JP4033741B2 - Correction method of transfer protective film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for correcting a transfer protective film, and in particular, an optical recording medium that does not want to contain foreign matter such as a coating defect of an ultra-fine protective film or ultra-fine dust, and a document for photoengraving. And a method for correcting a transfer protective film used for a photomask or the like which is a document for a printed wiring board.
[0002]
[Prior art]
Conventionally, as a method for protecting the surface of an optical recording medium such as a CD-R, CD-RW, or DVD, an ultraviolet ray is formed on a recording layer of an optical recording medium (hereinafter sometimes simply referred to as “recording medium”). Means have been taken to form a protective film by applying a curable coating agent by spin coating and irradiating with ultraviolet rays. However, the protective film formed by such a method has a problem that the yield is poor due to thickness unevenness, surface non-uniformity, and the like, resulting in high cost. In order to solve such a problem, for example, using a protective film transfer sheet for an optical recording medium in which a protective layer and an adhesive layer are sequentially laminated on a peelable support, the recording layer of the recording medium is used. An example is a method of transferring a protective film (Japanese Patent Laid-Open No. 8-180461). The protective film of the protective film transfer sheet employed in such a method does not cause problems such as surface non-uniformity because the shape of the support is transferred, and also transfers a protective film with a controlled thickness. Thickness unevenness does not occur. In addition, if a protective film with uneven thickness is produced during the production of a protective film transfer sheet, the recording medium itself will not be defective unless it is transferred to the recording medium. Yield could be improved remarkably compared with the coating method.
[0003]
However, when manufacturing such a protective film transfer sheet and when transferring the protective film, it is performed in a clean environment so that no foreign matter is mixed in, but completely prevents the introduction of minute foreign substances. I can't do it. For this reason, the recording medium on which the protective film mixed with foreign matter is transferred is not correctly recorded, reproduced, erased, etc. by the optical recording / reproducing apparatus, and the recording medium itself may become a defective product.
[0004]
On the other hand, conventionally, as a method for protecting a photomask, a means of bonding to a photomask through an adhesive layer of a protective film in which an adhesive layer is laminated on a thin plastic film such as polyethylene terephthalate has been taken. Recently, however, photomasks used for photoengraving manuscripts and printed wiring boards are becoming more complex and require higher resolution, so the protective film must be thinner. Has been. However, in the protective film having the above-described structure, when the plastic film is further thinned, the workability at the time of laminating on the photomask is deteriorated, and there is a problem that wrinkles, bubbles and the like are easily generated. In order to solve such a problem, for example, a protective film transfer for a photomask formed by sequentially laminating a protective layer and an adhesive layer on a peelable support, in the same manner as a protective film transfer sheet for an optical recording medium. There is a method of transferring a protective film onto an image layer of a photomask using a sheet (Japanese Patent Laid-Open No. 2001-337443). Although the protective film of the protective film transfer sheet employed in such a method is an extremely thin, non-stiff coating, it is held by the support until it is transferred to the photomask. Does not worsen and wrinkles, bubbles, etc. are not likely to occur.
[0005]
However, such a protective film transfer sheet for a photomask, like the protective film transfer sheet for an optical recording medium, cannot completely prevent the entry of minute foreign matters. There is a problem that the photomask itself becomes a defective product.
[0006]
[Problems to be solved by the invention]
Here, it is only necessary to peel off the transferred protective film and transfer a new protective film again from an adherend such as an optical recording medium or a photomask that has become defective due to the inclusion of foreign matter by the protective film transfer sheet. However, since the protective film itself is a thin film, it is difficult to peel off the transferred protective film from the adherend, and it is impossible to reattach the entire adherend. is there.
[0007]
Therefore, the present invention provides an adherend that protects a surface by transferring a protective film using a protective film transfer sheet, and after transferring the protective film, between the transferred protective film and the adherend, It is an object of the present invention to provide a method for correcting a transfer protective film in order to prevent the adherend itself from becoming a defective product when foreign matter is confirmed in the film.
[0008]
[Means for Solving the Problems]
The method for correcting a transfer protective film of the present invention comprises transferring a protective film to an adherend using a protective film transfer sheet having a protective film provided on a peelable support, and then transferring the protective film and the adherend. Or when a foreign substance is found in the protective film, a release agent is dropped on the protective film part where the foreign substance can be confirmed to swell the protective film part, and then the swollen protective film part is removed together with the foreign substance After that, the repair film is formed by dropping a protective film repair solution onto the defect portion of the protective film.
[0009]
Further, the transfer protective film correction method of the present invention is preferably the above transfer protective film correction method. Preferably, the protective film repair solution contains an ionizing radiation curable resin, and an overlay member is applied to a portion where the protective film repair solution is dropped. A repair film is formed by placing and curing by irradiation with ionizing radiation.
