JPH06100818B2 - Correction fluid for photoengraving - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a correction liquid for masking an unnecessary portion of an original film when making a printing plate in photolithography.

2. Description of the Related Art Conventional Problems and Their Problems The photolithographic correction fluid is used for the correction of the original film characters and plates, or the correction of the original film when synthesizing line drawings and halftone diagrams in photoengraving. Further, such a correction liquid is also used when performing multicolor printing of two or more colors by photolithography. That is, in order to perform multicolor printing, first, the number of original films corresponding to the number of printing colors is created from the original images. Then, a portion other than a portion corresponding to one specific color of each film is masked with a photolithographic correction liquid, and a photosensitive body such as a photosensitive resin plate is exposed using these films. Printing is performed using a plurality of printing plates for each color thus obtained.

The properties required for such a photolithographic correction fluid are as follows.

(I) Good adhesion to silver salt-gelatin film and hydrophobic film, (ii) Appropriate flexibility of coating film, (iii) Light-shielding property against ultraviolet light and light of 400 to 700 nm (Iv) When applying the correction liquid, application unevenness due to a brush or brush does not occur (good leveling property), (v) It is easy to dry the inside of the coating film, and the drying condition can be visually judged. ) Films coated with the correction fluid do not stick to each other, and there is no show-through, (vii) no contamination of the working environment due to solvents, etc. (viii) bubbles in the coating film generated when the correction fluid is applied to the film Disappears quickly.

However, conventionally, as a correction liquid, an aqueous correction liquid in which a rouge is dispersed in a water-soluble resin, or a quick-drying correction in which red and yellow oil dyes or pigments are dispersed in a solution in which a synthetic resin is dissolved in an organic solvent is used. There is only liquid.

That is, the former aqueous correction liquid has a slow drying rate and has poor adhesiveness to a hydrophobic film such as polyethylene terephthalate and cannot form a correction coating film.

On the other hand, since the latter organic solvent-based correction fluid uses an aromatic solvent, it has environmental health problems such as poisoning due to the solvent. In addition, since those containing oil dyes are quick-drying, a surface film is formed before the inside of the film is sufficiently dried. Block phenomenon,
Further, there is also a drawback that so-called show-through occurs in which color is transferred to the back surface of the laminated films by sublimation of the oil dye.

INDUSTRIAL APPLICABILITY The present invention has no environmental hygiene problem which has become a problem in recent years, and shows excellent adhesiveness even to a quick-drying hydrophobic film, and also has an excellent light-shielding property without blocking phenomenon, show-through, etc. It is intended to provide a correction liquid for photolithography as shown.

Means for Solving the Problems That is, the present invention provides (a) an alkali neutralized product of an acrylic acid ester-maleic anhydride copolymer, an alkali neutralized product of an acrylic acid ester-acrylic acid copolymer, and an acrylic acid ester. -Alkaline neutralized product of methacrylic acid copolymer, vinylpyrrolidone-vinyl acetate copolymer, polyvinylpyrrolidone, styrene-
One or more polymers selected from the group consisting of alkali neutralized products of maleic anhydride copolymers and alkali neutralized products of methyl vinyl ether-maleic anhydride copolymers; (b) pigments; and (c) ) A correction solution for photoengraving, which comprises a solvent selected from the group consisting of ethanol and a mixed solvent of ethanol and water.

As the polymer to be blended in the correction fluid of the present invention, a polymer that is soluble in alcohol or hydrous alcohol, has good adhesiveness to a hydrophobic synthetic resin, and has appropriate flexibility is selected.

Examples of such polymers include alkali neutralized products of acrylic acid ester-maleic anhydride copolymer, neutralized products of acrylic acid ester-acrylic acid copolymer, and neutralized products of acrylic acid ester-methacrylic acid copolymer. , Vinylpyrrolidone-vinyl acetate copolymer, polyvinylpyrrolidone, styrene-alkali neutralized product of maleic anhydride copolymer, methyl vinyl ether-alkali neutralized product of maleic anhydride copolymer, and these alone, Alternatively, two or more kinds are mixed and used.

Examples of the acrylic acid ester monomer and the methacrylic acid ester monomer include methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, phenyl, cyclohexyl ester and the like are preferable.

The alkali-neutralized product is a salt of a carboxyl group derived from maleic anhydride, acrylic acid, or methacrylic acid, which is an alkali metal salt, an ammonium salt, or an organic amine (for example, 2-amino-2-methyl-1-prohanol). It is in the form of.

