Scratches and dents were formed on the film, and a part of the transfer layer was agglomerated and broken during peeling of the base film. For this reason, in the electrode pattern formed using this transfer sheet, disconnection defects frequently occurred.
[0063]
【The invention's effect】
As described above in detail, according to the present invention, a transfer layer containing at least an inorganic component containing glass frit and conductive powder and an organic component capable of being removed by baking is formed on the base film with a peel strength of 0.2 g / Since the transfer sheet is provided so as to be peelable so as to be within the range of 25 mm or more and 30 g / 25 mm or less, the transfer film is transferred to the transfer medium. Can be peeled off, has good transferability, and has a peel strength within a range of 0.1 g / 25 mm or more and less than 30 g / 25 mm, and smaller than the peel strength between the base film and the transfer layer. When setting and providing a protective film on the transfer layer, the transfer layer does not cause cohesive failure of the transfer layer, and the base film and transfer layer do not peel off. In addition, the peeling of the base film and the transfer layer and the peeling of the protective film and the transfer layer may cause large tension fluctuations due to the peel strength being within the above range. In the case where the organic layer has photosensitivity, patterning accuracy by exposure / development can be improved. This makes it possible to form a high-definition pattern of electrodes.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an embodiment of a transfer sheet of the present invention.
FIG. 2 is a schematic cross-sectional view showing another embodiment of the transfer sheet of the present invention.
FIG. 3 is a schematic configuration diagram showing an example of a plasma display panel.
FIG. 4 is a process diagram for explaining an example of electrode pattern formation using the transfer sheet of the present invention.
[Explanation of symbols]
1,11 ... transfer sheet
2,12 ... Base film
3, 13 ... Transfer layer
14 ... Protective film
M ... Photomask

Claims (3)

In the transfer sheet for electrode formation of the plasma display panel,
A base film and a transfer layer provided on the base film so as to be peelable. The transfer layer contains at least an inorganic component including glass frit and conductive powder, and an organic component capable of being removed by baking. A transfer sheet characterized by having a peel strength between a film and a transfer layer in a range of 0.2 g / 25 mm to 5.0 g / 25 mm when measured under the following measurement conditions.
(Peel strength measurement conditions)
A sample (25 mm wide) is cut along the flow direction of the transfer sheet, the sample is peeled 180 ° at a speed of 100 mm 2 / min, and the peel strength is measured.   A protective film is provided on the transfer layer so as to be peelable, and when the peel strength between the protective film and the transfer layer is measured under the measurement conditions, the range is from 0.1 g / 25 mm to 2.5 g / 25 mm. The transfer sheet according to claim 1, wherein the transfer sheet is smaller than the peel strength between the base film and the transfer layer.   The transfer sheet according to claim 1, wherein the organic component has photosensitivity.

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