JPS62220381A - Scribe recording material - Google Patents

Abstract

PURPOSE:To provide a scribe recording material suitable for use on a high-speed plotter and easy to handle, by providing a protective layer consisting of a resin layer comprising a substance lubricity, on a scribe recording layer. CONSTITUTION:A resin layer as a protective layer comprising a substance having lubricity is provided on a scribe recording layer provided on a base. The substance is preferably added in an amount of 10-200wt% based on the amount of a high molecular weight compound. Since the protective layer has lubricity, it is less liable to be marred when being touched by fingers, nails or the like in handling this scribe recording material, and since the protective layer gives a low drag on a scriber, it does not impair high-speed drawing properties of the scribe recording material. In addition, due to the low drag of the protective layer on the scriber, the scribe recording layer is clearly scratched off following the scriber. Accordingly, when drawing an image by a plotter, edge parts of the image will not be rugged, and breaking of the image at an intersection of lines will not occur.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a scribe recording material that can be subjected to high-speed drawing using an automatic drawing machine in the field of photolithography.

(Prior Art) Conventionally, in the field of photolithography, scribing on recording materials,
It is widely used to draw a line drawing by scratching with a scribe needle, use this as a negative original, and print it on a photosensitive material such as lithographic film or 28 plate. This kind of line drawing production has traditionally been done manually, but with the recent development of automatic drawing machines, it has come to be done mechanically. Further, it is desired that drawing by an automatic drawing machine be performed at high speed from the viewpoint of improving efficiency.

On the other hand, materials used in such scribe recording methods include those in which a coating film of a synthetic resin mixed with a colorant and an inorganic pigment is formed on a transparent support, and a coating film made of a synthetic resin mixed with a coloring material and an inorganic pigment on a transparent support. There are known methods in which a coating film is formed by adding a coloring agent and a metal soap to the paint (Japanese Patent Publication No. 44-9042, Japanese Patent Application Laid-open No. 55-124696). Furthermore, a material in which a metal layer is provided on a scribe recording layer for the purpose of obtaining a high light-shielding density has been proposed (Japanese Patent Publication No. 44-9044).

(Problems to be Solved by the Invention) Conventional scribe recording materials are suitable for manual scribing or scribing using low-speed automatic drafting machines, but scribing at low speeds is inefficient, and the recent photolithography process However, when scribing at high speed with an automatic drafting machine using conventional scribe recording materials, for example, scribe marks may be left behind or the scribe needle may fly off, resulting in scribing problems. The image quality deteriorates, such as the edges of the image becoming jagged and the image missing at intersections of lines. Therefore, if positive printing is performed by increasing the stylus pressure in order to reduce defects such as leaving scribes and flying scribes during high-speed drawing, the wear of the stylus tip will increase and the support will be damaged. On the other hand, if the scribe recording layer is made to be easily scraped by the scribe needle in order to avoid leaving scribe marks or defects that degrade image quality during high-speed writing, the surface of the recording layer will be easily scratched by fingers, nails, etc. Handling during work becomes extremely difficult.

Therefore, an object of the present invention is to provide a scribe recording material that can be passed through a high-speed automatic drafting machine and is easy to handle.

(Means for Solving the Problems) That is, the present invention is characterized in that a resin layer as a protective layer containing a slippery substance is provided on a scribe recording layer provided on a support. This is a scribing recording material.

As the support for the recording material of the present invention, plastic films such as polyethylene terephthalate, polyimide, polycarbonate, polyethylene, polystyrene, polyvinyl chloride, cellulose diacetate, cellulose triacetate, etc. are used. These supports can also be subjected to antistatic treatment in order to prevent chips and the like from re-adhering during drawing.

The scribe recording layer of the present invention includes phenol resin,
Any of the conventionally known materials whose main components are a binder made of a polymer compound such as a cellulose resin or an alkyd resin, a colorant such as an organic pigment or dye, and an inorganic pigment such as silica, kaolin, talc, or calcium carbonate can be used. In particular, when the recording material of the present invention is used as a negative original for a photosensitive material, it is necessary to have an optical density sufficient to block irradiation light, and the optical density in the wavelength range of 350 to 450 nm should be at least 1.5. It is desirable to do so.

The scribe recording layer may be provided directly on the support, but in order to adjust the adhesive strength and/or eliminate scribe residue during recording, a polymer compound may be added between the support and the recording layer. It is also possible to provide a subbing layer.

