KR102030212B1 - Easily removable adhesive film and metal plate processing method - Google Patents

Abstract

The easily peelable pressure-sensitive adhesive film of the present invention is an easily peelable pressure-sensitive adhesive film whose adhesive strength is reduced by irradiation of ionizing radiation, and is formed by laminating an undercoat layer and an easily peelable pressure-sensitive adhesive layer on a transparent resin film in order. The layer contains an amine curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g, and the easily peelable pressure sensitive adhesive layer contains an ionizing radiation curable pressure sensitive adhesive. Since the undercoat layer contains an amine-based curing agent and a carboxyl group-containing resin in a specific acid value range, the easily peelable pressure-sensitive adhesive film having excellent solvent resistance while maintaining the adhesion between the base material and the undercoat layer and the adhesion between the undercoat layer and the easily peelable pressure-sensitive adhesive layer. Can be provided.

Description

Easily removable adhesive film and metal plate processing method

This invention relates to the easily peelable adhesive film used suitably as a sheet for temporarily fixing for dicing adherends, such as a silicon wafer and a glass wafer, or as a carrier sheet at the time of metal plate etching.

In order to prevent a crack at the time of processing with respect to a semiconductor capacitor, such as a ceramic capacitor, a silicon wafer, a glass wafer, etc., the adhesive film (henceforth an easily peelable adhesive film) which has a peeling property for temporary fixation is attached to a wafer. After sticking and processing the temporarily fixed wafer, such as grinding | polishing or dicing, the method of peeling from a wafer by reducing adhesive force of an adhesive film by addition of external energy, such as light or heat, is employ | adopted.

In addition, an easily peelable adhesive film is used also as a carrier sheet of metal plate etching. For example, an easily peelable adhesive film is affixed on a metal plate such as stainless steel to perform an etching process so as to have a desired shape with respect to the metal plate, and if necessary, an undercoat coating liquid is applied onto the metal plate to apply the metal plate to a target transfer object. Warriors

As such an adhesive film, the thing of patent documents 1-3 is mentioned, for example. These prior arts disclose that a peeling property can be obtained by using an ionizing radiation curable pressure-sensitive adhesive whose adhesive strength is lowered by ionizing radiation irradiation.

Japanese Patent Laid-Open No. 2-187478 Japanese Patent Publication No. 2002-343747 Japanese Patent Publication No. 2005-236082

Here, in the adhesive film as mentioned in patent documents 1-3, when apply | coating the undercoat coating liquid on a metal plate in a metal etching use as mentioned above, the solvent component in a coating liquid is scattered on an adhesive film, and the said adhesive film , The adhesion between the pressure-sensitive adhesive layer and the base material is lowered, and the peeling of the coating film of the pressure-sensitive adhesive layer occurs, so that workability such as when the metal plate is transferred to the transfer material may be lowered.

In order to prevent such peeling of a coating film, it can be considered to provide the undercoat layer which improves adhesiveness between a base material and an adhesion layer. In that case, it is preferable to use a thermosetting resin in order not to lower the adhesive force before adhesion of the ionizing radiation curable pressure sensitive adhesive used in the adhesive layer as the undercoat layer, but in the case of the thermosetting resin usually used as the undercoat layer, It was difficult to obtain an adhesive film having excellent solvent resistance while maintaining the adhesion between the undercoat layer and the undercoat layer and the adhesive layer.

In view of such circumstances, the present invention relates to an adhesive film having an undercoat layer and an easily peelable pressure-sensitive adhesive layer containing an ionizing radiation curable pressure-sensitive adhesive on a base material in order to provide adhesion between the base material and the undercoat layer, the undercoat layer, and the peeling off. It is an object to provide an easily peelable pressure-sensitive adhesive film having excellent solvent resistance while maintaining the adhesion of the pressure-sensitive adhesive layer.

The inventors of the present invention include a specific resin and a curing agent in the undercoat layer, so that the adhesiveness between the base material and the undercoat layer, the adhesion between the undercoat layer and the peelable adhesive layer can be excellent in solvent resistance. It has been found that the present invention has been reached.

