JP2003346648A - Phosphor transfer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor transfer film having a cushion layer capable of well burying a new photosensitive adhesive layer and a photosensitive phosphor layer according to their surface shape even between already-made phosphor pixels, in a process of forming phosphor pixels in turn on an adhered body with the use of the phosphor transfer film. <P>SOLUTION: At least one layer of the photosensitive adhesive layer 2 and the photosensitive phosphor layer are provided on a support body 5 and a cushion layer 4 consisting of a thermoplastic resin is fitted between the photosensitive phosphor layer 3 and the support body 5. The thermosetting resin used as the cushion layer 4 shows a transformation ratio of 3,000 to 30,000 μm/m°C at 120°C. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor transfer film used in a manufacturing process of a display using a phosphor as a display medium.

[0002]

2. Description of the Related Art A display using a phosphor as a display medium includes a cathode ray tube (CRT) as a representative, a plasma display (PDP), a field emission display (FED), and the like. Since these displays use a method in which color display is performed using the self-luminous color of the phosphor, phosphors suitable for each method are selected and used.However, the pattern accuracy of the phosphor pixels, the phosphor density, etc. The pixel state is greatly affected by display performance and quality. Also, since the method of forming the phosphor pixels affects the display price, the manufacturing method is also important.

[0003] Regarding the method of forming the phosphor layer, in the case of a CRT, a polyvinyl alcohol-ammonium dichromate (PVA-ADC) -based photosensitizer or a polyvinyl alcohol-sodium dichromate (PVA-SDC) -based photosensitizer is used. Slurry prepared by dispersing phosphors of each color emitting green, blue and blue is applied directly on the whole glass substrate one by one, dried and patterned (exposure, development and drying)
Are repeated to form phosphor pixels. In the case of PDPs and FEDs, the phosphor pixels are formed by screen-printing pastes in which red, green, and blue light-emitting phosphors are dispersed in polyvinyl alcohol, acrylic resin, or the like.

When a phosphor slurry is used, phosphor residue (stain on the background) may occur on other color pixels in quality, which is a serious problem. This is because, when a pixel in a stained portion emits light, the stained other color phosphor also emits light at the same time, so that the pixel emits light in a mixed color (color purity is reduced). As a result, color bleeding or the like is caused in an image formed on the phosphor screen, and a clear image cannot be obtained. The screen printing method using phosphor paste has poor printing accuracy (position accuracy, shape accuracy, film thickness accuracy), color unevenness of phosphor pixel thickness, and contamination due to phosphor paste on other color pixels. There is a big problem that is worse.

As a method for producing a phosphor screen of a display using a phosphor, a slurry method using a phosphor slurry and a screen printing method using a phosphor paste are generally used. In the manufacturing process of these phosphor screens, there is a problem that, besides the contamination of the pixels of other colors, the linearity of the pixel edge is deteriorated, chipped, and a defect is generated due to dust and foreign matter.

[0006] Further, in the phosphor coating of the CRT, it is difficult to make the coating thickness uniform since the slurry is injected into the panel glass and then the spin coating is performed. Therefore, the phosphor coating thickness is also determined for each adherend or each pixel. Tends to be uneven. Therefore, in the continuous production, the variation in the thickness of the phosphor applied directly causes the quality of the display image to deteriorate. Also, in the slurry method, not only is the manufacturing apparatus itself large and expensive, but also the manufacturing process becomes very complicated,
There is a problem that the manufacturing cost increases.

[0007] As a method of solving these problems, according to the characteristics of each display and the characteristics of the phosphor,
JP-A-2001-43796 and JP-A-200-43796 each use a method (transfer method) using a phosphor transfer film provided with an optimum thickness.
It has been proposed in Japanese Patent Application Laid-Open No. 1-220284. In the transfer method, a phosphor layer having a uniform thickness can be formed in advance on a support such as a plastic film, so that the dispersion of the phosphor coating thickness, which was a problem of the slurry method, can be prevented, and a slurry coating apparatus can be used. By using a small-sized transfer device instead of, the process can be simplified, the performance of the phosphor screen can be improved, and the manufacturing cost can be reduced.

[0008]

However, a phosphor transfer film used when a color display using a phosphor is manufactured by a transfer method has a photosensitive phosphor layer having a uniform thickness for each color. After transferring to the adherend together with the conductive adhesive layer, patterning (exposure, development, and drying) is performed to form phosphor pixels. However, since phosphor pixels are sequentially formed through the same process for the second and subsequent colors. In addition, since the photosensitive phosphor layer and the photosensitive adhesive layer are embedded between the formed pixels, it is difficult to sufficiently adhere to the adherend. According to the present invention, in the process of sequentially forming the phosphor pixels on the adherend using the phosphor transfer film, a new photosensitive adhesive layer and a new photosensitive phosphor layer are also provided between the already formed phosphor pixels. An object of the present invention is to provide a phosphor transfer film having a cushion layer that can be satisfactorily embedded following the surface shape.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, provided a cushion layer effective for transferring a phosphor layer to a transfer film. It has been found that the above problem can be solved by using a thermoplastic resin having thermal and mechanical properties for the cushion layer, and the present invention has been completed based on this finding. The characteristic of the cushion layer that is required is that the portion in contact with the adherend convex portion (the portion where the formed pixel exists) squeezes into the cushion layer side by heating and pressure during transfer with good response. The portion in contact with the (pre-formed pixel portion) is to be embedded so that the photosensitive adhesive layer and the photosensitive phosphor layer extend to the foot portion of the pixel.

