JPS5845990B2 - Sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light-shielding adhesive tape or sheet.

Light-shielding adhesive tapes or sheets are used in photolithography, and the one in which a coloring agent layer capable of shielding light at wavelengths that act on photosensitive materials is sandwiched with a polyester film, and an adhesive is provided on one side, was developed in the 1970s. It is described in No. 3557.

However, according to the embodiment of this invention, the colorant layer is directly adhered to the polyester film, but the concentration of the dye and pigment in the colorant layer must be high enough to block the light rays of wavelengths that act on the photosensitive material. This generally resulted in the drawback of poor adhesion between the colorant layer and the polyester film.

The present inventors have completed the present invention as a result of intensive study on such problems.

That is, the present invention mainly comprises a mixture of a vinyline chloride copolymer having a vinylidene chloride content of at least 85% (by weight) and a polyurethane initial condensate having active isocyanate residues on the corona discharge treated surface of a polyethylene terephthalate film. A coating layer of a composition containing a composition, on which a coating layer of a composition mainly consisting of a mixture of an oil-soluble dye, a linear saturated polyester, and a polyurethane initial condensate having active incyanate residues, and a urethane adhesive on the coating layer. The present invention relates to a light-shielding adhesive tape or sheet, characterized in that it is laminated with another polyethylene terephthalate film with an agent interposed therebetween, and a transparent pressure-sensitive adhesive layer is provided on one side of the laminated layer.

Next, the present invention will be explained in detail.

As the vinylidene chloride copolymer used in the present invention, there are various known types.

That is, vinylidene chloride-acrylonitrile copolymer,
Acrylic acid,
It is a copolymer obtained by copolymerizing methacrylic acid, etc.

The vinylidene chloride content is preferably at least 85%, and if it is less than that, there are problems such as poor solvent resistance.

Vinylidene chloride homopolymer is unsuitable in terms of heat stability, weather stability, and film flexibility.

Particularly preferred are vinylidene chloride-acrylonitrile copolymer and vinylidene chloride-vinyl chloride copolymer.

The polyurethane initial condensate having active incyanate residues used in the present invention includes various known types, but a particularly preferred one is a tolylene diisocyanate-hexanetriol initial condensate (Coronate manufactured by Nippon Polyurethane). L), hexaethylene diisocyanate-hexanetriol initial condensate (Coronate HL manufactured by Nippon Polyurethane), and the like.

As the oil-soluble dye used in the present invention, it is necessary to select a color type that can block light at a wavelength to which the photosensitive material is sensitive when the product of the present invention is used in a photosensitive material.
Moreover, the color density is appropriately determined depending on the exposure time of the photosensitive material and the illuminance of the light source.

The linear saturated polyester used in the present invention includes various known types.

For example, "Ester Resin 30" manufactured by Toyobo Co., Ltd. is a linear saturated copolymerized polyester.

As the urethane adhesive, Dainippon Ink's "Barbert EPSj and its hardener Henkel rUK6000" are used.
J and its curing agent, Morton Chemical Company “Adcor”
Examples include 503Hj and its curing agent.

In the present invention, a polyurethane initial condensate having active incyanate residues is mixed in the light-shielding colorant layer, and a vinylidene chloride copolymer mixed with the same polyurethane initial condensate is further used as a primer (undercoat layer). The activated incyanate residues of the polyurethane initial condensate are subjected to corona discharge treatment to firmly adhere the oxidized surface of the polyethylene terephthalate film and the light-shielding colorant layer through a curing reaction.

The present invention has water resistance, moisture resistance,
The present invention provides a light-shielding adhesive tape or coating with greatly improved chemical resistance.

The invention will be illustrated by the following examples.

Example 1, Comparative Example 1.2 Corona discharge treatment was applied to one side of a transparent biaxially stretched polyethylene terephthalate film with a thickness of 12μ, and a primer (undercoat layer) consisting of the following composition was applied to the treated side.
was applied and cured.

Next, a light-shielding transparent ink having the following composition was applied to the primer-coated surface of the primer-coated film to form a ruby-shaped layer with a thickness of 3 μm after drying, and the total thickness was 17 mm.
A film of μ was obtained.