That is, the easily peelable pressure-sensitive adhesive film of the present invention is obtained by laminating an undercoat layer and an easily peelable pressure-sensitive adhesive layer on a transparent resin film in sequence, and the undercoat layer has an amine curing agent and an acid value of 10 to 100 mgKOH / g. It contains carboxyl group-containing resin, and an easily peelable adhesion layer is characterized by including an ionizing radiation hardening type adhesive.

In addition, the easily peelable pressure-sensitive adhesive film of the present invention is characterized in that the easily peelable pressure-sensitive adhesive layer further comprises an isocyanate-based curing agent.

In addition, the easily peelable pressure-sensitive adhesive film of the present invention is characterized in that the ratio of the number of moles of aziridinyl groups contained in the amine-based curing agent to the number of moles of isocyanate groups contained in the isocyanate curing agent is 1.5 to 15.

In addition, the easily peelable pressure-sensitive adhesive film of the present invention is characterized in that the undercoat layer contains 3 to 30 parts by weight of the amine curing agent based on 100 parts by weight of the carboxyl group-containing resin.

In addition, the easily peelable pressure-sensitive adhesive film of the present invention is characterized in that the amine-based curing agent is a trifunctional aziridine compound.

Moreover, the processing method of the metal plate of this invention is A) the process of bonding together the surface which has an easily peelable adhesion layer of the easily peelable adhesion film of this invention to a metal plate, and B) this which adhered to a metal plate. Irradiating the peelable pressure-sensitive adhesive film with ionizing radiation to cure the peelable pressure-sensitive adhesive layer; C) forming a mask on a surface opposite to the surface having the peelable pressure-sensitive adhesive film of the metal plate, and immersing the metal plate in an etching solution to The process of removing the metal plate of the part in which the mask is not formed, and D) The process of removing a mask from a metal plate and peeling a peelable adhesive film, It is characterized by the above-mentioned. The said process B) and the process C) may precede any.

According to the easily peelable adhesive film of this invention, it can be made excellent in solvent resistance, maintaining the adhesiveness of a base material and an undercoat layer, and the adhesiveness of an undercoat layer and an easily peelable adhesive layer. Therefore, the said peelable adhesive film is used suitably as a sheet for temporarily fixing for dicing adherends, such as a silicon wafer and a glass wafer, or as a carrier sheet at the time of metal etching.

The peelable pressure-sensitive adhesive film of the present invention is obtained by laminating an undercoat layer and a peelable pressure-sensitive adhesive layer in order on a transparent resin film, wherein the undercoat layer has an amine curing agent and an acid value of 10 to 100 mgKOH / g. It contains carboxyl group-containing resin (Hereinafter, it may only be called carboxyl group-containing resin), The said peelable adhesion layer is characterized by including an ionizing radiation curable adhesive. Below, embodiment of each component of an easily peelable adhesive film is described.

Examples of the transparent resin film used in the present invention include polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polybutene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polybutadiene, polyurethane, polystyrene, Plastic films, such as a triacetyl cellulose, an acryl, a polyvinyl chloride, and a norbornene compound, are mentioned. Moreover, it is also possible to use the polymer film containing the compound which has a carboxyl group, or a laminated body of this and a general purpose polymer film as a polymer structural unit. As thickness of a transparent resin film, it is preferable to set it as 2-300 micrometers, Furthermore, it is 10-125 micrometers.

In addition, since the adhesive force of an easily peelable adhesion layer is reduced by irradiation of ionizing radiation, since the easily peelable adhesive film of this invention is mentioned later, JIS K7375: 2008 of a transparent resin film so that the fall mechanism of such an adhesive force may not be impaired. It is preferable to use a thing with a total light transmittance of 50% or more, preferably 80% or more.

Next, an undercoat layer contains an amine-type hardener and carboxyl group-containing resin whose acid value is 10-100 mgKOH / g. The amine curing agent crosslinks with the carboxyl group-containing resin in the undercoat layer to improve the solvent resistance of the undercoat layer. In addition, the carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g also reacts with an ionizing radiation curable pressure-sensitive adhesive and an isocyanate-based curing agent in an easily peelable pressure-sensitive adhesive layer described later, whereby the adhesion between the undercoat layer and the easily peelable pressure-sensitive adhesive layer is thereby obtained. It will also improve. Moreover, adhesiveness with a transparent resin film will also be improved by including the carboxyl group-containing resin whose acid value is 10-100 mgKOH / g in an undercoat layer.

