JPS6043652A - Photosensitive peel-off film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive peel-off film with an improved colored synthetic resin film layer (hereinafter referred to as beer coat layer), and more specifically, a film having a beer coat layer with excellent etching properties and beer properties. The present invention provides a photosensitive beer-off film.

The photosensitive peel-off film according to the present invention has a transparent support.
This photosensitive peel-off film is formed by sequentially providing a beer coat layer and a photosensitive photoresist layer on L. After exposure and development, the beer coat layer is etched with a J etching solution to form a relief image. Ru.

In general, a photosensitive peel-off film is exposed, developed, etched, washed, and dried to create a film cutout line that corresponds to the original drawing line, and the area surrounded by the film cutout line is separated to form a mask plate. Created. This Max plate is commonly used in the printing and plate making industry.For example, in order to print only lakes and marshes in a map with a color or pattern that is distinct from other parts, it is possible to print an area volume hole in the shape of a lake. It is necessary to make a negative or a corresponding positive with a pattern, and then create a printing plate for only that part, or to overlap it with a pattern negative and print it onto the printing plate. The negative or corresponding positive used in this case with a certain shape of area aperture is a mask plate.

Conventionally, the method for making these mask plates is to use a knife to make a photosensitive material called beer-off film, which has a colored synthetic resin film that has excellent light-shielding properties against active light and is easy to peel off from the base film. It is possible to cut out the cut lines faithfully to the original drawing, and then use the tip of the needle to touch the inner membrane of the groove. In this method, a beer-off film is layered on the original drawing,
Since the knife cuts are made by hand, the work can only be carried out by an experienced person, and since it takes a long time and relies on manual labor, the original drawings are not easily usable.

Attempts have also been made to improve these using photographic techniques. The first type is a photosensitive beer-off film in which a light-shielding dye or pigment is mixed in advance with a resin composition that undergoes a polymerization reaction and becomes insolubilized upon exposure to light and is coated on the film. When a positive line drawing original is placed on this film and exposed, the unexposed areas are eluted and washed with a solvent to obtain coating defect lines corresponding to the original image. In this method, the photosensitive wavelength range of the photo-insolubilized film itself overlaps with the absorption wavelength range of the light-shielding dye and pigment coexisting in the film, resulting in surprisingly low sensitivity of the culm, and the required baking time becomes extremely long, resulting in exposure. It has the drawback that heat rays from the light source are absorbed excessively, causing thermal dimensional changes in the original and the beer material, resulting in deterioration of accuracy. Also, it is dangerous because flammable organic solvents are used during the treatment process.

In the second type, soluble and highly light-shielding beer layers are provided on a film support, and the upper layer is made of beer layers.
A material coated with a silver cogenide gelatin emulsion. After exposing the upper silver halide gelatin photosensitive layer to light through a line drawing original, tanning and development is performed to dissolve the piratin that corresponds to the original image area, followed by washing with water and drying. Then, the lower layer is washed with water and dried. Peel 1 to 1 to dissolve the layer with a solvent to dissolve the radin and the beer - to dissolve the rhyme. After elution, wash and dry and use the tip of a sword to remove the skin fir and the area surrounded by the 7 cut lines. In this method, the first
Although the exposure time is shorter than that of the above type, the process is complicated and takes a long time, which is not satisfactory.

As a third type, polyvinyl alcohol, which is a water-soluble polymer material, and diazonyl 11, te 1 are coated on a film support as described in Japanese Patent Publication No. 50-27.402.
- A photosensitive film consisting of a photoinsolubilizing agent such as a lazonium compound and a weight [I] is prepared (J, a mask plate consisting of the steps of exposing it to light through a line drawing original, then dyeing, washing with water, and drying). This method has the advantage of not using a solvent in the processing solution, but because it uses a water-soluble photosensitive resin, it is susceptible to humidity effects and is even more difficult to brew. Since it is a dyed type, it requires a dyeing process, and has disadvantages such as temperature stagnation and a decrease in agricultural yield.

In addition, in a fourth type that attempts to solve these problems, an alcohol-soluble polyamide layer is provided as a beer coat layer on the transparent support -1-, and the layer is overlaid and exposed to light.
There is a photosensitive peel-off film in which first resist layers are sequentially provided.

In this type, an image is formed by etching the alcohol-soluble polyamide layer after exposure and development. Conventionally, the etching method for the alcohol-soluble polyamide layer is an aqueous solution mixed with an aromatic alcohol such as a lower alcohol. Processing method (Japanese Unexamined Patent Publication No. 55-1375
26), a method of treatment with an aqueous solution containing an aromatic neutral salt and alcohol (JP-A-55-137524, JP-A-55-137527) @ a method of treatment with an etching solution containing alcohol. However, the etching performance of these materials tends to change due to the evaporation of alcohol, they lack stability, and there is also a risk of ignition.

