JPS5846011B2 - Light-shielding masking film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light-shielding masking film comprising a light-shielding release layer provided on a plastic support.

More specifically, the present invention relates to a light-shielding masking film having a release layer with improved light-shielding properties, film properties, aging resistance, and easy peelability.

One of the uses of the light-shielding masking film obtained in the present invention is for use in photolithography, and by peeling off the necessary portions, various original drawings can be produced immediately.

Conventionally, the materials used for the release layer of masking films used for this purpose include resins such as vinyl chloride resin, vinyl chloride copolymers, nitrocellulose, and acetylcellulose, as well as plasticizers. However, the surface of the release layer was highly sticky and the peel strength was low, making it difficult to work.

In order to improve these drawbacks, we also proposed the use of a mixed resin of polyurethane resin and cellulose acetate resin.
(Special Publication No. 5l-25478), but it is still not sufficient.

The present inventors completed the present invention as a result of intensive research on this release layer in order to improve the above-mentioned drawbacks.

In the present invention, the release layer on the plastic support is made of a rubber-like substance that has good adhesion to the plastic support, a substance that is compatible with the rubber-like substance and does not become sticky at room temperature, and a light-shielding substance. This is a light-shielding masking film characterized by coating a mixture of dyes and pigments on the plastic support.
It is flexible, has excellent removability, and has a non-sticky surface.

In addition, when cutting the necessary part, it can be easily cut,
In addition, it has good sharpness and is excellent for obtaining precise photographic objects.

The present invention will be explained in more detail below.

Examples of the plastic support used in the present invention include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyoxybenzoate, or polycarbonate films.
Stretched or unstretched films may be mentioned.

A preferred rubber-like material having good adhesion to the plastic support is 2-IJ rubber.
Examples include an acrylonitrile-butadiene copolymer or an acrylonitrile-butadiene-carboxyl group-containing monomer terpolymer having an acrylonitrile content of 19 to 51 weight percent.

Next, in the present invention, materials that are compatible with the rubbery substance and are not sticky at room temperature and are used in combination with the rubbery substance include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, nitrocellulose (nitrogen content 10.8-12.2
weight%), polystyrene resin, polyacrylate resin, polyamide resin, polyvinyl acecool resin, etc.

One of the most preferred examples of these resins is vinyl chloride-vinyl acetate copolymer, and the copolymerization ratio of vinyl chloride monomer and vinyl acetate monomer is 91 to 83:9 by weight.
A terpolymer resin having a preferable range of 17 to 17 and containing a monomer containing a carboxyl group or a hydroxyl group may also be used.

To explain the materials of the colored release layer using nitrile rubber and vinyl chloride-vinyl acetate copolymer as an example, the mixing ratio of nitrile rubber and vinyl chloride-vinyl acetate copolymer is 10:90-50: by solid weight. The ratio is preferably 20:80 to 40:60.

When the mixing ratio of nitrile rubber is less than 10:90, adhesion to the plastic support is poor and the release layer easily peels off.

On the other hand, if the ratio of nitrile rubber is greater than 50:50, the characteristics of rubber will become noticeable, the elongation of the release layer will increase, and the work will become difficult.

An example of the manufacturing method of the present invention is as follows: A substance that is compatible with nitrile rubber and IJ rubber and is non-sticky at room temperature is dissolved in an organic solvent, a coloring agent is added and mixed, and then a plastic support is prepared by a known method. Just apply it on top and let it dry.

As the coloring agent, a dye or a pigment or a mixture of a dye and a pigment can be used.
In addition, if it has good compatibility with the mixed resin with a non-sticky substance and has little change in color tone against heat and ultraviolet rays, and satisfies the light-shielding properties of a light-shielding film, the color tone and structure of the dye will be acceptable. It is not limited to.

As the solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, etc. can be used.

Benzene, toluene, xylene, etc. can be used as diluents.

Further, the light-shielding masking film of the present invention can be suitably subjected to a matte finish for the purpose of preventing light reflection from the light-shielding layer.

Matting methods include mixing inorganic powder such as silica with the material of the release layer, or overcoating the release layer with a mixture of the release layer material and inorganic powder, but it is better to overcoat with an inorganic powder. It is effective because the amount of powder used is small.

Further, when applying a top coat, a coloring agent may or may not be used.

The amount of inorganic powder such as silica added for the matting process is preferably 30 to 60 parts by weight based on 100 parts by weight of the resin solid content, regardless of which method is used.

Next, the present invention will be specifically explained using examples.

Examples 1 to 7 and Comparative Examples 1 to 4 Biaxially stretched polyethylene terephthalate film,
Acrylonitrile (
, AN) with a content of 33% by weight of acrylonitrile-butadiene rubber (NBR; and a substance that is compatible with it and is non-sticky at room temperature: vinyl chloride/vinyl acetate/maleic acid (Vc/VAc/MA) = 86/ A mixture with a terpolymer of 13/1 (weight ratio) was dissolved in methyl ethyl ketone/toluene (MEK/TOL) = 2/1 (weight ratio), and a light-shielding dye Neozapon Red manufactured by BASF was added. A coating solution was prepared by mixing a dye mixture of 3 parts by weight of GE and 1 part by weight of Neozapon Orange GEL.