[0010]
More preferably, in the above-described method for correcting a transfer protective film, after the overlay member is placed, the protective film repair solution masks the part protruding from the defective part of the protective film and is cured by irradiating with ionizing radiation. A repair film is formed, and then the protective film repair liquid that has not been cured by the mask is removed.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The transfer protective film correction method of the present invention will be described with reference to FIGS.
[0012]
In the transfer protective film correction method of the present invention, the protective film 2 is transferred to the adherend 1 using a protective film transfer sheet in which a protective film is provided on a peelable support, and then the transferred protective film 2 and the coated film are coated. When the foreign material 3 is confirmed between the substrate 1 (FIG. 1) or in the protective film 2 (FIG. 2), the release agent 4 is dropped on the protective film portion 21 where the foreign material 3 can be confirmed (FIG. 3 and FIG. 4) The protective film portion 21 is swollen (FIGS. 5 and 6), and then the swollen protective film portion 21 is removed together with the foreign matter 3 (FIG. 7). The repair film 51 is formed by dripping the liquid 5 (FIG. 8) (FIG. 9).
[0013]
Here, the protective film transfer sheet used in the present invention is obtained by providing a protective film on a peelable support. Such a protective film is composed of at least a protective layer in contact with the support, and it is preferable that an adhesive layer or the like is laminated on the protective layer as necessary.
[0014]
Here, the protective layer becomes the outermost surface after the protective film is transferred to the adherend, and at least a thermosetting resin or an ionizing radiation curable resin is used to improve the performance of the protective film such as scratch resistance and solvent resistance. It is preferable that it is formed from what is included.
[0015]
In addition, the adhesive layer provided as necessary is a layer for facilitating adhesion to the adherend, and only one protective layer provides adhesion to the adherend and scratch resistance as a protective film. It is provided when it is difficult to achieve both solvent resistance. In order to further improve performance such as scratch resistance and solvent resistance, such an adhesive layer preferably has a high hardness of the adhesive layer itself, and the adhesive layer is at least a thermosetting resin or an ionizing radiation curable type. It is preferable that it consists of what contains resin.
[0016]
Next, the support is a base material when the protective film is laminated, and has a function of transferring the thin protective film onto the adherend with good workability. In order to improve the peelability of the protective film as necessary, it is preferable to use a support subjected to a release treatment such as providing a release layer on the surface of the support.
[0017]
Next, the adherend refers to a substrate whose surface is protected by transferring a protective film using a protective film transfer sheet. Therefore, the adherend is not particularly limited as long as the protective film of the protective film transfer sheet can be transferred, but in the present invention, for example, an optical recording medium or a photomask can be used to remove minute foreign matters. It is effective for those that cause inconvenience due to mixing. In particular, when the adherend is a photomask, the foreign matter causes an exposure failure due to a minute foreign matter. Therefore, the present invention is most effective when such an adherend is used. Is.
[0018]
Here, the photomask is one in which one surface of a base material is an image layer. For example, the image layer is made of an emulsion on which an exposure pattern is formed. As such a substrate, a material having a good ultraviolet transmittance is used, and for example, glass or plastic film is preferably used.
[0019]
As a method for transferring the protective film to the adherend using such a protective film transfer sheet, for example, first, the protective film of the protective film transfer sheet is attached to the adherend. Thereafter, heating and / or ionizing radiation irradiation is performed as necessary, the protective film is cured to provide scratch resistance and solvent resistance, and after improving the adhesion to the adherend, the support is peeled off. Can be mentioned.
[0020]
Next, after the protective film 2 is transferred to the adherend 1 using the protective film transfer sheet in this way, between the transferred protective film 2 and the adherend 1 (FIG. 1), or in the protective film 2 When the foreign matter 3 is confirmed in FIG. 2, a method for correcting the transfer protective film in which the protective film portion 21 that can confirm the foreign matter 3 is removed together with the foreign matter 3 and the repair film 51 is formed on the defective portion 22 of the protective film. explain.
[0021]
First, in order to remove the protective film portion 21 where the foreign material 3 can be confirmed together with the foreign material 3, the release agent 4 is dropped (FIGS. 3 and 4) to swell the protective film portion 21 (FIGS. 5 and 6).
[0022]
Here, the stripping agent is methylene chloride, toluene, chlorotoluene, acetone, ethylene glycol alkyl ether, N-methylpyrrolidone, propylene glycol methyl ether, ethyl-3-ethoxypropinate, etc. as a stripping component, mineral spirit, methanol as a diluent solvent In order to suppress these volatile components such as butanol and alkali allyl compounds, paraffin, amine, ethylamine, sodium hydroxide and the like, polymers such as methylcellulose are mixed as a viscosity agent. The protective film part 21 is swollen by dropping it on the protective film part 21 where the foreign substance 3 can be confirmed, and the foreign substance 3 can be removed together with the protective film part 21 by rubbing with a cotton swab or the like.
