JPH0934096A - Light-shielding masking film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film without causing blocking or a tacky state and showing good workability such that no dust deposits on the film and a coating film after peeled does not stick to hands due to electrification, by forming an antistatic layer containing a conductive (ion-conductive) resin on a light-shielding release layer. SOLUTION: This light-shielding masking film consists of a transparent supporting body and a light-shielding release layer, and further an antistatic layer containing a conductive (ion-conductive) resin is formed on the light- shielding release layer. It is preferable that the antistatic layer contains a matting agent. The conductive resin used for the antistatic layer is preferably a conductive acryl resin. As for the transparent supporting body, for example, a plastic film such as polyester and polypropylene can be used and the opposite surface of the film to the surface to be coated with the light-shielding release layer is subjected to antistatic treatment. It is preferable that the antistatic layer has <=10<11> Ω, more preferably <=10<9> Ω surface resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly used in photolithography to form a transparent image having a desired shape by cutting a light-shielding release layer on a support into a desired shape and removing unnecessary portions. The present invention relates to a light-shielding masking film.

[0002]

2. Description of the Related Art One of the purposes of using a light-shielding masking film is to use it for photolithography, by cutting the light-shielding release layer into the shape of the required portion and then removing the unnecessary portion of the light-shielding release layer. Various original drawings can be produced immediately. Conventionally, as the light-shielding masking film used for this purpose, a vinyl chloride resin, a vinyl chloride-based copolymer, nitrocellulose, acetyl cellulose, nitrile rubber, urethane is directly or through an adhesive release layer on a transparent support. It has been proposed to provide a light-shielding release layer containing at least one kind of rubber, acrylic rubber, etc. (JP-A-54-104902, etc.).

However, since both the plastic film as the support and the conventional light-shielding release layer have electrical insulation properties, the masking films may be separated from each other or between the masking films and other substances at the time of production or use. Films are charged by contact or friction when separating into individual films, the films block each other, dust or dirt adheres, and the film peeled by peeling electrification at the time of film peeling is in your hand There were various problems such as clinging to each other.

[0004] In order to solve such problems,
A light-shielding release layer containing an antistatic agent has been proposed (JP-A-58-108537, JP-A-61-1).
2336, JP-A-61-110141, etc.).

In the production of the light-shielding release layer containing the antistatic agent as described above, an antistatic agent which is completely compatible with the binder resin used in the light-shielding release layer, and conductive fine particles such as metal powder and carbon. When is added to the release layer as an antistatic agent, it must be added in an amount within a range capable of maintaining the stability of the release layer coating solution and the good physical properties of the release layer coating film. However, such an addition amount cannot obtain a sufficient antistatic effect, and if a large amount of an antistatic agent is added in order to obtain a sufficient antistatic effect, it becomes difficult to apply the coating liquid or light shielding is performed. Therefore, the physical properties of the coating film such as the film strength and the peeling property of the hydrophilic peeling layer are deteriorated.

When a high-molecular weight or low-molecular weight antistatic agent which is incompatible with the binder resin is used, the antistatic agent bleeds onto the surface of the light-shielding release layer, so that the surface becomes sticky, blocking, and the films adhere to each other. Problems such as deterioration of slipperiness at the time and poor adhesion to the plate-making tape occur.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is a light-shielding masking film which exhibits an antistatic effect effective in actual work, that is, dust or dirt does not adhere to the film. , The peeled film shows good workability so that it does not cling to your hands due to electrification, and at the same time it has no blocking or stickiness and has proper slipperiness, and vacuum adhesion with printer glass or photosensitive material during contact exposure. It is an object of the present invention to provide a light-shielding masking film which has good properties, has good releasability from a printer glass or a photosensitive material after exposure, and has good peeling workability.

[0008]

The present invention provides a light-shielding masking film in which a light-shielding release layer is provided on a transparent support, and a charge containing a conductive (ion conductive) resin on the light-shielding release layer. By providing an antistatic layer, it is possible to obtain a stable antistatic effect without causing problems such as deterioration of physical properties of the light-shielding release layer, and to provide a light-shielding masking film that can solve the above problems. is there.

