JPS604976B2 - developer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a crab light film in an electron tube such as a color television picture tube or a color crab light display tube, in particular, a previously developed low molecular weight polyvinyl alcohol (hereinafter referred to as PVA). It relates to a developer for a crab photo film using crab photo material slurry as the main component.

Usually, to form a colored crab-light surface, a crab-photon slurry of each color is used, which is a mixture of PVA as a photocurable binder and honeydew powder of each color in a solvent.

First, the crab photon slurry of one color is applied to the inner surface of the substrate on which the crab light surface is to be formed, such as the panel of a picture tube, and then exposed to light in a predetermined pattern. Wash off the unexposed areas with water. After the crab glaze of one color is formed into a predetermined pattern in this way, the crab glaze of each color is sequentially painted into a predetermined pattern using the same method using other crab phosphor slurries. By the way, in order to increase the luminance of the crab light, it is desirable to increase the packing density of the crab light as much as possible.

However, it has been impossible to increase the packing density with the conventional crab phosphor slurry mainly composed of high molecular weight PVA because it deteriorates the film quality. In order to solve this problem, the present applicant has previously developed a lepidopter slurry that can obtain a crab phosphor film with high luminance by increasing the packing density of the phosphor, that is, a low molecular weight
We have developed a crab phosphor slurry whose main component is PVA. First, this crab photon slurry will be explained.

This crab photon slurry has an average molecular weight of 10,000 to 50.
000 so-called low molecular weight PVA and 4 to 1 of this PVA
It has 0 times the amount (weight) of crab light, and its solid content is 30%.
(weight) or more by dissolving it in a solvent. Examples of PVA having an average molecular weight Mn of 10,000 to 50,000 include Denka Poval B-0 Fgosenol GL-0
Fukurare PVA205 (both are trade names and their MOn is approximately 20,000), etc. can be used. Incidentally, the PVA used in the conventional crab photon slurry has Mn of 6 or more.
In the above crab photon slurry, Mn is 10,000~
50,000 PVA is specified because if Mn is less than 10,000, the properties as a polymer will be lost and the function as a binder will be insufficient, and if Mn exceeds 50,000, the packing density of the crab phosphor will decrease. This is because improvement cannot be expected. In addition, the reason why the volume of the crab phosphor is selected to be 4 to 1 pm compared to the weight of PVA is because if the amount is less than 4 times, the packing density of the crab phosphor cannot be expected to improve, and if the volume exceeds the IM volume, the voids between the phosphor particles will increase. The binder is PVA
This is because the strength of the coating film itself decreases because it cannot be filled sufficiently. It is most preferable to select the ratio of the crab phosphor to PVA to be approximately 7:1 (by weight). Furthermore, the solid content in the slurry, i.e., the sum (weight) of each content of mainly PVA and crab phosphor, is selected to be 30% or more.If it is less than 30%, improvement in the packing density of crab phosphor cannot be expected. It's for a reason. According to such a crab phosphor slurry, a high crab phosphor packing density can be obtained with a small film thickness, so that a crab phosphor film with high luminance can be formed. An example of such a crab photon slurry is shown below. Denka Poval B
-05 (trade name manufactured by Denki Kagaku Co., Ltd.) 1 part by weight Crab phosphor powder (Z
nS:Ag) Particle size 5r 7 parts by weight Sodium hexametaphosphate (surfactant) 0.00 parts by weight Ammonium dichromate (light curing agent) 0.05 parts by weight Solvent 12.1 parts by weight By the way, high molecular weight PVA Water has generally been used as a developer for a crab-photo film using a conventional crab-photo substance slurry.

However, in the case of the above-mentioned crab photon slurry using low molecular weight PVA, when water was used as a developer, there were cases where good development processing could not be achieved. That is, the water solubility of low molecular weight PVA is greater than that of high molecular weight PVA, and
Even A has a wide molecular weight distribution. For this reason,
When the above-mentioned low-molecular-weight PVA slurry is applied, exposed to light in a predetermined pattern, and then developed with water, the least-exposed areas are dissolved and removed, while at the same time the crab-photon parts present in the crab-light areas are removed. The low molecular weight components that could not be made insoluble were dissolved, that is, a portion of the exposed area was dissolved, and the film retention properties of Appearance Gloss 3 were deteriorated as a whole. In view of the above-mentioned points, the present invention provides a developer for a photosensitive film, ie, a crab film, whose main component is low molecular weight PVA, which can improve the film retention properties thereof. It is something.