[0023]
When the foreign matter 3 is confirmed between the transferred protective film 2 and the adherend 1 (FIG. 1), dust is mixed when the protective film transfer sheet is bonded to the adherend 1. Or when it is confirmed in the protective film 2 (FIG. 2), dust is mixed in the production of the protective film transfer sheet, or the protective film resin component is hardened. is there.
[0024]
The size of the foreign material varies depending on the clean environment in which the work is performed. The size of the foreign material that can be corrected in the present invention varies depending on the application and the accuracy required for the adherend, but cannot be generally stated. For example, when the adherend is a photomask, If the foreign matter is 50 μm or more and 500 μm or less, anyone can easily modify the transfer protective film without requiring any special tips. The reason why foreign matters having a major axis of about 50 μm or more is that foreign matters having a size smaller than this will not cause an exposure failure when the photomask is exposed, and thus need not be corrected. The reason why the thickness is 500 μm or less is from the viewpoint of facilitating uniform formation of a repair film 51 described later.
[0025]
As a means for dripping the release agent 4, a microdroplet needle or a capillary tube or the like is used to make a fine droplet, or a needle with a pointed tip such as a sewing needle or a safety pin (hereinafter simply referred to as “needle”). The droplets attached to the tip of the brush or the brush may be adhered to the protective film portion 21 where the foreign matter 3 can be confirmed and dropped. Since the area of the protective film portion 21 is very small in many cases, it is desirable that the inner diameter of, for example, a microsyringe needle or a capillary tube is 200 μm or less.
[0026]
As described above, when the protective film portion 21 together with the foreign matter 3 is removed from the adherend 1 by the release agent 4, a part of the protective film 2 is lost, and a defective portion 22 is generated in the protective film 2 (FIG. 7). Hereinafter, the missing part 22 of the protective film lost by the release agent 4 in this way is simply referred to as “a defective part of the protective film”.
[0027]
Here, an adhesive member such as an adhesive tape is attached to the protective film portion 21 where the foreign material 3 can be confirmed without using the release agent 4, and the foreign material is removed from the adherend together with the protective film portion by peeling off the adhesive member. However, in order to remove foreign matter by such a method, a layer of air must exist between the adherend and the protective film due to the foreign matter on the adherend. It is impossible to remove ultra-fine foreign matter that does not contain the layer. Further, according to this method, it is impossible to remove minute foreign matters mixed in advance in the protective film.
[0028]
However, according to the present invention, the protective film is removed from the adherend 1 together with the foreign matter 3 by the release agent 4, so that an extremely fine foreign matter that does not allow an air layer to enter, or a fine foreign matter that is mixed in the protective film in advance. Foreign matter can also be removed.
[0029]
Next, the repair film 51 is formed by dropping the protective film repair solution 5 on the defect portion 22 of the protective film (FIG. 8) (FIG. 9), whereby the correction of the protective film 2 can be completed.
[0030]
As the protective film repair solution used here, a solution containing at least a resin capable of forming a repair film and appropriately added with a diluting solvent or an additive can be used.
[0031]
The protective film repair solution is required to allow the formed repair film to adhere to the adherend. Here, from the viewpoint of developing adhesiveness to the adherend, the protective film repair solution contains a thermoplastic resin such as a thermoplastic polyester resin, a thermoplastic acrylic resin, or a vinyl acetate resin as a resin for forming the repair film. It is preferable.
[0032]
Moreover, it is preferable that a protective film repair liquid is what can obtain high abrasion resistance and solvent resistance as the performance of the repair film formed. That is, it is preferable that the repair film has the same performance as the protective film part adhered to the adherend. Therefore, it is preferable to include at least a thermosetting resin or an ionizing radiation curable resin in the protective film repair solution.
[0033]
As the thermosetting resin, silicone-based, melamine-based, epoxy-based, aminoalkyd-based, urethane-based, acrylic-based, polyester-based, phenol-based crosslinkable resins that can be crosslinked and cured by heat can be used. In particular, when the adherend is a photomask, an acrylic thermosetting resin having good light resistance and ultraviolet transmittance is preferably used. These can be used alone, but it is desirable to add a curing agent in order to further improve the crosslinkability and the hardness of the crosslinked cured coating film.