The protective layer of the present invention contains a polymer compound as a binder resin and a lubricating substance.

Examples of lubricating substances contained in the protective layer include: 1) hydrocarbon lubricants such as paraffin, wax, and polyethylene;
2) Fatty acid lubricants such as stearic acid, 3) Fatty acid amide lubricants such as stearamide, valmitic acid amide, methylene bisstearylamide, etc., 4) Ester lubricants such as butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc. , 5) Alcohol-based lubricants such as cetyl alcohol, stearyl alcohol, polyglycol, polyglycerol, 6) Metal soap, 7) Talc, graphite,
Solid lubricants such as molybdenum disulfide and boron nitride, 8) silicone resins, 9) fluorine resins, 10) cross-linked polymethyl methacrylate, and 11) cross-linked polystyrene are mixed together. can be used, but especially 1), 2), 4), 5), 6) and 9
) is preferred.

The polymer compound used as the binder resin for the protective layer is
Any known polymeric compound having film-forming properties can be selected and used, but for example, phenol resin, It is desirable to use a polymer compound that is insoluble in a chlorinated hydrocarbon solvent, such as a maleic acid resin or a vinylidene chloride resin.

It is preferable to add the lubricating substance in an amount of 10% to 200% by weight based on the above-mentioned polymer compound, and the method for adding the lubricating substance is to dissolve it in a solution of the polymeric compound that will serve as the binder. Or disperse.

When a film-forming polymeric compound such as a silicone resin or a fluororesin is used as the lubricating substance, one component can serve both as the lubricating substance and the polymeric compound as a binder.

The thickness of the protective layer is required to be 0.1 μm or more from the viewpoint of the strength of the recording material, but from the viewpoint of high-speed drawing performance, it is preferably 5 μm or less, and particularly preferably 0.3 to 3 μm.

The surface of the protective layer is preferably rough from the viewpoint of preventing blocking (sticking) between recording materials and shortening the adhesion time during vacuum adhesion during printing.Methods for roughening the surface include 1. 2) A method of electrostatically adsorbing particles onto the protective layer; 3) A method of spraying particles onto the Wt retaining layer; 4) A method of applying a matting agent together with a binder for the protective layer; There is a method in which the protective layer is coated with an uneven surface, and 5) a method in which a thermoplastic polymer compound is contained in the protective layer and the uneven pattern is pressed while heating the surface of the protective layer. Among these methods, the method of applying a matting agent together with a binder is preferable because the degree of roughness of the surface can be easily adjusted. As the matting agent at this time, inorganic pigments, fine polymer powders, fine solid powders, etc. can be used, but it is preferable to use extender pigments such as silica, kaolin, talc, and calcium carbonate as the inorganic pigments. In addition, by making the surface of the protective layer rough,
In order to prevent blocking and/or shorten the vacuum adhesion time, the centerline average roughness (according to JIS, BO601-1982) when the cutoff value is 0.8 mm is 0.
It is desirable to have a rough surface of 0.05 to 10 μm, especially 0.05 to 10 μm.
It is desirable that the thickness be 1 to 5 μm.

In the protective layer, a colorant, a plasticizer, a surfactant, etc. can be appropriately added to the above-mentioned components.

The above-mentioned scribe recording layer, protective layer and optional undercoat layer can be applied by any conventionally known coating method such as reverse roll coating, wire bar coating, gravure coating, dip coating, etc. When coating the layer, it is necessary to use a solvent that does not dissolve the scribe recording layer.

(Effect of the invention) When a protective layer is provided on the scribe recording layer which is made easy to be scraped off by a scribe needle so as to pass through high-speed writing, the protective layer has slipperiness. for,
The protective layer does not impair high-speed writing ability because it is not easily scratched even when touched with fingers, nails, etc. during handling, and has low resistance to scribing needles. In addition, since the protective layer with slipperiness has low resistance to the scribing needle, the scribing recording layer follows the scribing needle and is scraped cleanly, resulting in jagged edges of the image when drawn by an automatic drawing machine. The image at the intersection of the image lines will not be chipped.Furthermore, if the surface of the protective layer is roughened, even if recording materials are stacked on top of each other, the entire surface will not come into contact with each other, so blocking will not occur. When they are in close contact, air can easily escape, so the contact time is shortened.