Commercially available products of the polymer used in the present invention include, for example, Julimer AT210, AT510, AT613, ET410, FC60 (manufactured by Nippon Pure Chemical Co., Ltd.).

The content of the above polymer in the correction fluid is 5 to 20% by weight.
Is preferred. If the amount of the polymer compounded is less than 5% by weight, the effect as a binder is poor and a good coating film cannot be obtained. On the other hand, if it exceeds 20% by weight, the matting property is lost (becomes smooth), and the viscosity of the correction liquid becomes too large, which causes difficulty in the coating operation.

Next, as the pigment to be added to the correction liquid of the present invention, a dispersion type pigment having an appropriate particle size is preferable, but any of the known pigments conventionally added to such correction liquid are preferably added. In particular, in order to clarify the modified portion, it is preferable to mix a black pigment and a white pigment, or to mix a red pigment, a yellow pigment and the like.

For example, yellow pigments include monoazo pigments, disazo pigments, insoluble monoazo pigments, red pigments include insoluble azo pigments, quinacdrine, etc., white pigments are preferably titanium white, and black pigments are preferably carbon black.

The amount of such a pigment compounded is usually 5 to 20% by weight. If the amount of the pigment compounded is less than this range, the light-shielding property is poor and the action as a correction liquid is insufficient. On the other hand, if it exceeds this range, the viscosity becomes too high and the pigment may be detached from the coating film.

As the solvent (or dispersion medium), ethanol or a mixed solvent of ethanol and water is used. In the case of a mixed solvent, the water content is preferably 60% by weight or less from the viewpoint of drying rate.

In addition, it is preferable to add 5 to 15% by weight of silicic acid anhydride to the correction solution of the present invention. By adding silicic acid anhydride, the air permeability inside the coating film is improved, the solvent is easily volatilized, and the drying condition can be confirmed as a change in the color of the coating film.
Further, there is a matting effect, and it becomes easy to distinguish between the portion to which the correction liquid is applied and the non-correction surface.

Further, in the present invention, it is preferable to add 0.1 to 1% by weight of an acetylene glycol-based or acetylene alcohol-based antifoaming agent. As such a defoaming agent,
Safinol 104, TG, PC, 61, 82, 440, 465, 4
Examples of the commercially available defoaming agent include trade names such as 85 (manufactured by Nissin Chemical Industry Co., Ltd.). With these fine particle size defoaming agents,
An excellent film without pinholes can be obtained even with an extremely thin correction film of 10 μm.

In order to produce the correction fluid of the present invention, first, the polymer is mixed with a solvent and dissolved by stirring, and then a pigment is added to this and pre-stirring is performed. Next, this mixture was mixed with a Glen Mill disperser (diameter 1-3 m).
(with m glass beads) with vigorous stirring to disperse the pigment in a certain size to obtain a uniform composition.
Pigment particles are used in terms of coating film drying, leveling and defoaming properties.
It is preferably 10 to 30 μm.

The correction solution thus obtained is applied to a portion of the original film such as a silver salt film or a polyethyleneethylene terephthalate film to be masked by a suitable means such as a brush or a brush.

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, all parts mean parts by weight.

Example 1 Component Blending amount (parts) Ethyl acrylate-maleic anhydride copolymer Alkaline neutralized product 11 Red pigment (resino carmine BR, Resino Color Industry Co., Ltd.)
4 Yellow pigment (Resino Yellow GB, Resino Color Industry Co., Ltd.)
3) White pigment (Titanium White R-550, Ishihara Sangyo Co., Ltd.) 6
Ethyl alcohol 66 Silicic anhydride (Cyloid, manufactured by Fuji Devison Co., Ltd.) 9.
5 Defoaming agent (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 Ethyl acrylate-maleic anhydride copolymer Alkaline neutralized product and ethyl alcohol were mixed and stirred. Next, the pigment and other components described above were added and pre-stirred, and further vigorously stirred using a Glen Mill disperser to prepare a correction solution.
A polyethylene terephthalate film was coated with this correction solution and dried at room temperature for 1 to 3 minutes to obtain a 7 μm coating film. There was almost no odor during coating and drying, and the working environment was good. Further, the obtained coating film showed an excellent masking effect.