Therefore, in order to solve the above-mentioned problems, a phosphor transfer film of the present invention has at least one photosensitive adhesive layer and a photosensitive phosphor layer on a support, and the photosensitive phosphor layer A cushion layer made of a thermoplastic resin is provided between the support and the support, and the thermoplastic resin used as the cushion layer is 3,000 to 30,000 μm / m ° C. at 120 ° C.
Which is characterized by a deformation rate of The glass transition temperature of the thermoplastic resin used as the cushion layer is -1.
0 to 35 ° C. and the softening point of the thermoplastic resin is 50
To 130 ° C., and the thermal melting temperature of the thermoplastic resin is preferably 180 ° C. or higher. The thermoplastic resin used as the cushion layer is an acrylate copolymer, an ethylene-vinyl acetate copolymer, a vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, a saponified product of ethylene and an acrylate copolymer, A resin selected from a saponified product of styrene and acrylate copolymer, a copolymer of styrene and isoprene, or a copolymer of butadiene, a polyester resin, and a polyolefin resin, and preferably has a molecular weight of 100,000 or more. The thickness of the cushion layer is preferably 20 to 60 μm. The thickness of the photosensitive adhesive layer is 0.5 to 3.0 μm
And the thickness of the photosensitive phosphor layer is preferably 3.0 to 25 μm. The glass transition temperature of the resin of at least one component contained in the photosensitive adhesive layer is preferably 0 ° C. or lower. Further, the photosensitive adhesive layer and the photosensitive phosphor layer have a composition containing a water-soluble photosensitive resin, wherein the water-soluble photosensitive resin is a stilbazolium group, and a stilquinolinium group, or 5- ( At least one selected from sodium salt of 4-azido-2-sulfobenzylidene) -3- (4,4'-dimethoxybutyl) rhodanine has 0.5 to 5.0 mol% as a photosensitive component addition group. Degree of polymerization 500-30
It is preferably a modified polyvinyl alcohol of No. 00.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to embodiments. FIG. 1 shows an embodiment of the structure of the phosphor transfer film according to the present invention. That is, on a support (base film) 5 provided with a cushion layer 4, a photosensitive phosphor layer 3 containing at least a phosphor emitting a predetermined color and a photosensitive resin, It has at least one photosensitive adhesive layer 2 for transferring the phosphor layer 3 and forming a good image, and a cover film 1 is provided for the purpose of protecting the photosensitive adhesive layer 2. An antistatic layer 6 is provided on the back side of the support 5. Hereinafter, each layer shown in FIG. 1 will be described.

As the cover film, a conventionally known plastic film can be used. For example, polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, triacetate and the like can be mentioned. In particular, a polyethylene terephthalate (PET) film with high mechanical strength and excellent thermal stability,
Alternatively, a polypropylene film (OPP film) which is inexpensive and excellent in releasability is preferable. The thickness of the cover film is not particularly limited, but is preferably 75 μm or less. This is because the stiffness of the transfer film is high when the cover film is over 75μm thick when finished in the product form of the transfer film, that is, when the cover film is finished in a roll-like product. It is anticipated that harmful effects such as the formation of cover film in which air enters between the adhesive layer and the adhesive layer, the increase in product weight per unit length, making it difficult to manufacture long rolled products, and the increase in manufacturing cost That is because

Further, it is preferable to provide a release layer in order to further stabilize the releasability between the base material of the cover film 1 and the photosensitive adhesive layer 2. Examples of the resin used for the release layer include urethane resins, melamine resins, silicone resins, and copolymers and mixtures thereof. The coating thickness of the release layer is not particularly limited, but is 0.5 to 5.0 μm.
Is preferred. Polypropylene film (OPP
When a substrate having releasability such as a film is used, it is not necessary to provide a release layer.

The photosensitive adhesive layer 2 is a general resin belonging to a class called a pressure-sensitive adhesive or a heat sealing agent, and / or a resin obtained by using a water-soluble photosensitive resin in combination with these resins. As the pressure-sensitive adhesive, generally known pressure-sensitive emulsion-type, solvent-type, and hot-melt-type pressure-sensitive adhesives, and water-soluble and UV-crosslinkable types can be used. As the heat sealing agent, generally known emulsion type or solvent type resins can be used. In order to form a photosensitive adhesive layer suitable for the present invention, the glass transition temperature (Tg) of at least one or more resin components contained in the photosensitive adhesive layer is preferably 0 ° C. or less. As for the photosensitive resin, generally known material systems can be used, and the compounding ratio can be arbitrarily determined according to the performance of the material.

The phosphor used in the photosensitive phosphor layer 3 differs depending on the type of display. As the phosphor for CRT, silver and chlorine-activated zinc sulfide phosphor (ZnS: Ag) are used as blue light-emitting phosphors. / ZnS: Ag, Cl), silver and aluminum activated zinc sulfide phosphor (ZnS: Ag, Al), and green and green activated phosphors are copper and aluminum activated zinc sulfide phosphor (ZnS: Cu, Al), copper , Gold and aluminum activated zinc sulfide phosphors (ZnS: Cu, Au, Al), manganese activated zinc silicate phosphors (Zn2SiO4: Mn), red europium and samarium activated yttrium oxysulfide phosphors (Y2O2S: Eu / Y2O2S: Eu, Sm) A manganese-activated zinc phosphate phosphor (Zn3 (PO4) 2: Mn) or the like can be used. Also,
BaMg as a blue light emitting phosphor as a phosphor for PDP
Al14O23: Eu, BaMgAl10O17: Eu, as a green light emitting phosphor
BaAl12O19: Mn, Zn2SiO4: Mn, (Ba, Sr, Mg) OaAl2O3: Mn,
(Y, Gd) BO3: Eu or the like can be used as the red light emitting phosphor. Further, as a phosphor for FED, ZnGa2O
4, SrTiO3: Pr or the like can be used.