Preferably, the antistatic layer contains a matting agent, whereby the light-shielding masking film of the present invention has vacuum adhesion to a printer glass or a photosensitive material at the time of contact exposure, and the printer glass after exposure. Further, the releasability from the light-sensitive material, the peeling workability, and the blocking prevention property are further improved.

The conductive resin used for the antistatic layer is preferably a conductive acrylic resin.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The transparent support of the light-shielding masking film of the present invention is provided to support the light-shielding release layer, and it is necessary to have transparency in order to use the light-shielding masking film as described above. Here, "transparency" means that the original has transparency to visible light such that the original can be easily visually recognized.

The transparent support is, for example, a plastic film of polyester, polypropylene, polyethylene, polystyrene, cellulose triacetate, polycarbonate or the like, which is a stretched or non-stretched film,
Examples thereof include a film whose surface opposite to the surface on which the light-shielding release layer is provided is antistatic-treated. When a roughened plastic film that has been subjected to a roughening treatment such as sandblasting or chemical treatment is used on the surface opposite to the surface on which the light-shielding release layer of the plastic film is provided, the vacuum of the film is reduced. It is effective in improving adhesion, blocking resistance and the like.

The transparent support preferably has a thickness of 25 to 250 μm.

The light-shielding release layer contains a light-shielding substance and is a layer which does not transmit light having a wavelength of about 300 to 550 nm.
It is provided on the transparent support.

The light-shielding release layer of the light-shielding masking film of the present invention may be one known in the art, and a polymer substance such as synthetic rubber or synthetic resin may be formed together with the light-shielding substance using a binder component. it can.

As the light-shielding substance, any substance can be used as long as it can block the transmission of actinic rays having the above-mentioned wavelength, but a coloring agent such as a dye or a pigment is usually used.

Examples of the polymer substance used as the binder component of the light-shielding release layer include polyester resin, acrylonitrile / butadiene rubber, acrylic rubber, ethylene / vinyl acetate rubber, urethane rubber, chloroprene rubber, polyvinyl chloride resin, vinyl chloride. / Vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / vinyl alcohol copolymer resin, vinyl chloride / vinylidene chloride copolymer resin, vinyl chloride / acryl copolymer resin, cellulose resin, acrylic resin and mixtures thereof Can be mentioned. As a concrete composition constituting the light-shielding release layer, for example, a composition comprising at least a nitrile rubber, a vinyl chloride / vinylidene chloride copolymer resin and a light-shielding substance, or at least a nitrile rubber and a vinyl chloride / vinyl acetate copolymer Examples thereof include a polymer resin and a light-shielding substance.

Further, between the transparent support and the light-shielding peeling layer, an adhesive peeling layer having tackiness capable of adhering again after peeling may be provided. By providing such an adhesive release layer, the adhesive strength of the light-shielding release layer to the transparent support can be adjusted, and even if the light-shielding release layer of a necessary portion is accidentally peeled off, that portion Can be reapplied to the transparent support.

Such an adhesive release layer should be made of, for example, natural rubber, chloroprene rubber, styrene / isoprene rubber, styrene / butadiene rubber, isoprene rubber, nitrile rubber, urethane rubber, synthetic resin adhesive or the like. The thickness is, for example, 0.01 to 10 μm, preferably 0.02 to 5 μm.

The antistatic layer of the light-shielding masking film of the present invention is provided on the light-shielding release layer and contains a conductive (ion conductive) resin. Since the conductive resin exhibits an antistatic effect by itself due to its conductivity, it is possible to avoid the deterioration of the film characteristics due to the addition of the antistatic agent and the problems due to the bleeding of the antistatic agent.

Examples of the conductive resin include conductive acrylic resin, sulfonated polystyrene, polyaniline, polypyrrole and the like. Among various conductive resins, the antistatic layer containing a conductive acrylic resin has particularly good coating properties and good adhesion to the light-shielding release layer, and shows good blocking resistance because it is not sticky and water resistant. And has sufficient antistatic effect.