That is, in the present invention, a developer is composed of water as a main component and a predetermined amount of PVA non-solvent mixed therein.

The amount of the PVA non-solvent to be added is such that the maximum molecular weight component of the unexposed PVA is dissolved within a practical range, and the minimum molecular weight component of the exposed PVA or a low molecular weight component in the vicinity is determined in the amount of PVA to be developed. The components are selected in amounts that do not dissolve within a practical range. Therefore, the amount of non-solvent added varies depending on the molecular weight of PVA contained in the crab-light film to be developed, and also varies depending on the type of non-solvent to be mixed. As a non-solvent for PVA, it is compatible with water and has a certain solubility parameter (
cohesive energy density) 6 is as small as possible, i.e. 8
It is desirable that the boiling point is in the range of 20 to 20, and that the boiling point is lower than the boiling point of water (100 qo). Here, the solubility parameter 6 was specified to be in the range of 8 to 20 as a non-solvent condition because if 8 is less than 8, it will not dissolve in water, and 6
If it exceeds 20, the solubility parameter of water approaches and the effect of lowering the solubility as a developer cannot be expected.

In addition, as a desirable condition for the nonsolvent, the boiling point of the nonsolvent is 100
The reason for selecting 0 or less is that the coating film dries quickly and is expected to improve workability.

On the other hand, if the boiling point is 100° C. or higher, it is necessary to modify the drying conditions of the coating film, and workability deteriorates. In the table below,
Some of the non-solvents for PVA that can be applied to the present invention are listed below. In addition, the solubility parameter 6 and boiling point (℃) of each nonsolvent
is shown in comparison with water. In the present invention, one or more PVA nonsolvents as shown in the table above are mixed with water to form a developer.

Next, examples of the present invention will be shown.

Figure 1 shows that in a developer mixture of water and acetone,
FIG. 3 is a diagram showing the relationship between the volume fraction of acetone and the development effect.

In the figure, the vertical axis shows the coating film residual rate of the PVA photosensitive film,
The volume fraction of acetone is shown. Curves a and a2 are for the exposed and unexposed areas, respectively, when a high molecular weight PVA photosensitive film having an average molecular weight of about 100,000 is used. Curves 0 and Q are for the exposed and partially exposed areas, respectively, when a low molecular weight PVA photosensitive film having an average molecular weight of about 20,000 is used. In addition, the exposure time is 6
$ec, developer dilution time is 1 hour (1800), and P
The content ratio of ammonium dichromate AOC and polyvinyl alcohol PVA in the VA photosensitive film was set to ADC/PVA=0.
It was set as 05.

As is clear from FIG. 1, water (at the position where the acetone fraction is 0) is suitable as a developer for high molecular weight PVA photosensitive films.

On the other hand, in the case of a low molecular weight PVA photosensitive film, when water is 100%, the coating strength residual rate in the exposed area is as low as about 45%, making it inappropriate to use water as a developer. However, the coating film residual rate in the exposed areas increases with the increase in acetone.
When the volume fraction of acetone is about 25%, the coating film residual rate is about the same as that of polymeric PVA (see curve 1). In addition, the residual rate of the coating film in the exposed area is approximately 25% by volume of acetone.
It is 0 up to approximately 0, and an insoluble portion appears from beyond this point (see curve b2). Therefore, as a developer for a photosensitive film, ie, a honeycomb film, whose main component is PVA having an average molecular weight of about 20,000, it is preferable to use a developer composition consisting of water mixed with 25% by volume or less of acetone within a practical range. Although not shown in the figure, as the average molecular weight of PVA changes, that is, as the average molecular weight decreases, the curve width moves to the right in the figure, and the practical range of acetone as a developer is 23% by volume as mentioned above.
The trend is to expand further. Furthermore, when the exposure time for a low molecular weight PVA photosensitive film is increased, the coating film residual rate in the exposed areas is improved. Curve Q is for the exposed portion when the exposure time is 18 $ec, and in this case, the amount of acetone mixed with water as a developer will widen its practical range. Figure 2 shows tetrahydrofuran (▲), methyl acetate (□), acetone (・), t-butyl alcohol (△), and isopropyl alcohol (x) as non-solvents listed in the table above. Low molecular weight P when the volume fraction of each non-solvent is changed in a developer prepared by mixing water with ethanol (marked) and ethanol (marked 0).
FIG. 2 is a diagram similar to FIG. 1, showing the development effect on a VA photoresist film.

