JPS6053705B2 - Manufacturing method of light-shielding sheet - Google Patents

Description

[Detailed description of the invention] This invention relates to a method for manufacturing a light-shielding sheet.

In particular, the present invention relates to a method for producing a light-shielding sheet, which is suitable for producing a light-shielding adhesive tape or sheet that has a pressure-sensitive adhesive layer on one side of the sheet and shields a desired area from light during photolithography. Photoengraving is a process in which a colorant that blocks light at wavelengths that affect photosensitive materials is sandwiched and laminated between two transparent films, especially polyester films such as polyethylene terephthalate, and an adhesive layer is provided on one side. It is well known that adhesives are used to shield desired areas from light.

Light-shielding adhesive tapes or sheets used for such purposes are disclosed in Japanese Utility Model Publication No. 50-3557 and Japanese Patent Application Laid-Open No. 52-6994.
It is proposed in the Otoko Gazette. In these tapes or stickers, it is necessary to sufficiently adhere the polyester film serving as the base material and the light-shielding layer, and it is difficult to obtain a practical product simply by applying the light-shielding layer. The latter proposes providing a primer layer to improve the adhesion between the polyester film and the light-shielding agent layer, but this inevitably increases the number of steps and costs.

In view of this background, the inventors of the present invention have completed the present invention after extensive research in order to solve the problems of the prior art.

The purpose of the present invention is to provide an industrially advantageous method for manufacturing a light-shielding sheet with high peel strength and stable quality through simple operations. The main components are polyester (component A), an isocyanate compound (component B), and a dye that is soluble in a solvent and has light-shielding properties (component C), and the weight ratio of each component is A:
B=100: 5~7ゝ(A+B):C■100■10
-100 is formed on the activated surface of each of two polyester films, and the light-shielding coating surfaces of the two polyester films are bonded together. The present invention is described in detail below.

The polyester material for the base polyester film used in the method of the present invention is a polyester having polyethylene terephthalate or ethylene terephthalate as its main constituent unit (for example, 7()C or higher), a polyhydric alcohol other than ethylene glycol, or a polyester other than terephthalic acid. Examples include copolymers containing carboxylic acid as a comonomer, and blends thereof.

Activation treatment is applied to the surface on which the coating film is formed, so that a coating film that is difficult to peel off can be easily formed on the polyester film. This activation treatment refers to a treatment conventionally performed or known for the purpose of imparting adhesive properties by generating polar and reactive atomic groups on the surface. Examples include surface oxidation treatment by flame, corona discharge, radiation irradiation, etc. The light-shielding coating layer formed on the activated surface of the polyester film obtained as described above is a linear saturated polyester (
The active main components are component A), an isocyanate compound (component B), and a solvent-soluble dye (component C), which are dissolved in a solvent and applied to the above-mentioned activated surface.

The above-mentioned linear saturated polyester is an amorphous polyester that is soluble in a solvent, and uses terephthalic acid and other acids (for example, phthalic acid, isophthalic acid, adipic acid, and sebacic acid) as the acid component, It is obtained by using ethylene glycol and other alcohol components (for example, propylene glycol, butanediol, diethylene glycol, triethylene glycol, neopentyl glycol, etc.) as the alcohol component, and is commercially available under the trade names of Byron 20 and Byron 300 manufactured by Toyobo Co., Ltd. There is !8. As the isocyanate compound of the above B component, at least 2
Polyols such as ethylene glycol and trimethylolpropane are added to tolylene diisocyanate, triphenylmethane triisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, or these isocyanates. Can be mentioned.

The dye for the above C component may be any dye as long as it is soluble in an organic solvent and can block light at the wavelength to which the photosensitive material is sensitive, and one or more dyes may be used in combination as appropriate. used.

The above A, B, and C components are dissolved in an organic solvent to form a solution that is easy to apply. In this case, the solvent used is:
Any organic solvent may be used as long as it dissolves the above three components, and specific examples include acetone, methyl ethyl ketone, cyclohexane, benzene, toluene, xylene, ethyl acetate, butyl acetate, and tetrahydrofuran.

If necessary, a curing catalyst such as an amine catalyst such as hexamethylenetetramine, a tin catalyst such as dibutyltin dilaurate, etc., may be added to the light-shielding coating layer forming component. It is essential that the above-mentioned A, B, and C3 components be blended within a specific range.

That is, the weight ratio of component B is within the range of 5 to 75 parts per 10 m of component A, and if the amount of component B is less than 5 parts or exceeds 75 parts, the light-shielding layer and the base polyester film may be mixed. adhesion becomes insufficient. Preferably 10-6
If the length is 0 m and less than 1 mm, the adhesive force may be insufficient, and if it exceeds 60 m, the light shielding layer becomes hard and somewhat lacks flexibility. Furthermore, for 1 (1) part of the A+B component, the C component is 10
~100 parts, preferably 2
0 to mark part.