Example 2 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Ingredients Content (parts) Ethyl acrylate-methacrylic acid copolymer Alkaline neutralized product (Jurimer AT-210, manufactured by Nippon Pure Chemical Co., Ltd.) 11 Red pigment (Resino Carmine BR, Resino Color Industry Co., Ltd.)
4 Yellow pigment (Resino Yellow GB, Resino Color Industry Co., Ltd.)
3) White pigment (Titanium White R-550, Ishihara Sangyo Co., Ltd.) 6
Ethyl alcohol 30 Purified water 36 Silicic anhydride (Syloid, manufactured by Fuji Davisson Co., Ltd.) 9.5 Defoamer (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1. As a result of forming a coating film, the same excellent masking effect was exhibited and the working environment was also good.

Example 3 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Component Blending amount (part) Acrylic ester-acrylic acid copolymer Alkaline neutralized product 10 Black pigment (carbon black) 6 White pigment (titanium white R-550, Ishihara Sangyo Co., Ltd.) 8
Ethyl alcohol 30 Purified water 36 Silicic anhydride (Cyloid, manufactured by Fuji Devison Co., Ltd.) 9.
5 Antifoaming agent (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1 to form a coating film. The same excellent masking effect was obtained. The working environment was also good.

Example 4 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Component Blending amount (part) Vinylpyrrolidone Vinyl acetate copolymer 12 Black pigment (carbon black) 5 White pigment (titanium white R-550, Ishihara Sangyo Co., Ltd.) 4
Ethyl alcohol 30 Purified water 33.5 Silicic anhydride (Cyloid, manufactured by Fuji Devison Co., Ltd.) 15
Defoaming agent (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1 to form a coating film. The same excellent masking effect was obtained. The working environment was also good.

Example 5 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Component Blending amount (part) Polyvinylpyrrolidone 12 Black pigment (carbon black) 5 White pigment (titanium white R-550, Ishihara Sangyo Co., Ltd.) 4
Ethyl alcohol 30 Purified water 33.5 Silicic anhydride (Cyloid, manufactured by Fuji Devison Co., Ltd.) 15 Defoamer (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1. As a result of forming a coating film, the same excellent masking effect was exhibited and the working environment was also good.

Example 6 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Component Blending amount (part) Styrene-maleic anhydride copolymer Alkaline neutralized product 9 Black pigment (carbon black) 6 White pigment (titanium white R-550, manufactured by Ishihara Sangyo Co., Ltd.) 5
Ethyl alcohol 30 Purified water 34.5 Silicic anhydride (Cyloid, manufactured by Fuji Davisson Co., Ltd.) 15 Antifoaming agent (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1. As a result of forming a coating film, the same excellent masking effect was exhibited and the working environment was also good.

Example 7 A correction fluid was produced in the same manner as in Example 1 with the following components and blending amounts.

Component Mixing amount (part) Methyl vinyl ether-maleic anhydride copolymer Alkaline neutralized product 11 Black pigment (carbon black) 5 White pigment (titanium white R-550, Ishihara Sangyo Co., Ltd.) 4
Ethyl alcohol 30 Purified water 34.5 Silicic anhydride (Cyloid, manufactured by Fuji Davisson Co., Ltd.) 15 Antifoaming agent (Safinol 104, manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 The obtained correction solution was applied in the same manner as in Example 1. As a result of forming a coating film, the same excellent masking effect was exhibited and the working environment was also good.

EFFECT OF THE INVENTION The correction liquid for photoengraving of the present invention has no environmental hygiene problems, has excellent quick-drying property, and has good adhesiveness to a hydrophobic film, and has no defects such as blocking phenomenon or show-through. .

Claims (3)

[Claims] 1. (a) Alkali-neutralized product of acrylic acid ester-maleic anhydride copolymer, alkali-neutralized product of acrylic acid ester-acrylic acid copolymer, alkali of acrylic acid ester-methacrylic acid copolymer Neutralized product, vinylpyrrolidone-vinyl acetate copolymer, polyvinylpyrrolidone, alkali neutralized product of styrene-maleic anhydride copolymer, selected from the group consisting of alkali neutralized product of methyl vinyl ether-maleic anhydride copolymer. A correction liquid for photoengraving containing one or more polymers, (b) a pigment, and (c) a solvent selected from the group consisting of ethanol and a mixed solvent of ethanol and water. . 2. A correction liquid for photolithography according to item (1), which contains silicic acid anhydride. 3. The correction liquid for photolithography according to item (1), which contains one or more acetylene glycol-based and acetylene alcohol-based antifoaming agents.