(Example) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Preparation of Samples> Preparation of Sample 1 A pigment dispersion having the following composition was prepared by milling in a ball mill for 24 hours.

Yellow pigment (Syn+ulerFast Yellow manufactured by Dainippon Ink and Chemicals)
ow) GTF (trade name) 64.5 parts Red pigment (SymulerFast Red 4015 (trade name) manufactured by Dainippon Ink and Chemicals) 10 parts Talc (LIS #100 manufactured by Naigai Talc) (Item Number))
50 parts toluene 1353
5 parts Methyl ethyl ketone 135 parts Next, a scribe recording layer coating solution having the following composition was prepared using the dispersion having the above composition, and this was coated on a polyester film having a thickness of 125 μm so that the thickness of the dry coating film was 3.5 μm. By using the reverse roll coating method, the coating speed is 1.
It was coated at 0 m/min and dried at 80° C. for 90 seconds to form a scribe recording layer. The optical density of the obtained sample was 3.0 as measured by a transmission densitometer (TD-904 manufactured by Macbeth) using a UV filter.

Epoxy resin (Epicoat 1 made by Yuka Shell Epoxy ■)
004 (Product name)) 30 parts Nitrocellulose (551/2 (Product number) manufactured by Daicel Chemical Industries ■)
20 parts Unsaturated polyester resin (Vylon 200 (trade name) manufactured by Toyobo ■) 10 parts Magnesium oleate 12 parts Pigment dispersion having the above composition 394.5 parts Toluene
71 parts methyl ethyl ketone
298 parts cyclohexanone
43 parts Leveling agent (Florado 430 (trade name) manufactured by 3M Corporation) 0.17 parts Next, a coating solution with the following composition was dispersed in a ball mill for 24 hours to prepare a wire bar with a wire diameter Q of 4 mm. make use of,
It was coated on the above scribe recording layer at a coating speed of 20 m/min and dried at 60°C to obtain a scribe recording material. The thickness of the protective layer at this time was 1.5 μm. Moreover, the surface roughness was 1 μm in center line average roughness.

Polyvinyl butyral resin (S-LEC BL-1 (trade name) manufactured by Suzui Kagaku Kogyo 01) 10 parts wax (Diamond wax (trade name) manufactured by Shinnihon Rika Gl)
3 parts kaolin (ASP400P (product number) manufactured by Ueya Kaolin Kogyo ■) 10
Part Isopropyl Alcohol 40 Parts Toluene 40 Parts Preparation of Comparative Sample I A dispersion having the following composition was mixed and stirred in a ball mill for 24 hours to prepare. Furthermore, thinner (solvent composition, ethyl acetate: isopropyl alcohol dimethyl ethyl ketone: toluene: xylene - 4:5:1:2:4:
4) 85 parts were added to prepare a coating solution. This coating solution was applied to a polyester film with a thickness of 125 μm at a rate of 50 g/rtr.
Comparative Sample 1 was prepared by applying the following coating amount and drying at 80° C. for 90 seconds.

Nitrocellulose lacquer 12008 (King Paint-!i!ri) 50 parts Calcium stearate 4 parts Chromium Vermilion 10 parts Preparation of Comparative Sample 2 The pond where no protective layer was provided was the same as Sample 1. 2 was produced.

Preparation of Comparative Sample 3 A coating solution with the following composition was prepared and applied onto the scribe recording layer of Sample 1 using a wire bar with wire diameter Q and 4 mm at a coating speed of 20 m/min, and then dried at 60°C. A scribe recording material was obtained. The thickness of the protective layer at this time is 0.8 μm
Met.

Polyvinyl butyral resin (S-LEC BL-1 (trade name) manufactured by Tansui Kagaku Kogyo ■) 10 parts Isopropyl alcohol 45 parts Toluene
45 parts Preparation of Comparative Sample 4 A coating solution having the following composition was prepared by dispersing it in a ball mill for 24 hours.
．． Comparative sample 4 was prepared by coating at a coating speed of 20 m/min using a 4 mm wire bar and drying at 60°C. The thickness of the protective layer at this time was 1.3 μm. Moreover, the surface roughness was 1 μm in center line average roughness.