The conductive acrylic resin is one in which the side-chain carboxylate portion of the acrylic resin is partially quaternized to make it ionic, and this ionic portion neutralizes static electricity and has an antistatic effect. I will get it. The conductive acrylic resin may be cationic, anionic or amphoteric.

The antistatic effect of the antistatic layer of the light-shielding masking film of the present invention can be defined by the surface resistance value of the antistatic layer formed by the above antistatic mechanism. it can. The antistatic layer of the light-shielding masking film of the present invention preferably has a surface resistance of 10 ¹¹ Ω or less, preferably 10 ⁹ Ω or less.

The acrylic resin used for the conductive acrylic resin is a long-chain thermoplastic resin obtained by polymerization or copolymerization of acrylic acid, methacrylic acid and their esters, and is generally obtained as a colorless transparent resin. To be
Specific examples of the acrylic resin include polymethylmethacrylate, methylmethacrylate / butylmethacrylate copolymer, methylmethacrylate / ethylmethacrylate copolymer and the like.

The conductive acrylic resin used in the antistatic layer of the light-shielding masking film of the present invention generally has a molecular weight of about 5,000 to 100,000, preferably about 10,000 to 80,000. When the molecular weight is 5000 or less, the film-forming property is poor, and it is generally difficult to polymerize an acrylic resin having a molecular weight of 100,000 or more.

The above-mentioned conductive acrylic resin is commercially available, for example, trade names of Elekondo PQ50B and PQA.
Elecondo series sold by 3 etc. (manufactured by Soken Chemical Industry Co., Ltd.), product name Saftomer STH89, ST2500, S
SAFTMER series (manufactured by Mitsubishi Chemical Co., Ltd.) sold under T2000H, etc., product name Julimer SP50T, SP
Julimer series (manufactured by Nihon Pure Chemical Co., Ltd.) sold under 65T, etc., trade name Sebian-A46704, 46739
Examples include Sebian-A series (manufactured by Daicel Chemical Industries, Ltd.) and the like, all of which can be preferably used in the present invention.

From the viewpoint of obtaining good blocking resistance, a conductive acrylic resin having a glass transition temperature of 50 ° C. or higher is preferable. If the temperature is lower than 50 ° C, blocking may occur when loaded in a warehouse in summer.

The thickness of the antistatic agent layer is generally 0.01.
10 to 10 μm, preferably 0.02 to 5 μm. 0.
If it is less than 01 μm, a sufficient antistatic effect cannot be obtained, and 10
If it is more than μm, the surface is likely to be cracked.

Further, the antistatic layer has a vacuum adhesion to the printer glass or the photosensitive material at the time of contact exposure, a releasability from the printer glass or the photosensitive material after the exposure, improvement of slipperiness, prevention of blocking, and surface protection. For the purpose of preventing glare, silica, alumina, inorganic matting agents such as calcium carbonate particles or silicone resin, benzoguanamine resin,
It is preferable to add an organic matting agent such as acrylic resin particles.

The average particle size of the matting agent is 0.01 to 15 μm.
m, preferably 0.02 to 10 μm. When the particle size is less than 0.01 μm, the desired effect cannot be obtained because the matting agent is too small, and when the particle size exceeds 15 μm, the particle pattern is conspicuous because the matting agent is too large, and at the same time, it is difficult to be retained in the antistatic layer. The amount of the matting agent added is preferably in the range of 0.3 to 50% by weight based on the weight of the conductive resin. Further, the antistatic layer, as long as it does not hinder the purpose of the present invention, to improve the adhesion with the light-shielding release layer, for improving the scratch resistance of the surface, polyester, polyacrylic, Acrylic / styrene copolymers, acrylonitrile / styrene copolymers, and other thermoplastic resins can be mixed, and leveling agents, defoaming agents, etc. for improving coatability can be added as necessary. it can.

The light-shielding masking film of the present invention is prepared, for example, by forming a light-shielding release layer on a transparent support optionally provided with an adhesive release layer in the same manner as in the conventional method, and then forming a light-shielding release layer on the transparent support. It can be produced by applying a solution in which a conductive resin is dissolved or dispersed in a solvent such as water or alcohol by a Meyer bar or the like and drying it to form an antistatic layer.