As the photosensitive resin used for the photosensitive adhesive layer and the photosensitive phosphor layer, any resin may be used as long as its solubility in water changes before and after exposure to ultraviolet light or visible light. A photosensitive agent may be mixed with the non-photosensitive water-soluble resin, or a photosensitive functional group may be present in the resin molecule.

As the water-soluble photosensitive resin, those generally known can be used. Especially stilbazolium groups,
And at least one selected from a stilquinolinium group and an azido group-containing functional group such as sodium salt of 5- (4-azido-2-sulfobenzylidene) -3- (4,4′-dimethoxybutyl) rhodanine. The seed is used as a photosensitive component addition group in an amount of 0.5 to
Modified polyvinyl alcohol having a degree of polymerization of 500 to 3000 and having 5.0 mol% is preferred. When a modified polyvinyl alcohol to which an azide group-containing functional group is added is used as the water-soluble photosensitive resin, it is particularly preferable to use polyvinyl pyrrolidone in combination.

It is necessary to select a material for the photosensitive adhesive layer according to the composition of the photosensitive phosphor layer. In other words, the photosensitive adhesive layer has good adhesiveness to the photosensitive phosphor layer while having adhesiveness to the adherend, and is not suitable for pattern formation by exposing and developing the phosphor layer and the adhesive layer. A material that does not cause residue in the image area is preferable. Further, the coating thickness needs to be optimized depending on the material. However, in the production of a display, the thickness of the adhesive layer is preferably 0.5 to 3 μm, and when the coating thickness is less than 0.5 μm, In many cases, the transferability of the photosensitive phosphor layer is deteriorated because the adhesiveness of the photosensitive phosphor layer is reduced. On the other hand, if the thickness of the adhesive layer is more than 3 μm, even if pattern formation is possible, in the case of CRT production, the phosphor pattern may be peeled off in the firing step. Therefore, a material that does not provide sufficient performance in this coating amount range is not preferable for this application.

The mixing ratio of the phosphor and the photosensitive resin in the photosensitive phosphor layer is as follows: phosphor / photosensitive resin = 97-80% by weight /
3-20% by weight is preferred. If the phosphor ratio is higher than this, the layer strength after photocuring becomes weaker, and the pixel surface may be shaved during development and the linearity of the pixel edge may be poor. The thickness of the photosensitive phosphor layer depends on the average particle size of the phosphor particles used, but can be adjusted in the range of 3.0 to 25 μm.

Reference numeral 5 denotes a support. As the support, a conventionally known plastic film similar to that shown in the description of the cover film can be used. The thickness of the support is not particularly limited, but a thickness of 25 to 150 μm is appropriate. When the thickness is 25 μm or less, the workability deteriorates, and the curl is remarkably generated when the antistatic layer and the cushion layer are provided, which is not preferable. 150
When the thickness is more than μm, not only is it difficult to manufacture a roll-shaped product, but also the heat transfer to the photosensitive adhesive layer during thermocompression bonding of the phosphor transfer film and the adherend with a hot roll during transfer to the adherend. Since the speed decreases, good transfer cannot be obtained unless measures such as raising the temperature of the hot roll, lowering the transfer speed, or sufficiently heating the adherend are taken. Since this is not preferable from the viewpoint of workability and economy, the thickness of the support is preferably as thin as possible. Particularly preferably, a thickness of 40 to 50 μm is suitable as a support.

Further, an antistatic layer 6 is provided to prevent dust from being mixed due to peeling charging. The surface resistance value of the plastic film is preferably 10 ⁶ Ω / □ to ⁹ Ω / □ according to the measurement method specified in JIS K6911. For this reason, it is preferable to use an antistatic treated film or a film provided with an antistatic layer of 6. The cushion layer 4 will be described later.

Here, the process of transferring the photosensitive phosphor layer and the photosensitive adhesive layer to the adherend based on the structure of the phosphor transfer film of FIG. 1 will be described below. First, the cover film 1 is peeled off from the photosensitive adhesive layer 2 to expose the photosensitive adhesive layer 2. Next, after the photosensitive adhesive layer 2 is adhered to the adherend by heating and pressing, the support 5 is peeled off between the photosensitive phosphor layer 3 and the cushion layer 4 together with the cushion layer 4 and the antistatic layer 6. . At this stage, only the photosensitive phosphor layer 3 and the photosensitive adhesive layer 2 are transferred to the adherend.

It is necessary to prepare the phosphor transfer film of the present invention for each color necessary for producing a color display. For example, in the case of a CRT, it is excited by an electron beam to emit red, blue and green light. Three transfer films each containing a phosphor to be used are required. Then, the photosensitive adhesive layer and the photosensitive phosphor layer are transferred one by one onto the panel glass to be adhered, and are subjected to pattern exposure with actinic rays using a high-pressure mercury lamp as a light source, development with water, and drying operations. A phosphor pixel is formed. The phosphor pixels of the second and third colors are also subjected to the operations of transfer, exposure, development, and drying in the same manner as described above to form phosphor pixels that emit red, green, and blue light when excited by an electron beam on the panel glass.