[0034]
As the curing agent, a compound such as polyisocyanate, amino resin, epoxy resin, carboxylic acid or the like can be appropriately used according to a suitable resin. In particular, it is desirable to use a curing agent that becomes a one-component curing reaction that causes a crosslinking reaction when heated to a certain temperature or higher without reacting at room temperature. As such a curing agent, a blocked isocyanate or the like using a method for blocking a catalyst or a functional group can be used.
[0035]
A blocked isocyanate is a compound obtained by reacting a free isocyanate group of an isocyanate group terminal precursor of a polyisocyanate with an active hydrogen group-containing compound (blocking agent) to make it inactive at room temperature, and above the temperature at which the blocking agent dissociates. When heated, the active isocyanate group is regenerated to cause a crosslinking reaction. Since such a blocked isocyanate contains an isocyanate component, particularly when the adherend is a photomask, the adhesion with the emulsion forming the image layer is improved and the durability of the protective film is improved. Can also fulfill.
[0036]
Polyisocyanate is obtained by polymerizing or copolymerizing an isocyanate monomer, and can be used without any particular limitation. Isocyanate monomers include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-diisocyanate cyclohexane, m- or p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12- And dodecamethylene diisocyanate.
[0037]
The blocking agent can be used without particular limitation, for example, phenolic, alcoholic, active methylene, mercaptan, acid amide, acid imide, lactam, imidazole, urea, oxime, Examples thereof include amines, imides, and hydrazine compounds. Specifically, phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, ethanol, diethyl malonate, ethyl acetoacetate, acetylacetone, butyl mercaptan, acetanilide, acetic acid amide, succinimide , Ε-caprolactam, imidazole, urea, thiourea, acetoaldoxime, acetone oxime, cyclohexane oxime, diphenylamine, aniline, carbazole, ethyleneimine, dimethylhydrazine and the like.
[0038]
The dissociation temperature of the blocking agent is preferably 100 ° C. or higher. By setting the temperature to 100 ° C. or higher, the block agent is not dissociated under a normal storage environment, and the preservability of the protective film repair solution can be maintained. Further, when the adherend is inferior in heat resistance like a photomask having a plastic film as a base material, the dissociation temperature of the blocking agent is preferably 120 ° C. or lower. By setting the dissociation temperature of the blocking agent to 120 ° C. or less, it is possible to prevent the precision of an adherend such as a photomask from being deteriorated due to a dimensional change due to thermal shrinkage of the plastic film.
[0039]
By using such a blocked isocyanate as a curing agent, the curing agent can be added in advance to the protective film repair solution, so that the work of forming the repair film is not complicated. Further, since the protective film repair solution does not cure unless heat exceeding the dissociation temperature of the blocking agent is applied, it is economically advantageous.
[0040]
Further, as the ionizing radiation curable resin, it is preferable to use a resin that is crosslinked and cured by irradiation with at least ionizing radiation (ultraviolet rays or electron beams). As such an ionizing radiation curable resin, one or two or more of a cationic photopolymerizable resin capable of photocationic polymerization, a photopolymerizable prepolymer or a photopolymerizable monomer capable of radical photopolymerization, and the like were mixed. Things can be used.
[0041]
Here, as the photocationic polymerizable resin, epoxy resins such as bisphenol-based epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, vinyl ether-based resins, and the like can be used.
[0042]
Examples of the photopolymerizable prepolymer include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and the like. (Meth) acrylates and the like can be used.
[0043]
Examples of the photopolymerizable monomer include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, (meth ) Butoxyethyl acrylate, butyl (meth) acrylate, methoxybutyl (meth) acrylate, phenyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethoxymethyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid lauryl, unsaturated carboxylic acid amides such as (meth) acrylamide, (meth) acrylic acid-2- (N, N-diethylamino) ethyl, (meth) acrylic acid Such as 2- (N, N-dibenzylamino) ethyl and (meth) acrylic acid-2- (N, N-diethylamino) propyl; Substituted amino alcohol esters of saturated acids, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerol tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanurate (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 3-phenoxy- Multifunctional compounds such as 2-propanoyl acrylate and 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, and trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol A polythiol compound having two or more thiol groups in a molecule such as tetrathioglycolate can be used.
[0044]
In addition, when such an ionizing radiation curable resin is used, various additives can be added to the protective film repair solution. However, when ultraviolet rays are used for curing, a photopolymerization initiator, an ultraviolet sensitizer is used. It is preferable to add an agent or the like. As this photopolymerization initiator, photo radical polymerization initiators such as acetophenones, benzophenones, Michler ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthone, onium salts, sulfonate esters, organic Examples include photocationic polymerization initiators such as metal complexes, and examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
[0045]
Further, as described above, a diluting solvent can be appropriately added to the protective film repair solution. However, the diluting solvent that can be added here is not particularly limited as long as it can dissolve the above-described resin. be able to. Specific examples include ethyl acetate, butyl acetate, toluene, xylene, methyl ethyl ketone, and the like. It is preferable to use a solvent having a low evaporation rate in order to obtain leveling properties of the protective film repair solution. As such a diluting solvent, propylene glycol monomethyl ether, xylene, butyl acetate, cyclohexanone, or the like is used.