[0033]

The light-shielding masking film of the present invention has a sufficient antistatic effect in practical work by adopting the above-mentioned constitution, has no blocking or stickiness, has proper slipperiness, and has an original directly on the mask. It has good adhesion to the plate-making tape when it is attached, and also has good vacuum adhesion to the printer glass or photosensitive material during contact exposure, and good separation from the printer glass or photosensitive material after exposure. And exhibits good peeling workability.

[0034]

The present invention will be described in more detail based on the following examples.

Example 1 A commercially available polyester film transparent support having a light-shielding release layer formed thereon (AK Popile EE # 400AM, manufactured by Kimoto Co., Ltd.) was coated with a conductive acrylic resin (elecond). PQ50B, solid content 50%, manufactured by Soken Chemical Industry Co., Ltd.) 1.0 part by weight, isopropyl alcohol 80.0 parts by weight and water 19.0 parts by weight to prepare an antistatic layer coating solution having a dry film thickness of 0. It was coated to a thickness of 1 μm and dried to obtain the light-shielding masking film of the present invention.

Example 2 A commercially available antistatic-treated polyester film transparent support having a light-shielding release layer formed on the surface opposite to the antistatic-treated surface (AK strip coat # 400AM, manufactured by Kimoto Co., Ltd.). ) On the light-shielding release layer, a conductive acrylic resin (Sebian-A4670).
4, solid content 30%, manufactured by Daicel Chemical Industries, Ltd. 20.0 parts by weight, silica (OK-412, particle size 3 μm, manufactured by Degussa) 1.0 part by weight, and isopropyl alcohol 9.0 parts by weight The layer coating liquid was applied by a Meyer bar so that the dry film thickness was 3 μm, and dried to obtain the light-shielding masking film of the present invention.

[Example 3] A commercially available polyester film transparent support, on which an adhesive release layer and a light-shielding release layer were sequentially formed (Kimomask # 400AM, manufactured by Kimoto Co., Ltd.), a conductive acrylic resin was applied on the light-shielding release layer. Resin (Saftmar STH
89, solid content 34%, manufactured by Mitsubishi Chemical Co., Ltd.) 2.9 parts by weight and 97.1 parts by weight of isopropyl alcohol, and a dry film thickness of 0.1 μm with a Mayer bar.
It was coated so as to have a thickness of m and dried to obtain the light-shielding masking film of the present invention.

Example 4 A commercially available antistatic-treated polyester film transparent support having a light-shielding release layer formed on the surface opposite to the antistatic surface (Chimopyre # 4).
00AM, manufactured by Kimoto Co., Ltd., on the light-shielding release layer, a conductive acrylic resin (Jurimer SP50T, solid content 20%,
For antistatic layer consisting of 5.0 parts by weight of Nippon Pure Chemical Co., Ltd., 0.05 parts by weight of silicone resin powder (Tospearl 130, manufactured by Toshiba Silicone Co., Ltd.), 90.0 parts by weight of isopropyl alcohol and 4.95 parts by weight of water. The coating solution was applied by a Meyer bar so that the dry film thickness was 3 μm, and dried to obtain the light-shielding masking film of the present invention.

[Comparative Example 1] A nitrile rubber (Nippole 1432J, Nippon Zeon Co., Ltd.) was formed on the surface opposite to the antistatic surface on an antistatic treated polyester film transparent support (Dia foil O100G, manufactured by Dia foil Co., Ltd.). 6.) 3.0 parts by weight, vinyl chloride / vinyl acetate copolymer (Vinylite VYHH, Union Carbide Co.) 7.
0 parts by weight, orange dye 0.7 parts by weight, silica (OK-41
2, Degussa) 0.2 parts by weight, leveling agent (Paintad M, Dow Corning) 0.1 parts by weight, cationic low molecular weight organic antistatic agent (synthetic amine ethoxylate, ATMER163, ICIS specialty C)
chemicals) 0.4 parts by weight, methyl ethyl ketone 44.3 parts by weight and toluene 44.3 parts by weight to prepare a light-shielding release layer coating solution having a dry film thickness of 2 with a Meyer bar.
It was applied so as to have a thickness of 5 μm to obtain a light-shielding masking film.