Here, as an amine hardening | curing agent, alicyclic polyamines, such as aliphatic polyamines, such as ethylenediamine, diethylenetriamine, and triethylenetetramine, isophoronediamine, 1, 3-bisaminomethyl cyclohexane, diaminodiphenylmethane, diaminodi Aromatic polyamines such as phenyl sulfone, linear diamines, tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine, secondary or tertiary amines, dimer acid, diethylenetriamine, triethylenetetramine, etc. Polyamide amine, melamine, the aziridine compound which has an aziridine group (ethyleneimine) obtained by making a polyamine react, etc. can be used. Particularly suitable are aziridine compounds.

Examples of the aziridine compound include monofunctional aziridine compounds (eg, aziridine, 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2- Phenylaziridine and the like), bifunctional aziridine compounds (e.g. neopentylglycol di (β-aziridinylpropionate), 4,4'-isopropylidenediphenol di (β-aziridinylpropionate) ), 4,4'-methylenediphenol di (β-aziridinylpropionate, etc.), trifunctional aziridine compounds (e.g. tetramethylolmethane-tri- (β-aziridinylpropionate) , Trimethylolpropane tris (β-aziridinylpropionate), glyceryl tris (β-aziridinylpropionate), etc., tetrafunctional aziridine compounds (e.g. tetraaziridinylmethacrylylene Diamine, tetraaziridinylmethylparaxylenediamine, tetramethylpropanetetraaziridinylpropionate, etc.), 6 A functional aziridine compound (for example, the thing of Unexamined-Japanese-Patent No. 2003-104970) is mentioned. Among these, it is preferable to use a trifunctional aziridine compound from a viewpoint of improving the solvent resistance of an undercoat layer. The amine curing agent mentioned above can also be used individually or in combination of 2 or more types.

A carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g refers to a resin having at least one carboxyl group in a molecule, and specifically, (meth) acrylic copolymer, vinyl copolymer, polyurethane resin, polyester resin, Polycarbonate resin, polyamide resin, polyimide resin, etc. are mentioned, It is also possible to use these individually or in combination of 2 or more types. Among these, polyester resin is used suitably from the adhesive viewpoint of a transparent resin film and an undercoat layer.

Examples of the polyester resin having an acid value of 10 to 100 mgKOH / g include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyallylate, polyethylene naphthalate, and ethylene-terephthalate-isophthalate copolymer. A system resin is mentioned. These resin may be used individually by 1 type, or may be used in combination of 2 or more type (for example, as 2 or more types of mixture). The acid value of polyester-type resin becomes like this. Preferably it is 20-80 mgKOH / g.

As content ratio of carboxyl group-containing resin and amine-type hardening | curing agent whose acid value is 10-100 mgKOH / g, it is preferable to contain 3-30 weight part of amine-type hardening | curing agents with respect to 100 weight part of carboxyl group-containing resin. By containing 3 weight part or more of amine-type hardening | curing agents, the improvement of the solvent resistance of an easily peelable adhesive film and the adhesiveness of an undercoat layer and an easily peelable adhesion layer can be made more sufficient. Moreover, by containing 30 weight part or less, the fall of the storage stability of a coating material can be prevented, and the adhesiveness of an undercoat layer and a transparent resin film can be prevented from falling. The content ratio of the carboxyl group-containing resin and the amine curing agent described above is preferably 5 to 20 parts by weight.

Moreover, it is preferable to contain particle | grains in an undercoat layer. By incorporating the particles in the undercoat layer, an uneven shape is formed on the surface of the undercoat layer, and the uneven shape is entangled at the interface of the peelable adhesive layer, thereby exhibiting the effect of anchoring to the adherend. This further improves the initial adhesion to the adherend. Such particles include resin particles such as acrylic resin particles, silicone resin particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles and urethane resin particles, and silica, clay, talc, calcium carbonate, Inorganic particles such as calcium sulfate, barium sulfate, aluminum silicate, titanium oxide, synthetic zeolite, alumina, smectite and the like.