Polyvinyl butyral resin (S-LEC BL-1 (product name) manufactured by Tansui Kagaku Kogyo ■) 10 parts kaolin (ASP400P (product number) manufactured by Ueya Kaolin Kogyo (111jJ)) 10 parts isopropyl alcohol 40 parts toluene
40 parts Example 1゜Sample 1 obtained as above and comparative samples 1 to 4
A test was conducted using an automatic drawing machine at different drawing speeds, and the results shown in Table 1 were obtained. However, in the table, the ○ mark means that it is suitable for practical use, the Δ mark means that it can be put to practical use, and the X mark means that it is not suitable for practical use.

The test method is as follows.

The film surface of the film surface strength recording material was rubbed with a finger, a nail, or a pencil, and the extent of scratches was visually evaluated.

Drawing aptitude Recording materials were set in an automatic drawing machine and drawing was performed, and image formation was visually evaluated.

Images drawn in the same manner as in the image quality drawing aptitude test were observed and evaluated using a magnifying glass with a magnification of 100 times.

The blocking recording material was left in an atmosphere of 50°C and 80% RH for 60 minutes, then left under the same conditions under a pressure of 800 g/cut for an additional 60 minutes, and then visually evaluated for adhesion when peeled off. did.

Example 2 A coating solution for a protective layer having the composition shown in Table 2 was prepared, and sample l
Samples 2 to 13 were prepared in the same manner as above.

For samples 2 to 13 above, all drawing speeds were set to 17 m/
The test was conducted in the same manner as in Example 1, except that Table 3
The results were obtained.

Table 3 The results in Table 3 demonstrate that all of the scribe recording materials of the present invention can be used in high-speed automatic drafting machines and that surface roughening is effective for preventing blocking.

Example 3 A protective layer coating solution having the composition shown in Table 4 was prepared, and Samples 14 to 17 were prepared in the same manner as Sample 1.

The obtained samples 14 to 17 were tested in exactly the same manner as in Example 2, and the results shown in Table 5 were obtained.

Table 4 Table 5 The results in Table 5 demonstrate that the effects of the present invention can be obtained when the lubricating substance is added in an amount of 10% to 200% by weight based on the binder resin.

Example 4 A colored liquid having the following composition was mixed and stirred in a ball mill for 24 hours to prepare.

Red dye (Neozapon Red GE (product name) manufactured by Bardische Aniline Soda Co., Ltd.) 74.5 parts Talc (ls ll & L100 (product number) manufactured by Naigai Talc ■) 100 parts Toluene
135 parts methyl ethyl ketone
135 parts Next, a coating solution with the following composition was prepared using the above coloring solution, and coated on a polyester film with a thickness of 125 μm using a reverse roll coating method so that the dry coating thickness was 3.5 μm. speed 10
A scribe recording layer was prepared by coating at a rate of m/min and drying at 80° C. for 90 seconds.

Epoxy resin (Epicoat 1 made by Yuka Shell Epoxy ■)
004 (product name)) 3Qi nitrocellulose (manufactured by Daicel Chemical Industries, Ltd. (7) SSI/2 (product symbol)) 20 parts unsaturated polyester resin (
Byron 200 (trade name) manufactured by Toyobo ■ 10 parts Magnesium oleate 12 parts Coloring liquid with the above composition 394.5 parts Toluene
71 parts methyl ethyl ketone
298 parts cyclohexanone
43 parts Relinking agent (Florado 430 (trade name) manufactured by 3M Corporation) 0.17 parts A protective layer having the composition of Sample 1 was applied and tested in the same manner as Sample 1 on this recording layer. The results were similar to those obtained by engineering.

Claims (1)

[Claims] 1) On the scribe recording layer provided on the support,
A scribing recording material characterized by being provided with a protective layer made of a resin layer containing a substance having lubricity. 2) The amount of the lubricating substance is 10% by weight to 2% by weight based on the resin.
Claim 1 characterized in that it is 00% by weight.
Scribe recording materials as described in Section. 3) The lubricating substance is one or a mixture of two or more selected from hydrocarbon lubricants, fatty acid lubricants, ester lubricants, alcohol lubricants, metal soaps, and fluorine resins. A scribe recording material according to claim 1 or 2. 4) The surface of the protective layer has a center line average roughness of 0.05 to 10 μm
Claims 1 to 3 are characterized in that the rough surface is
The scribe recording material according to any of Item 3.