[0046]
In addition, an additive such as a leveling agent may be added to the protective film repair solution as long as the above-described performance is not impaired.
[0047]
The various resins described above can be used alone, but several types can be mixed and used. For example, when the adherend is a photomask, by using a mixture of a thermoplastic resin and an ionizing radiation curable resin, the adhesion to the photomask is good, and the scratch resistance, solvent resistance, etc. A particularly excellent repair film can be formed.
[0048]
Next, as a means for dripping the protective film repair solution, as with the means for dripping the release agent 4 described above, a micro droplet is made and dropped using a microsyringe needle, a capillary tube, etc. This can be done by adhering a droplet attached to the brush to a defective portion of the protective film and dropping it. Note that the thickness of the repair film can be adjusted by the amount of liquid droplets.
[0049]
Further, as a means for forming a repair film from the protective film repair solution dropped on the defective portion of the protective film, when the repair liquid contains a diluted solvent, the diluted solvent is volatilized, and the repair liquid is heated. If a curable resin is included, heat the thermosetting resin to cure it, and if the repair liquid contains an ionizing radiation curable resin, apply ionizing radiation. By curing the protective film, the protective film repair solution can be coated to form a repair film.
[0050]
When forming the repair film by coating the protective film repair solution in this way, when the repair liquid dripped onto the defective portion of the protective film protrudes from the defective portion, the protective film repair that protrudes from the defective portion After removing the liquid, the thermosetting resin, the ionizing radiation curable resin, and the like can be cured.
[0051]
By removing the repair liquid that protrudes from the defective portion in this way, the repair film is not formed on the protective film to be repaired, and it is difficult to cause deterioration of light transmittance, generation of scattered light, and the like. be able to.
[0052]
Furthermore, when the protective film repair solution contains an ionizing radiation curable resin, the overlay member is placed on the protective film portion where the protective film repair solution has been dropped and cured by irradiating with ionizing radiation. It is preferable to form a repair film. Thus, the repair film excellent in flatness can be formed by placing the overlay member on the portion where the protective film repair solution is dropped.
[0053]
The size of the overlay member is not particularly limited, but when the protective film repair solution dripped onto the defective portion of the protective film is placed on the overlay member, the overlay member does not protrude from the overlay member. There is a need.
[0054]
As such an overlay member, when the ionizing radiation curable resin is an ultraviolet curable resin, a material having a high ultraviolet transmittance such as a plastic film or glass used in the above-mentioned photomask substrate is used. preferable.
[0055]
If the protective film repair solution is dropped onto the protective film part or an overlay member is placed on the protective film repair liquid in this way, the protective film repair liquid may protrude from the defective part of the protective film. It is preferable to form a repair film by masking the exposed portion and irradiate with ionizing radiation to cure, and then remove the protective film repair solution that has not been cured by the mask. After placing the overlay member, if the repair film is cured by irradiating with ionizing radiation without masking the part protruding from the protective film defect part, the protective film repair liquid is not removed by the release agent. It hardens above and cannot be removed. However, by masking the protective film repair liquid that has protruded from the defective portion of the protective film in this way, the protective film repair liquid that has not been cured by the mask can be easily removed after the repair film is formed.
[0056]
Examples of the method for masking the protruding portion include a method of applying a color so as to trace the protruding portion using a masking pen for plate making or an opaque pen for plate making on the overlay member. Here, “masking” means shielding the wavelength range of the irradiated ionizing radiation.
[0057]
In this way, as a method of removing the protective film repair liquid part that protrudes from the defective part of the protective film and the protective film repair liquid part that has not been cured by the mask, it is possible to wipe off with a cotton swab soaked with an organic solvent, etc. Can be done. In addition, as an organic solvent here, an alcohol type | system | group, a ketone type | system | group, an aromatic hydrocarbon type | system | group, an alcohol ester type | system | group, etc. can be used.
[0058]
In addition, as a means for curing the curable resin contained in the protective film repair solution, when the curable resin uses a blocked isocyanate as a curing agent, the curable resin is heated to a temperature higher than the temperature at which the blocking agent dissociates. Promotes the curing reaction of the resin. Further, when the curable resin is an ionizing radiation curable resin, it can be cured by irradiating with ionizing radiation.