The cushion layer 4 is provided to stably perform the above-described transfer process. In particular, since the thickness of the phosphor pixel is usually 3 to 25 μm, in the process of forming the pixels of the second and subsequent colors, the cushion layer is necessary to properly transfer the photosensitive adhesive layer and the photosensitive phosphor layer between the already formed pixels. Depending on the material properties, the phosphor pixel thickness is about 2 to 2
Four times the thickness is required. If the thickness of the cushion layer is lower than the thickness of the phosphor pixel, it is difficult to reliably transfer between the pixels. For example, as shown in FIG. Air trapping (tenting) 9 occurs between the surface and the side surface of the formed phosphor pixel 7 rising from the adherend surface, and transfer failure tends to occur. If the thickness of the cushion layer exceeds 100 μm, it depends on the thermal conductivity of the resin used. However, the thermal conductivity from the heat roll during transfer decreases, so that the cushion layer cannot be sufficiently softened, and the distance between the formed phosphor pixels is reduced. It is difficult to transfer a new photosensitive adhesive layer and photosensitive phosphor layer so as to embed them.

Accordingly, the function of the cushion layer 4 is to assist the transfer of the photosensitive adhesive layer and the photosensitive phosphor layer to glass or the like to be adhered. In the case of transfer to a surface having a relatively high degree of flatness such as a sheet glass, the transfer can be stably performed to the glass surface if the cushion layer has a certain degree of thermal softening property and elasticity. However, when another phosphor transfer film is transferred onto an adherend on which phosphor pixels are already provided, it becomes difficult to embed a new photosensitive phosphor layer evenly between the already provided pixels.

FIG. 2 shows this state. As is apparent from FIG. 2, the air pool 9 generated near the formed pixel 7 is clearly shown.
The photosensitive adhesive layer 2 is not sufficiently adhered to the adherend 8 in the portion. As an extreme example, when a photosensitive adhesive layer and a photosensitive phosphor layer are similarly transferred onto a formed pixel using a phosphor transfer film to which a cushion layer has not been applied, the photosensitive area between the tops of the pixels is exposed. Although the adhesive layer adheres, the space between pixels is completely void, and the newly transferred photosensitive adhesive layer surface does not reach the surface of the adherend. Therefore, there is a problem that although the apparent transfer itself is possible, the transferred photosensitive adhesive layer and photosensitive phosphor layer are all washed away during patterning, and a new pixel cannot be formed.

In order to solve the above problem, it is effective to provide the transfer film with the cushion layer 4 so as to have a structure as shown in FIG. However, when the resin used for the cushion layer 4 has poor deformability, air pockets still remain as shown in FIG. In such a state, the area of the photosensitive adhesive layer in contact with the adherend becomes smaller than the size of a desired pixel, so that it is difficult to form a good pixel. In order to minimize the occurrence of air pockets and obtain better pixels, raise the surface temperature of the heat roll used for transfer, apply a higher pressure during transfer to form a photosensitive adhesive layer and a photosensitive phosphor layer between pixels. Methods for adjusting the transfer conditions themselves, such as embedding, can be considered, but these methods have the drawback that the transfer film is likely to wrinkle.

Therefore, it is more preferable to use a resin having high deformability and elasticity for the cushion layer 4. When a deformation stress is applied from the outside, deformation occurs with good response, and when there is no external deformation stress, a thermoplastic resin which maintains a certain degree of hardness is suitable for the cushion layer.

The present inventors have developed a thermomechanical analyzer (TMA).
Was used to evaluate the above characteristics, and found that the characteristics correlated well with the transferability of the actual transfer film. Specifically, a measurement similar to the method of measuring the softening point of a resin prescribed in JIS K7196 was performed to determine the deformation ratio of the cushion layer at 120 ° C. As a result, the deformation rate is 3000 to
It has been found that if a cushion layer made of a resin of 30,000 μm / m ° C. is provided, the photosensitive phosphor layer and the photosensitive adhesive layer can be transferred well between the formed pixels.

The method of measuring the deformation rate of the cushion layer 4 will be described in more detail. TMA is a TM made by TA Instruments
The measurement was performed in the needle insertion mode using A2940 type. The test piece 10 has a thickness of 20 to 80 after drying various thermoplastic resins.
A cushion layer 11 was formed by applying a 50 μm-thick polyethylene terephthalate film (PET film) 12 to a thickness of 50 μm. As shown in FIG.
The test piece 10 having a size of mm × 10 mm was sandwiched between a quartz glass probe 14 having a diameter of 2 mm and a quartz glass table 13, and a 20 g load was applied to the probe 14 during the measurement. Then, the test piece 10 and the probe 14 were heated and heated at a heating rate of 20 ° C./min while applying a constant load, and the deformation rate (unit: μm / m ° C.) of the resin when the temperature reached 120 ° C. was read.

Generally, the thermal expansion coefficient (unit: μm / m ° C.) is known as the deformation rate that can be measured by TMA, and its coefficient α
Can be calculated by the following equation. Here, the meaning of each symbol is as follows. α: coefficient of thermal expansion (unit: μm / m ° C.) L: initial length of sample (unit: m) δL: change length of sample (unit: μm) δT: changed temperature (unit: ° C.) K: measuring instrument In the evaluation method shown in the present invention, the L and δL use the thickness of the test piece, and the thickness change of the test piece when a stress is applied in the compressing direction is measured. The rate is not strictly a coefficient of thermal expansion. Further, during the measurement, the probe sinks into the inside of the test piece, and the thickness of the test piece changes so that the measurement value becomes a negative value. Since the actual deformation ratio is complicated when the value is a negative value, it is expressed by an absolute value. This deformation ratio was used as a characteristic index when various thermoplastic resin coating films were used as cushion layers.