In addition, in FIG. 2, only the exposed part is shown, and the curve b・
curve Q shows the lower limit when acetone is used, and the curve Q shows the lower limit when each other nonsolvent is used. As is clear from this figure 2,
All of the developing solutions using the above-mentioned non-solvents exhibit remarkable development effects.

Among them, a developer using acetone (curve et al.) is the most effective, followed by methyl acetate (circle mark), t-butyl alcohol (△ mark), inbropyl alcohol (x mark),
Ethanol (marked 0), followed by tetrahydrofuran (marked ▲). As a result, in the developer according to the present invention, although there are some exceptions, in general, the smaller the solubility parameter 6 value of the nonsolvent, the greater the effect as a developer. On the other hand, the composition of the developer according to the present invention described above can be applied to the solvent of the photoluminescent slurry using the above-mentioned low molecular weight PVA.

That is, the formation of the color crab light surface is performed by applying the photoluminescent slurry of the first color as described above, exposing it to light in a predetermined pattern, and then washing and removing the exposed portion with a developer. Forms a crab photobody membrane. Next, the second color is applied to the entire surface including the first color crab light body waist.
After applying the total color phosphor layer IJ-1, the same process is repeated to form a crab phosphor film of the second color, and thereafter a tertiary crab phosphor film is formed in the same manner. By the way, in this case, if water as a subsidiary or a substance containing a slight amount of alcohol as the main component is used as a solvent for the crab photon slurry using low molecular weight PVA, the second color crab photon slurry or When the 38th honey phosphor slurry is applied to the entire surface, the first color crab phosphor film or the second color crab phosphor film that has already been formed is partially covered by the solvent in the crab phosphor slurry. A scum is formed that dissolves. Therefore, if a solution having the same composition as the above-mentioned developer, that is, a solution prepared by mixing a specific amount of PVA non-solvent with water, is used as the solvent in the crab photon slurry made of such low molecular weight PVA, the second or When the third color crab light slurry is applied to the entire surface, the previously formed crab light film is not dissolved, and a good colored crab light surface can be formed. As described above, by using the developer according to the present invention, it is possible to satisfactorily develop a crab phosphor film using a crab phosphor slurry using low molecular weight PVA that obtains a high phosphor packing density, and thus the luminescence brightness can be improved. It is possible to form a highly accurate crab light surface with high precision.

[Brief explanation of drawings]

Figure 1 is a characteristic curve diagram showing the development effect on a PVA photosensitive film when the volume fraction of acetone is varied in a developer consisting of water and acetone. FIG. 3 is a characteristic curve diagram showing the development effect on a low molecular weight PVA photosensitive film when the volume fraction of each non-solvent is changed in a developer consisting of the following. Figure 1 Figure 2

Claims (1)

[Claims] 1. In a developing solution for a photosensitive film whose main component is low molecular weight polyvinyl alcohol with an average molecular weight of 10,000 to 50,000, the maximum molecular weight component of unexposed polyvinyl alcohol is dissolved within a practical range and exposed polyvinyl alcohol is used. Methanol, ethanol, isopropyl alcohol, t-butyl alcohol, acetone, methyl acetate, tetrahydrofuran, polyvinyl alcohol in an amount that does not dissolve the minimum molecular weight component of alcohol within a practical range.
A developer characterized by dissolving a non-solvent such as dioxane in water.