[0059]
As a method of irradiating ionizing radiation (ultraviolet rays or electron beams), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, etc. are used to irradiate ultraviolet rays, Cockloft Walton type, Bandel graph. A method of irradiating an electron beam using various electron accelerators such as a type, a co-transformer type, an insulated core transformer type, a dynamitron type, and a high frequency type can be employed.
[0060]
【Example】
Examples of the present invention will be described below. “Part” and “%” are based on weight unless otherwise specified.
[0061]
[Example 1]
1. Preparation of protective film transfer sheet
A mold release layer coating liquid a having the following composition is applied to one surface of a polyethylene terephthalate film (T-600E: Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 50 μm, and dried to release a mold having a thickness of about 1 μm. A support provided with a layer was prepared.
[0062]
<Release layer coating solution a>
・ Polyvinyl methyl ether / maleic anhydride copolymer
(GANTREZ AN119: ISP) 50 copies
・ 414 parts of distilled water
・ Meta-modified alcohol 36 parts
[0063]
Next, a protective layer coating liquid b and an adhesive layer coating liquid c having the following composition are sequentially applied onto the release layer of the support and dried to thereby form a protective layer having a thickness of about 2 μm and a thickness of about 2 μm. Were laminated to form a protective film. At that time, the protective layer was dried and then cured by ultraviolet irradiation with a high-pressure mercury lamp.
[0064]
<Protective layer coating solution b>
・ Photopolymerizable prepolymer (64% solids)
(Urethane acrylate)
(Unidic V4005: Dainippon Ink and Chemicals) 50 copies
・ Photo radical polymerization initiator
(Irgacure 184: Ciba Specialty Chemicals)
・ Toluene 110 parts
[0065]
<Coating liquid c for adhesive layer>
・ Photo cationic polymerizable resin
(Bisphenol A type epoxy resin)
(Adekaoptomer KRM-2410: Asahi Denka Kogyo Co., Ltd.) 1.5 parts
・ Photo cationic polymerization initiator
(Triphenylsulfonium salt)
(Adekaoptomer SP-170: Asahi Denka Kogyo Co., Ltd.) 0.1 part
・ Acrylic adhesive resin (solid content 40%)
(SK Dyne 1102: Soken Chemical Co., Ltd.) 4 parts
・ 20 parts of ethyl acetate
・ Propylene glycol monomethyl ether 10 parts
[0066]
2. Transfer of protective film and removal of foreign matter
Using the laminator, the adhesive layer of the protective film transfer sheet obtained above is applied to the image layer on which the circuit pattern of the photomask having the circuit wiring pattern formed on the surface of the polyester film as an adherend is formed at 100 ° C. It stuck by the heated heat roll. Next, the adhesive layer was cured by irradiating ultraviolet rays with a high-pressure mercury lamp, and then the support was peeled off from the protective film, and the protective film was transferred to a photomask.
[0067]
A foreign substance having a major axis of about 100 μm, a foreign substance having a major axis of about 300 μm, and a foreign substance having a major axis of about 60 μm are found in the transferred protective film between the transferred protective film and the photomask. The agent was dropped onto the protective film part where each foreign substance could be confirmed, and the swollen protective film part was removed together with the foreign substance using a cotton swab. The release agent was dropped using a sewing needle (ordinary long needle 2: Clover).
[0068]
<Release agent d>
・ Methylene chloride 30 parts
・ Methanol 5 parts
・ 0.1 parts of paraffin
・ Hydroxybutyl methylcellulose
(Metros SM4000: Shin-Etsu Chemical Co., Ltd.) 0.3 copies
[0069]
3. Drop of protective film repair solution and formation of repair film
The protective film repair solution e having the following composition was dropped onto the portion where the protective film was lost as described above using a brush (Microswab TX730: TEXWIPE).
[0070]
<Protective film repair solution e>
・ Thermoplastic acrylic resin (solid content 40%)
(LMS-55: Mutual Chemical Industry Co., Ltd.) 6 parts
-Photopolymerizable prepolymer (100% solid content)
(Pentaerythritol triacrylate)
(KAYARAD PET-30: Nippon Kayaku Co., Ltd.) 3 parts
・ Methyl ethyl ketone 3 parts
・ Photo radical polymerization initiator
(Irgacure 184: Ciba Specialty Chemicals) 0.3 parts
[0071]
Here, after the diluted solvent in the dropped repair liquid was volatilely dried at 80 ° C. for 3 minutes, a polyester film having a thickness of 25 μm was placed as an overlay member from above, and the portion where the wet spread spread out from the defective portion of the protective film was The overlay member was colored and masked using a masking pen (Kimoto Paque P: Kimoto Co., Ltd.), irradiated with ultraviolet rays with a high-pressure mercury lamp, and the repaired solution dropped was cured to form a repair film. Next, the overlay member was peeled off, and the protective film repair solution that was not cured by the mask was wiped off with a cotton swab soaked with methyl ethyl ketone.