FIG. 4 shows an example of the TMA measurement. Since the probe sinks into the test piece as the temperature rises, the change in the thickness of the cushion layer with respect to the temperature becomes a curve as shown in the figure. Here, the temperature at which the probe started to sink into the sample was defined as the temperature at which the resin used for the cushion layer became soft, that is, the softening point. The temperature at which the probe was completely immersed in the resin and reached the PET film was defined as the temperature at which the resin used for the cushion layer melted into a liquid state, that is, the melting temperature. The softening point and the melting temperature are important characteristics in evaluating the thermophysical properties of the resin suitable for the cushion layer, but the ease of deformation cannot be expressed only by these two characteristics.
Therefore, the deformation rate of the cushion layer at an arbitrary temperature of the cushion layer must be considered. In the present invention, the deformation rate of the resin is the rate of change of the resin at 120 ° C., and the rate of change at the circle mark on the TMA curve in FIG. 4, that is, the slope of the curve is read.

The deformation ratio read from the slope of the TMA curve at 120 ° C. is also affected by the load applied during the TMA measurement and the thickness of the thermoplastic resin layer, that is, the cushion layer.
For example, the deformation ratio shows a slightly different value depending on the magnitude of the applied load, but the shape of the curve tends to hardly change. From this, if you measure with a constant load,
In the present invention, the measurement load was set to 20 g because it is considered that physical properties capable of judging the superiority of the resin are obtained. When only the thickness of the cushion layer using the same type of thermoplastic resin is changed, the deformation rate at 120 ° C. tends to be smaller as the cushion layer is thinner. From this, it is also possible to adjust the deformation rate by adjusting the thickness of the cushion layer, and use a resin that falls within the range of the deformation rate specified in the present invention by adjusting the thickness as the cushion layer. it can. The temperature range in which the deformation rate is to be evaluated also changes depending on the transfer conditions (surface temperature of the heat roll, printing pressure between the adherend and the heat roll) when using the phosphor transfer film. In the present invention, since thermal transfer in a temperature range of 80 ° C. or higher is assumed, 120 ° C. was set as the evaluation temperature of the deformation rate.

Comparing the properties obtained by the above method with the transferability of the actual phosphor transfer film, the deformation rate at 120 ° C. is 3000 to 30000 μm / m ° C., and preferably, the melting temperature exceeds 180 ° C. When a plastic resin is used for the cushion layer, more preferably, when the thickness of the cushion layer is in the range of 20 to 60 μm, the photosensitive adhesive layer and the photosensitive phosphor layer are more efficiently transferred between the formed pixels. It was possible. When the thermophysical properties of the resin suitable for the cushion layer 4 are evaluated from another viewpoint, the glass transition point temperature of the resin having the above characteristics is -10 to 3
It has been found that a resin having a temperature of 5 ° C. and a softening point of 50 to 130 ° C. exhibits particularly excellent performance. In addition,
The glass transition point temperature was measured using a differential scanning calorimeter (manufactured by TA Instruments: Model 910 DSC) with reference to the measurement method specified in JIS K7121.

As described above, the material of the cushion layer 4 is preferably a thermoplastic resin, for example, an acrylic ester copolymer, a saponified product of ethylene and an acrylic ester copolymer, and styrene and an acrylic ester. Saponified copolymer, ethylene-vinyl acetate copolymer,
Examples include an ethylene ethyl acrylate copolymer, a copolymer of styrene and isoprene, or a copolymer of butadiene, a polyester resin, and a polyolefin resin. These resins can be used alone, mixed in an appropriate combination, or laminated in an appropriate combination. If necessary, a plasticizer may be added. In the present invention, a molecular weight of 10 including acrylic resin and vinyl acetate resin is used.
More than ten thousand thermoplastic resins were particularly preferred resins for the cushion layer.

On the other hand, when a resin having a melting temperature considerably lower than 180 ° C., for example, a low-density polyethylene resin is used for the cushion layer, the resin is melted by the heat of the heat roll used at the time of transfer and flows out from the end face of the transfer film. Problems such as the fact that the molten resin entangled in the heat roll or protruding from the film adheres to the surface of the adherend and hinders the peelability of the support are likely to occur. Also, when a material having an extremely large deformation rate (see the TMA curve of B in FIG. 5) is used for the cushion layer, the softening and melting of the resin occur in an extremely narrow temperature range. Molten resin protrudes from the end face, which is not preferable.

When the thermoplastic resin of the present invention is used for the cushion layer, the thickness of the cushion layer, which has been difficult to make thin with conventional low-density polyethylene resin, can be reduced by up to 70%. It is economically advantageous in producing a transfer film.

After laminating the phosphor transfer film using the thermoplastic resin of the present invention for the cushion layer on the adherend including the already formed pixels, the peeled cushion layer has the pixels formed on the adherend. A mark in which the portion (convex portion) is cut in a pattern is observed in a concave shape, but the depth of the mark of the pixel is much deeper than that of the low-density polyethylene resin. It has been confirmed that the inlaid trace of the pixel is restored with time, and the pixel trace disappears after a few days at room temperature, and is completely restored to a flat state before lamination after one week. . This also indicates that the thermoplastic resin of the present invention has elasticity suitable as a material for a cushion layer.

A release layer can be formed between the cushion layer and the photosensitive phosphor layer, if necessary, or a wax-like release component is internally added to the inside of the cushion layer. It is possible to do. Depending on the type of resin used for the cushion layer, the release of the photosensitive phosphor layer is stabilized by providing a release layer or internally adding a release component, and the transfer of the phosphor layer to the adherend is prevented. The effect of making it easier can be exhibited.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The features of the present invention will be described below in more detail with reference to embodiments. Here, the usefulness of the present invention is exemplified for a transfer film for forming a phosphor used for CRT, but the present invention is not limited to these transfer films for forming a phosphor.