The blending ratio of each of the above components is as shown in Table 1.

The coating solution was applied using a roll coater onto a biaxially oriented polyethylene terephthalate film having a thickness of 100 .mu.m, and dried in an oven for 1 minute to obtain a ruby-colored transparent film having a thickness of 125 .mu.m.

As a result of measuring the light transmittance of the film using a spectrophotometer, it was found that the film did not transmit light of 220 to 560 nanometers, and had good light-shielding properties.

Furthermore, the film surface of the example was not sticky, and the film base and coating film had appropriate peel strength.

Comparative Examples 2 and 3, in which the peel strength (max, There wasn't.

As seen in Examples 1 to 7, it is found that the peel strength can be adjusted by changing the blending ratio of the resins.

The results of Examples 1 to 7 and Comparative Examples 1 to 4 are summarized in Table 1.

The peeling type was classified into type A (Figure 1) and type B (Figure 2) based on the peeling behavior measured using Autograph 5I2000 (manufactured by Shimabara Seisakusho).

The same classification was performed in the examples described below.

Examples 8 to 16 NBRs with different AN contents that adhere well to biaxially stretched polyethylene terephthalate films and those with different compositions of vinyl chloride resins that are compatible with them and are non-sticky at room temperature. and BA as a dye.
Examples 1 to 7 using SF Neozapon Orange RE
The coating solution was prepared in the same manner as above.

The coating solution was applied onto a biaxially stretched polyethylene terephthalate film having a thickness of 125μ, and the total thickness was 150μ.
An amber transparent film was obtained.

The compounding ratio of the coating liquids and the properties of the coated films of Examples 8 to 16 are summarized in Table 2.
All had good light-shielding properties, with no light rays of 0 to 520 nanometers passing through.

Example 17 133 parts by weight of NBR with an acrylonitrile content of 33% by weight was used as a rubber component that adhered well to a biaxially stretched polyethylene terephthalate film, and nitrocellulose R was used as a substance that was compatible with this and did not become sticky at room temperature.
S”A25ec167 heavy’ MEK of mixture with M part
A mixture of 3 parts of Varifast Red manufactured by Orient Chemical Co., Ltd., which is a light-blocking dye, and 1 part of Varifast Orange was added to a solution of /TOL (2/1) per 100 parts by weight of the resin content of the above solution. A coating solution was prepared by mixing 14 parts by weight.

The coating solution was coated on a biaxially stretched polyethylene terephthalate film having a thickness of 125 μm, and after drying, the entire film had a thickness of 15 μm.
A ruby-colored transparent film of 0 μm was obtained.

The ruby-colored film was a non-tacky, peelable film that did not transmit light rays of 220 to 590 nanometers, but could transmit light rays of wavelengths greater than 590 nanometers.

The peeling type is B type, and the peeling strength is 3051/251.
It was n11L.

Examples 18-19 In place of nitrocellulose in the string of Example 17,
Acrylonitrile/styrene (AN/ST) copolymers were used, and the blending ratios were varied as shown in Table 3.

Example 20 The composition of Example 17 was the same as Example 1 except that polyacrylic ester was used instead of nitrocellulose and the blending ratio of NBR and polyacrylic ester was 1:1.
A coating solution similar to that in Example 7 was prepared.

The peeling was of type B, and the peeling strength was 400 P725 mm.

Example 21 A lacquer containing 35 parts by weight of hydrated silica powder mixed with 100 parts by weight of the solid content of the coating liquid in place of the dye in the coating liquid in Example 4 was further applied on the coated surface of Example 4, A ruby-colored film having a total diameter of 128 μm and a transparent appearance with no surface gloss was obtained.

Before cutting the peeling line with a knife on the surface of the film,
It has been found that writing can be done in advance with a writing instrument such as a pencil or ballpoint pen, and even when photographed with a plate-making camera, no halation occurs, making it possible to work with reflected light.

It was also found that the film had the same peeling behavior as Example 4.

Example 22 The coating solution of Example 4 was applied to a polyethylene terephthalate film having a thickness of 125 μm to obtain a ruby-colored film having a total thickness of 140 μm.

A solution obtained by adding 40 parts by weight of hydrated silica powder (Syroid 244 manufactured by Fuji Davison ■) to the coating solution of Example 4 based on 100 parts by weight of the solid content of the coating solution was further applied onto the coating surface. A ruby-colored peelable film having a total size of 153 μm was obtained.

It was found that the film of this example also had the same writability and antihalation properties as Example 21.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing the peeling behavior of type A. FIG. 2 is a drawing showing the peeling behavior of type B.

Claims (1)

[Claims] 1 A resin selected from (1) nitrile rubber, (2) vinyl chloride resin, nitrocellulose, polystyrene resin, polyacrylate resin, polyamide resin, and polyacetal resin mixed in solution on a plastic film support. and (
3) A light-shielding masking film comprising a release layer made of a three-component mixture of light-shielding dyes and pigments.