Although the particle diameter of a particle | grain is not limited, 0.3 micrometer-12 micrometers are preferable as an average particle diameter, and 0.7 micrometer-6 micrometers are more preferable. Moreover, it is preferable that it is 0.1 weight part-10 weight part with respect to 100 weight part of resin of an undercoat layer, and, as for content of particle | grains, it is more preferable that it is 0.5 weight part-5 weight part. In addition, "particle diameter" means what computed by converting the particle volume measured by the Coulter counter method into the sphere.

In addition, the undercoat layer includes crosslinking agents such as alkyl etherified aminoformaldehyde resins, polyisocyanates, block isocyanates, polyanilines, polythiophenes, polypyrroles, polyfurans, and the like within the range of not impairing the function of the present invention. Antistatic agents such as polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, antifoaming agents, anti-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments other than the above-mentioned particles, dyes It is also possible to suitably contain a lubricant and the like.

Although the thickness of an undercoat layer is not specifically limited, In order to improve the adhesiveness of a base material and an easily peelable adhesion layer, 0.2 micrometer-10 micrometers are preferable, and 0.5 micrometer-5 micrometers are more preferable.

Next, the easily peelable pressure sensitive adhesive layer contains an ionizing radiation curable pressure sensitive adhesive. The ionizing radiation curable pressure sensitive adhesive should be firmly adhered to an adherend such as a metal plate before irradiation of ionizing radiation (ultraviolet or electron beam), and after irradiation, it should not be peeled off even if immersed in the etching solution and should also prevent corrosion of the etching solution.

As an ionizing radiation curable adhesive which comprises such an easily peelable adhesion layer, it is mainly formed from an acryl-type copolymer and an ionizing radiation polymeric compound.

As an acryl-type copolymer, the homopolymer which makes the ester of acrylic acid or methacrylic acid the main structural unit, or the copolymer with acrylic acid or methacrylic acid or its ester, its acidamide, etc., and other copolymerizable comonomers, or a mixture of these polymers to be. As the monomer and the comonomer thereof, for example, alkyl esters of acrylic acid or methacrylic acid, for example methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, glycidyl ester, hydroxymethyl ester, 2- Hydroxyethyl ester, hydroxypropyl ester, the amide of acrylic acid or methacrylic acid, and N-substituted amide, For example, N-hydroxymethylacrylamide or methacrylic acid amide, etc. are mentioned.

Moreover, as an ionizing radiation polymeric compound, it is a compound containing two or more functional groups which have carbon-carbon double bonds, such as an acrylate group, in 1 molecule. This is because the acrylate group exhibits relatively high reactivity with respect to ionizing radiation, and is preferable in view of reactivity and workability, such as being able to select various acrylic pressure-sensitive adhesives. As an ionizing radiation polymeric compound which contains two or more carbon-carbon double bonds in 1 molecule, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol monohydroxy (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylic Rate, 1,6-hexanediol (meth) acrylate, neopentylglycol di (meth) acrylate, esterified product of (meth) acrylic acid and polyhydric alcohol, ester acrylate oligomer, 2-propenyl-3-butenyl An anurate, an isocyanurate, an isocyanurate compound, etc. are mentioned. These ionizing radiation polymeric compounds can be used individually or in mixture of 2 or more types.

As the compounding quantity of the ionizing radiation polymeric compound in an easily peelable adhesion layer, since it changes with kinds of the selected compound, it cannot say uniformly, For example, it is 0.5 with respect to 100 weight part of acrylic copolymers in an ionizing radiation curable adhesive. It is about -200 weight part, and especially 1-50 weight part is more preferable. When the compounding quantity of an ionizing radiation polymeric compound becomes too large with respect to the compounding quantity of an acryl-type copolymer, there exists a tendency for content of a low molecular weight substance to increase and it becomes difficult to maintain the shape and performance as an easily peelable adhesion layer. In addition, if the amount of the ionizing radiation polymerizable compound is too small relative to the amount of the acrylic copolymer, even if the ionizing radiation is irradiated, the adhesion of the easily peelable pressure-sensitive adhesive layer remains so that glue remains on the adherend such as a metal plate when peeling off the pressure-sensitive adhesive film. There is a possibility.

When the peelable adhesive layer is cured by ultraviolet irradiation as ionizing radiation, it is possible to use additives such as a photopolymerization initiator, a photopolymerization accelerator, and an ultraviolet sensitizer.