On the other hand, it can be treated with water-soluble lyricylic acid 1~liul\, hydrated [1ral, or promal hydrated method (Japanese Patent Publication No. 49-45321), an alkali metal compound of halogenated 71nol, or Method of treating halogenated benzoic acid with an aqueous solution of an alkali metal compound (
A method in which alcohol is treated with an etching solution such as JP-A No. 57-124'349 has also been shown, and the etching properties of -C are almost satisfactory.

However, photosensitive beer off-fill 1\ uses this alcohol-soluble ↑4 polyamide for the peel coat layer.

However, the strength of the film is still not satisfactory.

That is, since the strength of the coating is weak during beer work, the coating has the disadvantage of being easily broken during beer, resulting in poor workability. Increasing the thickness of the beer coat layer made of alcohol-soluble polyamide increases the strength of the film, but this is not a preferred method since it increases the time required for etching and reduces image reproducibility.

In order to solve these problems, the present inventors conducted intensive research on the material of the peel coat 1 layer that has excellent etching properties and beer properties, and as a result, they discovered that polyvinyl polymer resin and polyester resin that is compatible with it have been developed. It was discovered that by using a peel coat layer containing the above-mentioned polyamide, a photosensitive beer-off film with excellent etching properties and beer properties compared to those using conventional Al:1-l soluble polyamide in the peel coat layer can be obtained. This invention has been achieved.

That is, the present invention relates to a photosensitive beer-off film comprising a layer of Beer-2 1 containing a polyvinyl formal resin and a polyester resin compatible therewith on a transparent support, followed by a photosensitive photoresist layer thereon. .

Conventional photosensitive beer-off films using alcohol-soluble polyamide in the peel coat layer have drawbacks such as low film strength and poor beer workability due to embedding such as excessive film elongation.

In order to solve this problem, we took measures such as increasing the R taste of the film or mixing a hard resin that suppresses the elongation of the film, but if the thickness of the film was increased, the etching time would increase by one hour, and Side etch became noticeable and image reproducibility deteriorated, and when a hard resin was mixed, the film easily lifted from the support due to shock during handling, making it impossible to achieve Ifi 1m as a photosensitive beer-off film. There is a risk that the beer will run out, and neither of these results will be favorable, making it undesirable as a means for improving beer workability.

However, the material of beer Tl-1-1ti3 according to the present invention? When using q, a relatively thin film can be obtained (even with It is possible to obtain a photosensitive peel-off film that has high film strength, good beer workability, and no peeling of the film from the support base. Compared to film, it can significantly improve beer workability.

In addition, a layer mainly composed of alcohol-soluble polyamide resin (copolymerized nylon) is provided between the peel coat 1 layer containing polyvinyl formal resin and polyester resin according to the present invention and the support, and a peel coat layer made of 2Fdf& As a photosensitive beer-off film with a structure in which a photoresist layer is provided on the peel coat layer, the unevenness is 0. It is possible to improve the poor beer properties due to certain reasons such as low film strength and large film elongation, and obtain a photosensitive beer-off film with good beer properties and etching properties.

The transparent support used in the present invention has good flexibility,
In addition, polyesters such as polyethylene terephthalate, polycarbonates, and
There are films such as acetic acid cell [coarse], glass plates, etc., and biaxially stretched polyJ ethylene terephthalate film is particularly preferred because it is excellent in strength, dimensional stability, transparency, etc.

As for the polyvinyl formal resin used in the Peel-to-1 scrap of the present invention, the molecular volume, degree of saponification, and degree of formalization of the polyvinyl raw material are selected depending on the mechanical strength and chemical properties of the required film. is completed, formal component 75-85 wt%, degree of polymerization 300-11
00 is preferred.

Next, polyester resins which are compatible with polyvinyl formal resins are used as poly-1-nystyl resins, such as linear saturated polyester resins having a molecular iJ of 2,000 to 20,000.

Adhesion to the support, toughness of the film, physical properties of the film,
From the chemical properties of the film related to etching properties, its composition,
All you have to do is decide the degree of polymerization, etc.

What is the fruit of polynisder resin in the present invention? Its role is extremely important as a peel second layer.When polyvinyl formal resin is used alone, the film is difficult to catch on the edge of a knife when working with beer, resulting in poor workability, but this can be improved by mixing it with polyester resin. I can do it. In addition, it improves adhesion to the support and prevents the film from peeling off to the hour wheel due to impacts during handling, and when used as a two-layer peel coat layer, it improves adhesion to the layer below. Prevents intercostal detachment.