[0072]
[Example 2]
1. Preparation of protective film transfer sheet
The following adhesive layer coating solution f was used instead of the adhesive layer coating solution c of Example 1, and after coating and drying, the adhesive layer was cured by curing at 60 ° C. for 48 hours. A protective film transfer sheet was obtained in the same manner as in Example 1.
[0073]
<Coating liquid f for adhesive layer>
・ Thermosetting acrylic resin (solid content 50%)
(Acridic A-814: Dainippon Ink and Chemicals) 10 parts
・ Isocyanate curing agent (solid content 60%)
(Takenate D110N: Mitsui Takeda Chemical Company) 1.5 parts
・ Acrylic adhesive resin (solid content 40%)
(SK Dyne 1102: Soken Chemical Co., Ltd.) 20 copies
・ 50 parts of ethyl acetate
・ Methyl ethyl ketone 50 parts
・ Propylene glycol monomethyl ether 100 parts
[0074]
2. Transfer of protective film and removal of foreign matter
Adhering the adhesive layer of the protective film transfer sheet obtained above on the image layer of the photomask having the circuit wiring pattern formed on the surface of the glass as the adherend, using a laminator, The support was peeled from the protective film, and the protective film was transferred to a photomask.
[0075]
A foreign substance having a major axis of about 100 μm, a foreign substance having a major axis of about 300 μm, and a foreign substance having a major axis of about 60 μm are found in the transferred protective film between the transferred protective film and the photomask. The agent was dropped onto the protective film part where each foreign substance could be confirmed, and the swollen protective film part was removed together with the foreign substance using a cotton swab. The release agent was dropped using a needle in the same manner as in Example 1.
[0076]
3. Drop of protective film repair solution and formation of repair film
The protective film repair solution g having the following composition is dropped onto the portion where the protective film is lost as described above, and the portion that protrudes from the defective portion of the protective film with the dropped protective film repair solution is wiped off with a cotton swab soaked with methyl ethyl ketone. Then, the repair liquid was cured by heating at 130 ° C. for 120 minutes to dissociate the blocking agent of blocked isocyanate.
[0077]
At the time of dropping, a capillary tube (EM minicaps 0.5 micro: HIRSCHMANN LABORGERATE) having an inner diameter of about 70 μm is used, and the amount of the dropped liquid is reduced to about 0.5 μl, so that the formed repair film The thickness was about the same as the surrounding protective film.
[0078]
<Protective film repair solution g>
・ Thermoplastic acrylic resin (solid content 40%)
(LMS-55: Mutual Chemical Industry Co., Ltd.) 10 parts
・ Thermosetting acrylic resin (solid content 50%)
(Acridic A-814: Dainippon Ink and Chemicals) 10 parts
・ Block isocyanate curing agent (solid content 75%)
(Blocking agent dissociation temperature: 130 ° C.)
(Bernock DB-980K: Dainippon Ink and Chemicals) 0.9 parts
・ Methyl ethyl ketone 110 parts
・ 110 parts of propylene glycol monomethyl ether
[0079]
[Comparative Example 1]
A protective film transfer sheet was prepared in the same manner as in Example 1, and the protective film was transferred to the same adherend (photomask) as in Example 1 in the same manner as in Example 1.
[0080]
Protective film portions where two foreign substances are found between the transferred protective film and the photomask, and one foreign substance is found in the transferred protective film. An adhesive member (cellophane adhesive tape CT-405A-18: Nichiban Co., Ltd.) was rubbed with a nail and pressure-bonded, and then peeled off vigorously.
[0081]
Since the foreign matter having a major axis of about 300 μm between the transferred protective film and the photomask could be removed together with the protective film portion, the defective portion of the protective film was repaired in the same manner as in Example 1. A film was formed.
[0082]
However, the foreign matter having a major axis of about 100 μm between the transferred protective film and the photomask and the foreign matter having a major axis of about 60 μm in the transferred protective film could not be removed together with the protective film portion.
[0083]
[Comparative Example 2]
A protective film transfer sheet was prepared in the same manner as in Example 2, and the protective film was transferred to the same adherend (photomask) as in Example 2 in the same manner as in Example 2.
[0084]
Protective film portions where two foreign substances are found between the transferred protective film and the photomask, and one foreign substance is found in the transferred protective film, and foreign substances having the same size as in Example 2 can be found and the respective foreign substances can be confirmed. An adhesive member (cellophane adhesive tape CT-405A-18: Nichiban Co., Ltd.) was rubbed with a nail and pressure-bonded, and then peeled off vigorously.