Acetophenone, benzophenone, Michler's ketone, benzoin, benzyl methyl ketal, benzoyl benzoate, (alpha)-acyl oxime ester, thioxanthone etc. are mentioned as a photoinitiator.

In addition, the photopolymerization accelerator can reduce the polymerization impairment caused by air during curing and increase the curing speed. Examples thereof include p-dimethylamino benzoic acid isoamyl ester and p-dimethylamino benzoic acid ethyl ester. Moreover, n-butylamine, triethylamine, tri- n-butylphosphine etc. are mentioned as a ultraviolet sensitizer.

Moreover, it is more preferable to contain an isocyanate type hardening | curing agent in an easily peelable adhesion layer. By containing an isocyanate-based curing agent in the easily peelable pressure-sensitive adhesive layer, the crosslinking with the ionizing radiation curable pressure-sensitive adhesive at the time of forming the easily peelable pressure-sensitive adhesive layer not only improves the coating film strength of the easily peelable pressure-sensitive adhesive layer but also crosslinks with the carboxyl group-containing resin in the undercoat layer. Therefore, the adhesiveness of an easily peelable adhesion layer and an undercoat layer will also improve.

The isocyanate-based curing agent may be a polyfunctional compound having two or more isocyanate groups, and for example, diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, 1,5-naph Aromatic diisocyanates such as thiylene diisocyanate, xylylene diisocyanate and toluylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexyl methane diisocyanate; Can be.

The content of the ionizing radiation curable pressure sensitive adhesive and the isocyanate curing agent is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation curable pressure sensitive adhesive. By containing 0.1 weight part or more of isocyanate hardening agents, adhesiveness of an undercoat layer and an easily peelable adhesion layer can be made more sufficient. Moreover, by containing 10 weight part or less, the adhesive force before ionizing radiation irradiation can be maintained.

Moreover, it is preferable that the ratio (molar ratio) of the number-of-moles of the aziridinyl group contained in the amine-type hardener in an undercoat layer with respect to the number-of-moles of the isocyanate group contained in an easily peelable adhesion layer is 1.5-15. By setting the molar ratio of the aziridinyl group to the isocyanate group in such a range, the balance between the crosslinking of the isocyanate-based curing agent and the hydroxyl group-containing resin and the crosslinking of the amine-based curing agent and the hydroxyl group-containing resin become suitable, and the solvent resistance of the undercoat layer Not only can this be particularly excellent, but also the adhesiveness of an undercoat layer and an easily peelable adhesion layer can be improved more.

Furthermore, such a peelable pressure-sensitive adhesive layer may be formed of other crosslinking agents such as alkyl etherified melamine compounds, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc.), plasticizers, and fillers. And additives such as anti-aging agents may be appropriately included.

Although the thickness of an easily peelable adhesion layer is not specifically limited, It is 5 micrometers-100 micrometers, Preferably it is 7 micrometers-50 micrometers, More preferably, 10 micrometers-30 micrometers from a viewpoint of preventing a punching process titration and the penetration of etching liquid. to be.

Moreover, in the adhesive film used by this invention, it is preferable that a separator is provided in the surface of an easily peelable adhesion layer from a viewpoint of handleability. Although it does not specifically limit as such a separator, For example, polyethylene laminate paper, polypropylene, polyethylene, polyester, polycarbonate, triacetyl cellulose, polyvinyl chloride, acryl, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride Plastic film, such as a copolymer, and the thing which performed the mold release process to one side of the said plastic film, etc. are mentioned.

Although the thickness of a separator is not specifically limited, When handling property is taken into consideration, it is 10 micrometers-250 micrometers, Preferably it is 20 micrometers-125 micrometers, More preferably, 30 micrometers-100 micrometers are used.

As a method of manufacturing the peelable adhesive film of this invention as mentioned above, the material which comprises the above-mentioned undercoat layer is mixed, for example, and it is set as the undercoat layer coating liquid, and a conventionally well-known coating method, for example, a bar After coating on a transparent resin film by a coater, a die coater, a blade coater, a spin coater, a roll coater, a gravure coater, a flow coater, a spray, screen printing, etc., it is dried as needed, and then constitutes an easily peelable adhesive layer. The materials are mixed to form an easily peelable pressure-sensitive adhesive layer coating liquid, and are similarly applied onto the undercoat layer by a conventionally known coating method, and then obtained by heating and drying as necessary. Moreover, the above-mentioned separator is bonded together to the said peelable adhesion layer as needed.