If the proportion of C component exceeds 10%, the adhesive strength between the polyester base film and the light-shielding layer will be insufficient, and if it is less than 1%, the dye concentration in the light-shielding layer will become low, and the desired light-shielding performance will not be achieved. In order to achieve this, the layer must be made excessively thick, making it undesirable as a light-shielding sheet. As described above, an organic solvent solution containing the three components A, B, and C as essential active ingredients is prepared, and this is applied to the activated surface of a polyester film using conventional means, heated, and cured. have them do it.

The production of a light-shielding sheet from this material and the structure of the obtained light-shielding sheet will be explained with reference to the accompanying drawings.

Figure 1 shows two polyester films with a light-shielding coating.
FIG. 2 is an enlarged cross-sectional view of an adhesive sheet with a pressure-sensitive adhesive layer provided on one side of the light-shielding sheet of the present invention, and FIG. 3 is an enlarged cross-sectional view of the light-shielding sheet of the present invention showing the state before lamination. FIG. 2 is an enlarged cross-sectional view of another example of a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive on one side. In the figure, 1 and 2 are polyester films, 3 and 4 are light-shielding coatings, 5 and 6 are activated surfaces of the polyester films, 7 is a pressure-sensitive adhesive layer, and 8 is an adhesive layer.

As shown in FIG. 1, two polyester films having light-shielding coatings produced as described above are laminated together so that the respective light-shielding coatings 3 and 4 are in contact with each other.

This adhesion is achieved by pressing under heat to achieve a strong bond. A pressure-sensitive adhesive coated on one side of this bonded structure is shown in FIG. Further, adhesive may be used for the above bonding, and a product in this case is shown in FIG. As the adhesive, for example, a polyurethane adhesive, a polyethylene amine adhesive, a thermosetting acrylic resin adhesive, or an ethylene-vinyl acetate adhesive is used. The material shown in Figures 2 and 3 is used as a light-shielding adhesive tape or sheet in photolithography, but a release paper is pasted on the pressure-sensitive adhesive layer 7 to prevent adhesion during storage and transportation. It is better to leave it there.

Although the light-shielding coating films 3 and 4 do not necessarily have to have the same composition, it is preferable that they have the same composition from the viewpoint of simplifying the manufacturing operation.

The light-shielding sheet produced as described above consists of coating a polyester film with a light-shielding coating layer having a specific composition and blending ratio, and then forming the light-shielding coating layer with another laminate having a similar structure. By laminating them together, they have excellent peeling resistance as seen in the examples below, and the light-shielding coating layers are stacked, so even if there is a pinhole in one layer, the overall photo There is no fear of printing defects during plate making, and a light-shielding sheet of stable quality can be obtained.

Next, examples and comparative examples of the method of the present invention will be shown.

In these examples, parts are parts by weight. Example 1 A light-shielding transparent coating liquid having the following composition was applied to the corona discharge treated side of a transparent biaxially stretched polyethylene terephthalate film with a thickness of 12 μm that had been subjected to corona discharge treatment on one side,
Curing was carried out between the two walls in an atmosphere of 12 (s) to form a coating layer having a light-shielding property and having a thickness of 2.5 μm.

The thickness of the obtained laminated film was 14.5μ. Linear saturated polyester (manufactured by Toyobo Co., Ltd., Byron 200)
15 parts Isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L solid content 75%) 15 parts Oil-soluble infrared dye (manufactured by Ciba Geigy Co., Ltd., Orazole Red 2B)
1 Oil-soluble yellow dye (manufactured by Ciba Geigy, Orazole D-2GL) 1
0m Tetrahydrofuran 18% Methyl Ethyl Ketone 20W) Next, the two laminated films obtained in the above manner were put together so that the light-shielding coating layers were in contact with each other, and passed through a laminating roll to form a light-shielding film with a transparent coating layer. Got a sheet.

The temperature of the laminating roll is about 120C. A pressure-sensitive adhesive was applied to one side of the sheet thus obtained, and a release paper was further placed thereon to obtain a light-shielding adhesive sheet. Example 2 When laminating two polyethylene terephthalate film laminates having the same light-shielding coating layers as in Example 1, a urethane adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., Takerakku A37l and A light-shielding sheet with a transparent coating layer was obtained by laminating the sheets through a laminating roll at a roll temperature of approximately 7 (s).

A pressure-sensitive adhesive was applied to one side of this sheet, and a release paper was further layered on top of the pressure-sensitive adhesive to obtain a light-shielding adhesive sheet. Example 3 A light-shielding transparent coating liquid having the following composition was applied to the corona discharge treated surface of the same polyethylene terephthalate film as in Example 1, and cured for 2 hours in an atmosphere of 120°C to a thickness of 5 μm. A light-shielding coating film was formed.