Example 1 A transfer film having the structure shown in FIG. 1 was produced as follows. (1) A 50 μm thick polypropylene film (OPP film) manufactured by Tocello was used for the cover film.
A photosensitive solution having the following composition was prepared, coated on a OPP film using a Meyer bar so that the coating thickness was 1.7 μm, and dried at 90 ° C. for 2 minutes in a hot air circulation type dryer. Then, a photosensitive adhesive layer was formed.

[0042] (Photosensitive composition for forming photosensitive adhesive layer) 35% by weight of photosensitive resin (modified PVA with photosensitive component added)       5- (4-azido-2-sulfobenzylidene) -3- (4,4'-dimethoxy       Cybutyl) rhodanine sodium salt introduction rate: 1.5 mol%,       Average degree of polymerization: 1100 Polyvinylpyrrolidone (K-120, manufactured by ISP) 15% by weight Acrylic emulsion 20% by weight       (Iodozol 3E0001, manufactured by NSC Japan) 20% by weight of water-soluble nylon (AQ nylon P-70, Tg-30 ° C, manufactured by Toray) 10% by weight of vinyl acetate emulsion       (Movinyl 185E, Tg0 ° C, Clariant Polymer) 950% by weight of methanol 950% by weight of water

(2) Teijin Dupont 5
A 0 μm PET film (provided with an antistatic layer on the back surface: surface resistance value of 10 ⁸ Ω / □) was used, and MR-7768 was added thereto.
(Acrylic acid ester copolymer: Tg 9 ° C, manufactured by Mitsubishi Rayon Co., Ltd.) was applied using a Meyer bar, and dried at 120 ° C for 4 minutes in a hot-air circulating drier to form a cushion layer having a thickness of 60 µm. . The deformation rate of the cushion layer resin was measured by the method described above, and the values are shown in Table 1 (the same applies hereinafter). Next, a photosensitive solution having the following composition was prepared, and was coated on the above-mentioned release layer using a Meyer bar so that the coating thickness was 12 μm.
After drying for a minute, a photosensitive phosphor layer was formed.

[0044] (Composition of photosensitive solution for forming phosphor layer)     Green light emitting phosphor (ZnS: Cu, Al) 94% by weight     1.2% by weight of photosensitive resin (modified PVA with photosensitive component added)           5- (4-azido-2-sulfobenzylidene) -3- (4,4'-dimethoxy           Cybutyl) rhodanine sodium salt introduction rate: 1.5 mol%,           Average degree of polymerization: 1700     Polyvinylpyrrolidone (K-30, manufactured by ISP) 4.8% by weight     123% by weight of water

(3) Lamination of phosphor transfer film The film obtained in (1) and (2) is bonded to the photosensitive adhesive layer surface of the film (1) and the photosensitive phosphor layer surface of the film (2). After stacking them facing each other, they were nipped in a laminator. The two films were bonded together under heat and pressure to obtain a green light-emitting phosphor transfer film. The bonding conditions are shown below. Pasting temperature: 120 ° C Pasting pressure: 2 kgf / cm ² Pasting speed: 2 m / min

Example 2 Example 1 was repeated except that a red light emitting phosphor (Y2O2S: Eu) was used as the composition of the photosensitive liquid for forming the photosensitive phosphor layer.
In the same manner as in the above, a red light emitting phosphor transfer film was obtained.

Example 3 A blue light emitting phosphor transfer film was obtained in the same manner as in Example 1 except that a blue light emitting phosphor (ZnS: Ag) was used as the composition of the photosensitive liquid for forming the photosensitive phosphor layer. .

The phosphor transfer films which emit light of three colors of green, red and blue shown in Examples 1 to 3 were patterned by the following procedure, and three types of fluorescent light were applied to the inner surface of the panel glass of CRT CRT glass. A body pixel was formed. First, after the cover film is peeled and removed, the photosensitive adhesive layer of the phosphor transfer film is placed on the panel glass to be adhered so that the photosensitive adhesive layer is in contact with the cover glass. ^{The two} were adhered by rolling at a speed of 700 mm / min while applying a pressure of ² .
Next, the support was peeled off at the interface between the photosensitive phosphor layer and the release layer, and the photosensitive phosphor layer was transferred onto the panel glass together with the photosensitive adhesive layer. Then, pattern exposure was performed using actinic rays. A high-pressure mercury lamp was used as a light source, and a quartz glass mask on which a pixel pattern on a grid was formed was inserted between the light source and the photosensitive phosphor layer. Exposure is 10-40mJ
The amount of energy was adjusted. After water sprayed from the nozzle in a mist state was sprayed for 2 minutes to perform development, compressed air was sprayed for 3 minutes to dry the panel glass and the phosphor pixels. These series of operations were performed three times to form phosphor pixels of three colors. The results of the evaluation of the transferability are shown in Table 1 below. Even if the transfer order of the phosphor transfer film of Examples 1 to 3 is used in any order, the transferability is extremely good, and even when the phosphor transfer film emitting light of a different color is transferred onto the formed pixels, The photosensitive adhesive layer and the photosensitive phosphor layer could be embedded in about 90% or more of the area between the formed pixels. Good C without peeling and falling off of pixels by patterning
A phosphor pixel for RT could be manufactured. The formed phosphor pixels did not peel off from the panel glass even after firing, and maintained a good state. In addition, 2-3
After transferring the phosphor transfer film of the color on the formed pixels, the state of the transfer between the formed pixels can be observed by looking through the back of the transfer surface, that is, the outer surface of the panel glass with a microscope (adhesion between the photosensitive adhesive layer and the glass surface). State) and the embedding property can be observed. If there is an air pocket or a transfer failure portion, the portion looks white, so that the area of the embedded portion can be calculated from the micrograph.