[0085]
Since the foreign matter having a major axis of about 300 μm between the transferred protective film and the photomask could be removed together with the protective film portion, the defective portion of the protective film was repaired in the same manner as in Example 2. A film was formed.
[0086]
However, the foreign matter having a major axis of about 100 μm between the transferred protective film and the photomask and the foreign matter having a major axis of about 60 μm in the transferred protective film could not be removed together with the protective film portion.
[0087]
In both the first and second embodiments, relatively large foreign matters and small foreign matters between the transferred protective film and the photomask, and foreign matters in the transferred protective film can be easily removed. By dripping the protective film repair solution onto the defective portion of the film, the repair film can be formed on the defective portion of the protective film, and the protective film after transfer can be easily corrected. Further, in Example 1, the protective film repair liquid that has not been cured by the mask can be easily removed after the repair film is formed by masking the protective film repair liquid that has protruded from the defective portion of the protective film. did it.
[0088]
On the other hand, in Comparative Examples 1 and 2, both of the relatively large foreign matters between the transferred protective film and the photomask had an air layer between the adherend and the protective film due to the foreign matters. The foreign matter can be removed together with the protective film portion, and the protective film after transfer can be easily corrected in the same manner as in Examples 1 and 2. However, since the relatively small foreign matter between the transferred protective film and the photomask was an extremely fine foreign matter that did not allow the air layer to enter, the foreign matter could not be removed together with the protective film portion. Moreover, the foreign matter in the transferred protective film could not be removed.
[0089]
【The invention's effect】
According to the method for correcting a transfer protective film of the present invention, in an adherend that protects the surface by transferring the protective film using a protective film transfer sheet, after transferring the protective film, the transferred protective film and the coated film are transferred. When a foreign object is found between or in the protective film, a release agent is dropped on the protective film part where the foreign object can be confirmed to swell the protective film part. After removing the protective film, the transferred protective film can be partially corrected by dropping the protective film repair solution onto the defective part of the protective film to form a repair film. Can be prevented.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a state in which foreign matter is sandwiched between an adherend and a protective film.
FIG. 2 is a cross-sectional view showing a state where a protective film mixed with foreign matter is transferred.
FIG. 3 is a cross-sectional view showing a state where a release agent is dropped on the protective film portion where foreign matter is confirmed in FIG.
4 is a cross-sectional view showing a state in which a release agent is dropped on a protective film portion where foreign matter is confirmed in FIG. 2;
FIG. 5 is a cross-sectional view showing a state where a protective film portion in which foreign matter is confirmed in FIG. 3 is swollen by dripping of a release agent.
6 is a cross-sectional view showing a state in which the protective film portion in which foreign matter is confirmed in FIG. 4 is swollen by the dropping agent.
FIG. 7 is a cross-sectional view showing a state in which a foreign substance is removed from an adherend together with a protective film, and a defective part of the protective film is generated.
FIG. 8 is a cross-sectional view showing a state in which a protective film repair solution is dropped on a defect portion of the protective film on the adherend.
FIG. 9 is a cross-sectional view showing a state in which a repair film is formed on a defect portion of a protective film on an adherend.
[Explanation of symbols]
1 ... Adherence
2 ... Protective film
21 ... Protective film portion with foreign matter confirmed
22 ... Defects in protective film
3 ... Foreign matter
4 ... Release agent
5 .... Protective film repair solution
51 ... Repair film

Claims (4)

After transferring the protective film to the adherend using a protective film transfer sheet provided with a protective film on a peelable support, foreign matter is present between the transferred protective film and the adherend or in the protective film. In the case of confirmation, a release agent is dropped on the protective film portion where foreign matter can be confirmed to swell the protective film portion, and then the swollen protective film portion is removed together with the foreign matter, and then the protective film is applied to the defective portion of the protective film. A method for correcting a transfer protective film, wherein a repair film is formed by dripping a repair liquid. The method for correcting a transfer protective film according to claim 1, wherein the protective film repair solution contains an ionizing radiation curable resin, and an overlay member is placed on a portion where the protective film repair solution is dropped, and ionizing radiation is irradiated. A repair method for a transfer protective film, which comprises forming a repair film by curing. 3. The method for correcting a transfer protective film according to claim 2, wherein after the overlay member is placed, the portion where the protective film repair solution protrudes from the defective portion of the protective film is masked and irradiated with ionizing radiation and cured. A repair film is formed by forming a repair film, and then removing the protective film repair liquid that has not been cured by the mask. 4. The method for correcting a transfer protective film according to claim 1, wherein the protective film transfer sheet is a protective film transfer sheet for a photomask, and the adherend is a photomask. A method for correcting a transfer protective film for a photomask, which is characterized.

Images