Comparative Example 2 The same as Comparative Example 1 except that the amount of antistatic agent was changed to 0.6 part by weight, the amount of methyl ethyl ketone was changed to 44.2 parts by weight, and the amount of toluene was changed to 44.2 parts by weight. A light-shielding masking film was obtained.

The surface resistance values (Ω) on both sides of the light-shielding masking films obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were measured by a super insulation resistance tester (Yokogawa-Hewlett Pa).
(manufactured by Cckard Co., Ltd.), and the properties that affect workability when actually used and the blocking prevention property were evaluated. The results are shown in Table 1.

[0042]

[Table 1] The fluffiness of the film at the time of peeling in Table 1 is 20
When a light-shielding masking film sample having a width of 0 mm and a width of 25 mm was prepared and the light-shielding peeling layer was peeled by hand at a peeling speed similar to that during normal use, the peeled light-shielding peeling layer film was manually charged. The result of observing whether or not there is a sickle is shown.

The ash during rubbing the film was determined by rubbing the light-shielding release layer surface 10 times with a plate-making wiping cloth, and then bringing the ash of dried tobacco close to a distance of 3 cm to attach the ash to the film by charging. The results of observation are shown.

The adhesiveness to the plate-making tape is 100 μm in thickness.
m, 10 cm x 10 cm transparent polyester film was secured to the light-shielding release layer surface at four corners with a plate-making tape, and when the whole film was corrugated by hand, between the plate-making tape of the transparent film and the light-shielding release layer It was evaluated by observing whether or not "floating" occurred. The case where no floating was observed was evaluated as “good”, and the case where floating was observed was evaluated as “poor”.

All the above measurements were performed at 20 ° C. and 60%.
It was conducted in an atmosphere of RH.

The antiblocking property was evaluated at 50 ° C., 10
It is a result of a blocking promotion test when it piled up at a pressure of 50 g / cm ² for 24 hours in an atmosphere of% RH. The case where no blocking was observed was evaluated as good, and the case where blocking was observed was evaluated as bad. All samples were simultaneously placed in the same atmosphere under the above conditions to evaluate blocking.

As can be seen from the above results, the light-shielding masking films of Examples 1 to 4 have a sufficiently low surface resistance of the light-shielding peeling layer, and the film on the peeling causes electrification of the coating film, and the film is apt to wrap around the hand or rub against the film. No ashing was observed, and good results were obtained in terms of adhesion to the plate-making tape and blocking prevention.

These light-shielding masking films are free from frictional electrification and exfoliation electrification during the contacting work and the peeling work during the exposure of the printer, and are easily peeled off when they are peeled from the glass or the original film without dust. Further, since the surface has good slipperiness and is not sticky, vacuum adhesion and alignment can be easily performed. The coating strength and peeling strength of these light-shielding masking films were the same as those of the comparative examples.

[0049]

According to the present invention, the printer glass has a sufficient antistatic effect in actual work, does not have blocking or stickiness, has proper slipperiness and adhesiveness with a plate-making tape, and is used for printer glass during contact exposure. It is possible to provide a light-shielding masking film which has good vacuum adhesion to a photosensitive material or the like, and good removability from the printer glass or the photosensitive material after exposure.

Claims (4)

[Claims] 1. A light-shielding masking film having a light-shielding release layer on a transparent support, wherein an antistatic layer containing a conductive resin is provided on the light-shielding release layer. 2. The light-shielding masking film according to claim 1, wherein the antistatic layer has a surface resistance of 10 ¹¹ Ω or less. 3. The light-shielding masking film according to claim 1, wherein the antistatic layer contains a matting agent. 4. The light-shielding masking film according to claim 1, wherein the conductive resin is an acrylic resin-based conductive resin.