Comparative Example 1 In Example 1, Mirason M11 was used as the cushion layer.
A green phosphor transfer film was prepared in the same manner except that 80 μm of P (softening point: 105 ° C., low density polyethylene: manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) was formed on a support by extruding a molten film using a T-die. .

Comparative Example 2 In Example 2, Mirason M11 was used as the cushion layer.
A red phosphor transfer film was prepared in the same manner except that 80 μm of P (softening point: 105 ° C., low density polyethylene: manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) was formed on a support by extruding a molten film using a T-die. .

Comparative Example 3 In Example 3, Mirason M11 was used as the cushion layer.
A blue phosphor transfer film was prepared in the same manner except that 80 μm of P (softening point: 105 ° C., low-density polyethylene: manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) was formed on a support by extruding a molten film using a T-die. .

Phosphor pixels were formed in the same manner as described above by using the phosphor transfer films which emit light of three colors of green, red and blue shown in Comparative Examples 1 to 3, respectively. As shown in Table 1,
In this case, the transfer is possible up to the second color, and even if the second color phosphor transfer film is transferred onto the pixels of the first color, the photosensitive adhesive layer and the photosensitive adhesive cover about 65% of the area between the formed pixels. The phosphor layer could be embedded, and the pixel did not peel off during patterning, and a phosphor pixel for a CRT could be produced. However, for the third color, since the interval between the formed pixels is narrower, the photosensitive adhesive layer and the photosensitive phosphor layer of the third color are buried only in about 50% of the area between the formed pixels, which is desirable. It was difficult to form quality pixels. This phenomenon was not changed even if the transfer order of each color was changed.

Example 4 In Example 1, MR-7774 was used as the cushion layer.
(Acrylate copolymer: Tg 0 ° C., manufactured by Mitsubishi Rayon Co., Ltd.) was applied using a Meyer bar, and dried at 120 ° C. for 4 minutes in a hot air circulating drier to form a 25 μm thick cushion layer. Except for the above, a green phosphor transfer film was prepared in the same manner.

Example 5 In Example 2, MR-7774 was used as the cushion layer.
(Acrylate copolymer: Tg 0 ° C., manufactured by Mitsubishi Rayon Co., Ltd.) was applied using a Meyer bar, and dried at 120 ° C. for 4 minutes in a hot air circulating drier to form a 25 μm thick cushion layer. Except for the above, a red phosphor transfer film was produced in the same manner.

Example 6 In Example 3, MR-7774 was used as the cushion layer.
(Acrylate copolymer: Tg 0 ° C., manufactured by Mitsubishi Rayon Co., Ltd.) was applied using a Meyer bar, and dried at 120 ° C. for 4 minutes in a hot air circulating drier to form a 25 μm thick cushion layer. Except for the above, a blue phosphor transfer film was produced in the same manner.

Phosphor pixels were formed in the same manner as described above by using the phosphor transfer films emitting light of three colors of green, red and blue shown in Examples 4 to 6. As shown in Table 1,
Even if the transfer order of the phosphor transfer films of Examples 4 to 6 is used in any order, the transferability is good, and even in the case of the second color and the third color, an area of about 75% or more between the formed pixels is exposed. The photosensitive adhesive layer and the photosensitive phosphor layer could be embedded. Good C without peeling and falling off of pixels by patterning
A phosphor pixel for RT could be manufactured. The formed phosphor pixels did not peel off from the panel glass even after firing, and maintained a good state.

COMPARATIVE EXAMPLE 4 In Example 1, Byron 140 was used as the cushion layer.
0 (polyurethane resin, Tg83 ° C., manufactured by Toyobo Co., Ltd.) using a Meyer bar, and dried in a hot air circulating drier.
A green phosphor transfer film was prepared in the same manner except that drying was performed at 0 ° C. for 4 minutes to form a cushion layer having a thickness of 50 μm.

Comparative Example 5 In Example 2, Byron 140 was used as the cushion layer.
0 (polyurethane resin, Tg83 ° C., manufactured by Toyobo Co., Ltd.) using a Meyer bar, and dried in a hot air circulating drier.
Drying was performed at 0 ° C. for 4 minutes to produce a red phosphor transfer film in the same manner except that a cushion layer having a thickness of 50 μm was formed.

Comparative Example 6 In Example 3, Byron 140 was used as the cushion layer.
0 (polyurethane resin, Tg83 ° C., manufactured by Toyobo Co., Ltd.) using a Meyer bar, and dried in a hot air circulating drier.
A blue phosphor transfer film was prepared in the same manner except that drying was performed at 0 ° C. for 4 minutes to form a cushion layer having a thickness of 50 μm.

Phosphor pixels were formed in the same manner as described above using the phosphor transfer films which emit light in three colors of green, red and blue shown in Comparative Examples 4 to 6. As shown in Table 1,
In this case, although the first color can form good pixels,
In the second color, the photosensitive adhesive layer and the photosensitive phosphor layer could be buried only in an area of less than about 40% between the formed pixels, and a desired quality pixel could not be formed. Further, in the case of the third color, the photosensitive adhesive layer and the photosensitive phosphor layer could not be embedded between the formed pixels at all, and the pixels could not be formed. This phenomenon was not changed even if the transfer order of each color was changed.