Next, a urethane adhesive (Morton Chemical, Atocoat 503H) was applied to a transparent biaxially stretched polyethylene terephthalate film having a thickness of 12 μm that had been treated with corona discharge, and the light-shielding transparent ink was applied to the surface coated with the urethane adhesive. A film having a total thickness of 30 microns was produced which was laminated to the surface and the ink layer was sandwiched with a transparent biaxially oriented polyethylene terephthalate film.

A product of the present invention was completed by providing a pressure-sensitive adhesive layer on one side of this film and a release coat layer on the other side.

Comparative Example 1 is the product of Example 10 of the present invention except that the primer is removed, and Comparative Example 2hL is the product of the present invention of Example 1 except that the transparent ink composition is a polyurethane initial stage containing an endogenous incyanate residue. This excludes condensates.

It will be easily understood from the following results that the products of the present invention have greatly improved water resistance and moisture resistance compared to these comparative examples.

A tape peel test is generally performed to test the adhesion between a film and a primer, or the adhesion between a light-shielding ink and a primer after a film is primed and a light-shielding ink is applied.

This test is called the "Scotch tape test" or the like.

Normal tape test: After applying a primer to a 12μ polyester film or applying a light-shielding ink to a polyester film with a primer in between, dry and fix it, then apply it under the conditions of 20℃ x 60RH% for 48 hours.
After aging, a cellophane adhesive tape was pasted onto the coated surface, and then the tape was rapidly peeled off to examine the adhesion of the coated film.

Water-resistant tape test: Primer or light-shielding ink was applied in the same way as in the normal tape test.

After the film was aged for 48 hours under the conditions of 20'q x 60RH%, it was further immersed in water at 40°C for 3 hours,
Thereafter, water droplets adhering to the surface of the sample were removed with dry paper, and immediately a cellophane adhesive tape was pasted onto the surface coated with the primer or light-shielding ink, and then the tape was rapidly peeled off.

Moisture-resistant tape test: As with the normal tape test, a 12μ polyester film coated with a fryer or light-shielding ink was aged for 48 hours at 20°C and 60% RH, and then aged at 40°C and 90% RH for 24 hours. Immediately after conditioning, a cellophane adhesive tape was pasted onto the surface coated with the primer or light-shielding ink, and then the tape was rapidly peeled off.

The evaluation of the above tape test was indicated by the following symbols.

■The primer or light-shielding ink did not fade at all and remained 100% of the tape bonded area...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・◎2,
Part of the fryer or light-shielding ink was smudged and more than 80% of the tape bonding area remained...
・・・・・・・・・・・・・・・・・・・・・
・・・−・・・03, Same as above, some peeling remained, and the area was more than 60%・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...△4, same as above, some parts were exposed and the remaining area of primer or light-shielding ink was 60% or more...
・・・・・・・・・・・・・・・・・・・・・・・・
...... In order to evaluate the bond strength, Tensilon was used without hollowing at a tensile speed of 30 cm/mvt and a chuck width of 1 inch.
Measurements were made under the conditions of 20'CX60RH% with a chuck interval of 100, and the flaking strength was expressed as the average value of these sample diagonal pieces.

The laminate film was conditioned under conditions similar to the normal tape test, water-resistant tape test, and moisture-resistant tape test, and the measured values were defined as the normal peel strength, water-resistant peel strength, and moisture-resistant peel strength, respectively.

[Brief explanation of drawings]

The drawing is a sectional view showing one embodiment of a light-shielding adhesive tape or sheet according to the present invention. 1.11...Colorless and transparent polyester film layer, 2...Transparent colorant layer, 3...Primer (undercoat layer), 4... Urethane adhesive layer, 5...pressure sensitive adhesive layer, 6... release coat therefor.

Claims (1)

[Claims] 1. A composition mainly consisting of a mixture of a vinyline chloride copolymer having a vinylidene chloride content of at least 85% (by weight) and a polyurethane initial condensate having an active incyanate residue, on the corona discharge treated surface of a polyethylene terephthalate film. a coating layer of a composition mainly consisting of a mixture of an oil-soluble dye, a linear saturated polyester, and a polyurethane initial condensate having active incyanate residues, and a urethane adhesive is interposed in the coating layer. 1. A light-shielding adhesive tape or sheet comprising: a polyethylene terephthalate film laminated thereon, and a transparent pressure-sensitive adhesive layer provided on one side of the laminated layer.