Furthermore, the etching time can be significantly shortened by using polyester resin which is soluble in alkali.

The mixing ratio of polyvinyl formal resin and polyester resin is in the range of 95:5 to 50:50, especially 90:10 to 6.
A range of 0:40 is preferred.

If the mixing ratio is less than 95:5, the adhesion between the support and the lower layer will be poor, and the film will simply peel off, no longer functioning, and the film will begin to peel off with the edge of a knife during beer work. Furthermore, the time required for etching may become longer, resulting in lower workability.

On the other hand, if the ratio of polyester resin is more than 50:50, the etching time will be shortened, but the strength of the film will be reduced, the elongation will be too high, and if it is applied directly to the support, the adhesion to the support will be poor. Too much beer will make working difficult.

In addition, the physical properties such as the hardness of the film can be roughly controlled1.
The third component resin may be mixed for six purposes. In this case, various resins having physical properties suitable for the purpose are selected from resins that are compatible with polyvinyl polymer resin and polynisder resin.

Examples include mixing nonol resins, nitrocellulose, etc. for the purpose of improving the hardness of the film. In that case, the mixing amount is suitably up to 40% of the total resin solid content.

When a two-layer peel coat layer is used, the performance of the beer coat layer, which is mainly composed of an alcohol-soluble polyamide resin, can be further improved by mixing, for example, an alkali-soluble acrylic resin with the alcohol-soluble polyamide resin.

This is because by mixing an alkali-soluble acrylic resin with an alcohol-soluble polyamide resin, it is possible to improve the poor beer properties caused by the woody nature of the polyamide resin, which makes the film soft and easy to stretch.

The mixing ratio of polyamide resin and acrylic resin is 90:10
A range of 50:50 is preferred. If the mixing ratio is less than 90:10, the purpose of mixing acrylic resin will not be achieved, and conversely, if the acrylic resin is more than 50:50, the flexibility of the film will be impaired, resulting in a brittle film. There is a risk that performance may deteriorate. In addition to the acrylic resin, resins suitable for the above-mentioned purposes may be appropriately selected and used in combination.

By providing a peel coat layer made of a mixture of the polyvinyl formal resin and polyester resin on this beer coat layer, the strength of the film is increased, and even with a relatively thin film thickness, the peel coat layer has excellent beer properties. A good peel coat layer can be obtained.

Further, in order to form a light-shielding colored image, it is necessary to incorporate coloring substances such as dyes and pigments into this Beer Co-1 layer. In order to form a colored image with sufficient light-shielding properties with a thin peel coat layer, the mixing ratio of the coloring substance is necessarily high, but in this case, in order to shorten the time required for J etching, it is necessary to Preference is given to using dyes that are soluble in the liquid.

In addition, as the material for forming the photosensitive photoresist layer used in the present invention, when forming a positive-positive type photosensitive photoresist layer, for example, there is a photosensitive resin composition using 〇-quinonediazide as a photosensitizer, When forming a negative-positive type photosensitive photoresist layer, for example, 2.
There are photosensitive compositions in which an azide-based photosensitizer such as 6-di(4'-azidobenzal)cyclohequilinone is mixed with a phenol novolac, but the composition is not limited thereto.

Incidentally, development of a single layer of the photosensitive photoresist 1 using these photosensitive materials can be carried out using an alkaline aqueous solution such as sodium hydroxide, tertiary sodium phosphate, or thorium carbonate. The method for forming an image on a photosensitive beer-off film according to the present invention involves first placing an original film on the film surface of a photosensitive photoresist layer, and then activating the film using a capsior arc lamp, mercury lamp, chemical lamp, metal halide lamp, etc. Exposure to light. Next, sodium hydroxide, tertiary sodium phosphate, and sodium carbonate.

alkaline aqueous solution such as sodium silicate ((l!
(I may contain alcohol, surfactant, etc.) to remove the photosensitive photoresist layer. developing【
Regarding the exposed portion of the peel coat layer, an aqueous solution of a salt such as sodium salicylate or sodium trichloroacetate, which does not dissolve the remaining fluorine resist layer but can dissolve the beer coat layer, and 1 to luenesulfonic acid. The image is dissolved and removed by treatment with an etching solution such as an aqueous solution of an acid such as , sulfo-monoricylic acid, maleic acid, FIIN, or formic acid, an aqueous solution of chloral hydrate, cresol, or ethylene dichloride, and an image is formed. LI formed? Regarding the II image, any part surrounded by the film defect line can be selectively rubbed with the edge of a knife or the like.