The total thickness is 17μ. Linear saturated polyester (manufactured by Toyobo Co., Ltd., Byron 300)
3C8 polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L) 6 parts red dye (manufactured by Ciba Geigy Co., Ltd., Orazole Red 2
B) 4.2m
Yellow dye (manufactured by Ciba Geigy, Orazole D-2GL)
4.? Tetrahydrofuran
n-part methyl ethyl ketone
The laminated film obtained in the above manner is
Total thickness including the light-shielding coating layer used in Example 1: 14.5
The laminated film of μ and the light-shielding coating layer were laminated together using a laminating roll having a temperature of about 7 C) to obtain a light-shielding sheet with a transparent coating layer.

A pressure-sensitive adhesive was applied to one side of this sheet, and a release paper was layered on top of it to form an adhesive light-shielding sheet.

Comparative Example 1 A light-shielding sheet was obtained in the same manner as in Example 3, except that the following composition was used as the coating layer forming composition described in the first part of Example 3.

Linear saturated polyester (manufactured by Toyobo Co., Ltd., Byron 300)
3. Polyisocyanate compound (1) Coronate L manufactured by Honpolyurethane Co., Ltd.
) 1 part red dye (manufactured by Ciba Geigy, Orazol Red 2B)
4 parts yellow dye (manufactured by Ciba Geigy, Orazole Yellow 2GL) 4 parts tetrahydrofuran n part methyl ethyl ketone 140 tff) Comparative Example 2 Except for the point that the following was used as the coating layer forming composition.
A light-shielding sheet was produced in the same manner as in Example 1 except for the above.

Linear saturated polyester (manufactured by Toyobo Co., Ltd., Byron 200)
30m polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L
) 4 red dye (manufactured by Ciba Geigy, Orazol Red 2B)
15 parts yellow dye (manufactured by Ciba Geigy, Orazole Yellow 2GL)
15 parts - Tetrahydrofuran 2
70m methyl ethyl ketone 230W
) Comparative Example 3 The following was used as a coating layer forming composition,
Except for the point where the thickness of the coating layer was 0.8μ, the rest was carried out.
A light-shielding sheet was produced in the same manner as in Example 1.

Linear saturated polyester (manufactured by Toyobo Co., Ltd., Byron 200)
3 Polyisocyanate compound (manufactured by Tamoto Polyurethane Co., Ltd., Coronate L)
15 parts = red dye (manufactured by Ciba Geigy, Orazole Red 2B)
31 parts yellow dye (manufactured by Ciba Geigy, Orazole Yellow 2GL)
31 parts Tetrahydrofuran 56 Tomethyl ethyl ketone 4B parts Peel strength of the light-shielding sheets obtained in the above examples and comparative examples and A, B and C forming the light-shielding coating layer in each example
The mixing ratio of the components is shown in the table below. Peel strength was measured according to the following method.

The light-shielding sheet in each example was tested using an Instron tensile tester at a tensile speed of 20 mm/min, with a test piece width of 25 mm and 2 (generations).
The 180-width peel strength was measured under the conditions of ×60% RH, and the average peel strength of the test piece was determined.

Looking at the above table, it can be seen that the sheets of Examples 1 to 3 produced by the method of the present invention have sufficient interlayer adhesive strength.

On the other hand, in the case of Comparative Example 1, in the composition of the light-shielding coating film on one side, the amount of component B blended relative to 100 parts of component A was too small, resulting in insufficient adhesion between the light-shielding coating layer and the polyester film. It is. In Comparative Example 2, in the composition of the light-shielding coating film, the blending amount of component B to 10 parts of component A was too large, and the adhesive force between the light-shielding coating film and the polyester film was insufficient. In Comparative Example 3, in the composition of the light-shielding coating film, the amount of C component relative to 100 m of (A+B) was too large, so the adhesive force was similarly insufficient.

The above explanations in the main text and the description of the examples are for the purpose of helping the understanding of the present invention, and the present invention is not limited by these descriptions, and other changes may be made within the gist of the invention. Examples and modifications can be taken.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an enlarged cross-sectional view illustrating a mode of implementing the method of the present invention, FIG. 2 is an enlarged cross-sectional view of an example of a light-shielding sheet obtained by the method of the present invention, and FIG. is an enlarged cross-sectional view of another example of a light-shielding sheet obtained by the method of the present invention.

Claims (1)

[Claims] 1 The main components are a linear saturated polyester (component A), an isocyanate compound (component B), and a dye that is soluble in a solvent and has light-shielding properties (component C), and each component has a weight ratio of A:B=
100:5-75, (A+B):C=100:10-1
A light-shielding property characterized by forming a light-shielding coating film within the range of 0.00 on the activated surface of each of two polyester films, and bonding the light-shielding coating surfaces of the two polyester films together. Seat manufacturing method.