The characteristics of the cushion layer and the transfer performance of the phosphor transfer film shown in the above Examples and Comparative Examples are summarized in Table 1 below. In addition, the evaluation of the phosphor pixel forming ability in Table 1 is as follows, and if it is “○” or more, it can be used as a non-defective product without any problem. ◎: A pixel having a desired size and a sharp edge could be formed. ：: A pixel having a desired size could be formed. △: A pixel smaller than the desired size was formed. Possible to form ×: A pixel was significantly smaller than the desired size pixel, or no pixel could be formed

[0062]

[Table 1]

As shown in Comparative Examples 1 to 3, a phosphor transfer film was prepared by using a conventionally used low-density polyethylene resin for the cushion layer.
Even if the thickness was increased to μm to provide cushioning, the photosensitive adhesive layer and photosensitive phosphor layer could be embedded only in an area of less than 60% between the formed pixels in the third color. On the other hand, if the thermoplastic resin of the present invention is used for the cushion layer, the photosensitive adhesive layer and the photosensitive phosphor layer can be embedded up to 78% between the formed pixels even if the cushion layer has a thickness of 25 μm. . That is, it is clear from this table that good phosphor pixels for phosphor displays can be formed by using the thermoplastic resin having the physical properties shown in the examples for the cushion layer.

[0064]

As described in detail above, according to the phosphor transfer film of the present invention, in the process of sequentially forming the phosphor pixels on the adherend by using the phosphor transfer film, the phosphor transfer film has already been formed. A new photosensitive adhesive layer and photosensitive phosphor layer can be satisfactorily embedded between the formed phosphor pixels following the surface shape. Therefore, it is possible to stably form the pixels of the phosphor display, which has been conventionally difficult. Further, since the phosphor transfer film of the present invention can significantly reduce the thickness of the necessary cushion layer,
The manufacturing cost of the phosphor transfer film can be reduced as compared with the related art.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a phosphor transfer film according to the present invention.

FIG. 2 is a cross-sectional view showing a state in which a phosphor transfer film is laminated on an adherend glass having formed pixels.

FIG. 3 is a conceptual diagram showing a method of measuring a TMA of a cushion layer resin.

FIG. 4 is a diagram showing an example of TMA measurement of a cushion layer resin.

FIG. 5 is a diagram showing a preferable state and an unfavorable state of the deformation rate of the cushion layer resin.

[Explanation of symbols]

1 Cover film 2 Photosensitive adhesive layer 3 Photosensitive phosphor layer 4 Cushion layer 5 Support 6 Antistatic layer 7 Pre-formed pixels 8 adherend

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01J 11/02 H01J 11/02 B (72) Inventor Hisashi Nakajima 1551 Todaira, Higashimatsuyama-shi, Saitama Nippon Paper Industries Co., Ltd. Higashi-Matsuyama Works (72) Inventor Michiaki Muraoka 1551 Higashidaira, Higashimatsuyama City, Saitama Prefecture Nippon Paper Industries Co., Ltd. 2H025 AB11 AB17 CC11 CC14 DA01 DA35 DA40 5C028 FF14 HH14 5C040 GG09 JA19 MA22

Claims (7)

[Claims] 1. A photosensitive material comprising at least one photosensitive adhesive layer and a photosensitive phosphor layer on a support, and a cushion layer made of a thermoplastic resin provided between the photosensitive phosphor layer and the support. The thermoplastic resin used as the cushion layer is 1
A phosphor transfer film having a deformation rate of 3000 to 30000 μm / m ° C. at 20 ° C. 2. The thermoplastic resin used as the cushion layer has a glass transition temperature of −10 to 35 ° C.,
And the softening point of the thermoplastic resin is 50 to 130 ° C.,
2. The phosphor transfer film according to claim 1, wherein the thermoplastic resin has a heat melting temperature of 180 [deg.] C. or higher. 3. The thermoplastic resin used as the cushion layer may be an acrylic ester copolymer, an ethylene vinyl acetate copolymer, a vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, or a copolymer of ethylene and an acrylic ester. A saponified compound, a saponified product of styrene and acrylate copolymer, a copolymer of styrene and isoprene, or a copolymer of butadiene, a polyester resin, and a resin selected from polyolefin resins, and having a molecular weight of 100,000 or more. The phosphor transfer film according to claim 1 or 2, wherein: 4. The thickness of the cushion layer is 20 to 60 μm.
The phosphor transfer film according to any one of claims 1 to 3, wherein m is m. 5. The photosensitive adhesive layer has a thickness of 0.5 to 3.0 μm.
5. The phosphor transfer film according to claim 1, wherein the photosensitive phosphor layer has a thickness of 3.0 to 25 μm. 6. 6. The phosphor transfer according to claim 1, wherein the glass transition temperature of the resin of at least one component contained in the photosensitive adhesive layer is 0 ° C. or less. the film. 7. A composition in which the photosensitive adhesive layer and the photosensitive phosphor layer contain a water-soluble photosensitive resin, wherein the water-soluble photosensitive resin is a stilbazolium group, a stilquinolinium group, or 5- (4-azido-2-sulfobenzylidene)-
At least one selected from the group consisting of sodium salt of 3- (4,4'-dimethoxybutyl) rhodanine and 0.5 to 5.0 mol% of a photosensitive component addition group having a polymerization degree of 500 to 3000;
The phosphor transfer film according to any one of claims 1 to 6, which is a modified polyvinyl alcohol.