After exposure, the photoresist layer and the underlying Beer Co. I layer are treated at once with an aqueous solution containing an alkali and a salt such as sodium salicylate, or a processing solution containing a small amount of alcohol if necessary. It is also possible to form an image by dissolving and removing it.

The present invention will be further explained below with reference to Examples.

Examples 1-3 Biaxially oriented poly, [tyrene alephthalate film (10
0μ loaf), apply a film forming solution with the following composition to a dry film thickness of 8μ.
The film was coated with a buif coater to give a coating film of n1, and dried in an oven at 100°C for 2 minutes to form a peel coat layer.

Polyvinyl formal resin (PVF 82j4i4
%PVΔ6 heavy can%PVAC12 heavy f1%Average insect polish approx. 9
50) A-polyester polyester resin (Borini [Stel] with an average molecular weight of 116,000 m, consisting of 25 mol% prephthalic acid, 25 mol% isophthalic acid, and 50 mol% 1,4-butanediol)
8 parts by weight Neo 1f Bonred GE (red dye manufactured by BASF)
120 heavy tears J Ethyl l? ITI Solve 70 parts methanol 125 parts by weight l Toluene 485 parts by weight (Each resin addition ff1A, B is listed in the table.)Next, the following resist forming solution was applied to the above Beerco-1・H to a dry film thickness of 2μ.
It was coated with a wire bar so as to have mrL, and dried in an oven at 100°C for 2 minutes to form a photosensitive photoresist layer, thereby obtaining a photosensitive peel-off film. 11 parts of alkali-soluble pheno-crucvolac ≧ 1.2-naf+-'quinonediazido-5-sulboni t
Synthesis of chloride and alkali-soluble fl phenol novolac resin Iogim part Butyl acetate 108 heavy parts Cyclohexanone 27 parts , 1m distance l) \ et al 4
Exposure is carried out for 0 seconds, and then treated with an η image etching solution having a solution temperature of 30'C as described below to dissolve and remove the photoresist layer and peel coat layer in the exposed areas, forming both a.

Then, rinse under running water for 30 seconds and dry.

Sodium salicylate 35 tbsp omega parts Sodium to lithium hydroxide 0.3 parts by weight Water 64.7 parts Development time, physical properties of the film, beer properties, etc. It's eight.

Examples 1 to 3 show good beer properties with high film strength and low elongation. Further, during handling, the film of the support 1 etc. does not come off.

In Comparative Example 1, the adhesion to the support was poor and the film peeled off easily. Also, the etching time is long.

Moreover, Comparative Example 2 had poor beer properties because the film had little sclerosis and had a large elongation. In Comparative Example 3, although the elongation of the film decreased, the film strength was insufficient, so the beer quality was satisfactory.
6-Also, the etching time becomes longer.

Example 4 Biaxially oriented poly-[thione alephthalate I film (1
00μ thick) and dry film w3μ of the following composition 0 film forming solution on top
Form a Y (7-bar coating, dry in an oven at 100°C for 2 minutes, and peel) so that the thickness is 1.

80 parts by weight of a copolymer of caprolactam, hexamethylene diamine adipate and 4,4'-diaminodicyclo[1-hexylmethane adipate 1] 20 parts by weight of an acrylic acid/methacrylic acid ester copolymer Neozapon Red G E 20@Amount 8 parts ethyl cellosolve, 1 part methanol, 11 parts GOO, and then applied the film forming solution of Example 2 on top of this beer w and -ha to a dry film thickness of 5 μm using a knife knife 1-CG cloth. , and dried in an oven at 100° C. for 2 minutes to form a beer coat layer with a two-layer structure.

Thereafter, a layer was formed on the photo resist 1 in the same manner as in Examples 1 to 3, and images were formed by exposing, developing and etching. The results are shown in the table. As shown in the table] - 9 for tsuging time: 1 for bad beer quality;! tiY Photosensor 1 (I was able to drink 1 beer ΔTsunoiru l\).

(Note) The tensile strength, elongation, and peeling force of the film were measured using Toyo Baldwin Y'TENs I LON, IJTM-m model.

Tensile speed: Tensile strength -200g/min.

Peeling force - 100mm/min Peeling force was measured using 1806 beer.

*1 The film was too stretched and could not be measured. Example 5 A negative resist forming solution having the following composition was applied onto the layer of Beerco-1 obtained in Example 2 using a wire bar so that the dry film thickness was 2 μm.1. The photoresist was dried in an oven at 100° C. for 2 minutes to obtain a photosensitive film.

Alkali-soluble phenolic novolac resin 10 parts by weight 2,6-di (4'-azidoben amount fJ) cyclohexane 2 mm parts Butyl acetate 86 single parts cyclohexanone 22 parts of double phase When an image was formed by exposure and development in the same manner as in Example 3, it showed good beer properties as in Example 2.

October 5, 1980 Commissioner of the Japan Patent Office Wakagi Rifurogimo Kawa Q 1, Incident Indication Showa (58th year 1) +; TI+ri No. 151208G
2. Name of the invention Photosensitivity, 1. Cow beer off film 3.? Relationship with the case of those who commit illegal acts Special i'F Client Address 1 Marunouchi, Chiyoda-ku, Tokyo = 4-5 Name (
234) Sanyo M-Saku Valve Co., Ltd. 4, Agent 41 Address: 16 Kanda Higashimono-cho, Chiyo 10-ku, Tokyo 1
01 English Building 3rd floor Akirall1llll book Detailed explanation of the invention Ji and 9 letters [
Claims [0, Top 6, Contents of the amendment As shown in the attached sheet Contents of the sleeve stopper (1) Feature 1'1 The top of the scope of claims has been corrected as shown in the attached sheet.

(2) Revised the Detailed Description of the Invention section as follows: 1F.

1, Ming ■ tin page 2, line 14 r j# III+! This was created due to a lack of it! ,'! 1 and 1
The skin lIj, j missing line is created, and this film missing line is corrected as 1, 1 2, and on the same page line 16, ``Maks belly I is there 1 mask version 1
Corrected.

3. Particularly harmful bacteria, page 4, line 1, r 71!71! , 1 chipping and abrasion j1 is corrected as [film chipping line].

4. On page 5, line 5 of the specification box, the text "Tetra\noI311 compounds" has been replaced with "Te1-Lazonium compound 1do W.

5, Akinu S: Aii page 9th line - 10th line l-2F
: When used as a peel coat layer of 1i15 ii-, the adhesion with the lower layer is 1, which means "Roughly alcohol soluble 1!"
1. A material mainly composed of polyamide is placed below (J2 layer width)
When using a beer coat layer, correct this layer to be IJ11.

6. Delete the statement ``Used as a coloring substance'' on page 14, lines 7-8 of Meine III.

7. Add the following sentence between lines 10 and 11 on page 16 of the statement box.

1-In this way, a photosensitive 'IQ beer-off film in which a peel coat layer containing the polyvinyl polymer resin and polyester resin of the present invention as main components is provided on a transparent support, or an alcohol-soluble film is further added under the peel coat layer 1. Photosensitive 111 beer-off film with a two-layer structure consisting of 1 to 1 layers of peel-off film with a layer mainly composed of 1 F polyamide 191 resin 1.1. The film strength of the peel coat layer is high and the film is elongated. 11 (<, sales (this film has a close contact Pi), beer = l'l 1 spoiled, and photosensitive beer off film C important 6 light, present (t (1 change of etching, Ill It can be said that it is an epoch-making photosensitive material that is superior to the conventional technology.1 Claims 1. A colored synthetic resin coating on a transparent support, A photosensitive beer-off product characterized in that the colored synthetic resin film is made of a polyvinyl formal resin, a polyester resin that is compatible with the polyvinyl formal resin, and a light-shielding dyed face layer 1. film.

2. Alcohol-soluble polyamide resin on transparent support,
A colored synthetic resin film layer containing a light-shielding dye and pigment as a main component is provided, and a colored synthetic resin film layer consisting of a polyvinyl formal resin, a polyester resin compatible with the polyvinyl formal resin, and a light-shielding dye and pigment is provided. A covering photosensitive beer-off film characterized by comprising a coating layer and a photosensitive photoresist layer in this order.

Claims (1)

[Claims] 1. A colored synthetic resin film layer and a photosensitive photoresist layer are sequentially laminated on a transparent support, and the colored synthetic resin film layer is made of a polyvinyl formal resin and a polyester resin compatible with the same. and a light-shielding dye and pigment. 2. Alcohol-soluble polyamide resin on a transparent support,
A colored synthetic resin film layer containing a light-shielding facial cleanser as its main component is provided, and then layered on top of it, a colored synthetic resin film layer consisting of a polyvinyl formal resin, a polyester resin compatible with this, and a light-shielding dye and pigment is formed. It is characterized in that a resin film layer and a photosensitive photoresist layer are provided in this order.