Further, for example, an undercoat layer is formed on one side of the transparent resin film in the same manner as described above, and in parallel with this to form an peelable pressure-sensitive adhesive layer in the same manner as above on the separator, and then the underside of the transparent resin film The peelable adhesive film of this invention can be obtained by bonding together the surface in which a coat layer was formed, and the surface in which the peelable adhesion layer of a separator was formed.

In addition, although the above description demonstrated an example of the manufacturing method of the easily peelable adhesive film of this invention, this invention is not limited to this, For example, an easily peelable adhesion layer, an undercoat layer, a transparent resin film on a separator You may produce by forming in order.

In addition, with respect to the method for producing an easily peelable pressure-sensitive adhesive film, a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g contained in the undercoat layer coating liquid and an isocyanate curing agent contained in the easily peelable pressure-sensitive adhesive layer coating liquid are crosslinked. From the viewpoint of providing sufficient adhesion between the undercoat layer and the easily peelable pressure-sensitive adhesive layer, the undercoat layer and the easily peelable pressure-sensitive adhesive layer are each reacted with a carboxyl group-containing resin and an amine curing agent in the undercoat layer before they are bonded. It is preferable that reaction of ionizing radiation curable resin and an isocyanate type hardening | curing agent in a peelable adhesion layer does not respectively complete.

The easily peelable adhesive film of this invention can be used as a general adhesive film. In particular, it is suitable as a carrier sheet for etching the temporarily fixed adhesive film or metal plate when processing a semiconductor material, such as glass and silicon, and can maintain the adhesiveness of a base material and an easily peelable adhesion layer at the time of processing or an etching, and Workability can be made favorable.

Below, the processing method of the metal plate which is one of the aspects of use of the easily peelable adhesive film of this invention is demonstrated. That is, the processing method of the metal plate of this invention is A) bonding a surface which has an easily peelable adhesion layer of the easily peelable adhesive film of this invention to a metal plate, B) ionizing radiation to the surface which adhered the easily peelable adhesive film. Irradiating and hardening the peelable adhesion layer, C) The mask member is bonded to the surface opposite to the surface which has the peelable adhesion film of a metal plate, and the said metal plate is immersed in etching liquid, and the mask member is not masked. The process of removing the metal plate of a part, D) The process of peeling a mask member and an easily peelable adhesive film from a metal plate is included. The easily peelable adhesion layer hardening process B) and the metal plate removal process C) may precede any.

In addition, the metal plate processing method of the present invention may further include a step of transferring the metal plate to the desired transfer material by applying the undercoat coating liquid to the metal plate E) after the metal plate removal process C). In this case, it is preferable to perform transfer process E) after peeling a mask member in process D), but before peeling an easily peelable adhesive film. In addition, the peelable adhesive layer hardening process B) may be performed after the transfer process E) before peeling off the peelable adhesive film, and is performed before or before the metal plate removing step C) or between the metal plate removing step C) and the transfer step E). You may also

The metal plate processing method of this invention is characterized by using the easily peelable adhesive film of this invention as a carrier sheet at the time of etching a metal plate, The material used by each process, and the conditions of each process are the objectives and uses of metal processing. Depending on the conventional materials and processing conditions can be adopted. For example, the mask member may be not only a sheet-like member but also a coating film of a photoresist, and the etching solution and etching conditions are appropriately changed depending on the type and thickness of the metal to be subjected.

An easily peelable pressure-sensitive adhesive film in which an undercoat layer and an easily peelable pressure-sensitive adhesive layer are laminated in order on a transparent resin film as in the present invention, wherein the carboxyl group has an amine-based curing agent and an acid value of 10 to 100 mgKOH / g in the undercoat layer. By containing a resin containing the ionizing radiation-curable pressure-sensitive adhesive in the easily peelable pressure-sensitive adhesive layer, it becomes excellent in solvent resistance when used for metal etching, for example, the coating film peeling of the peelable pressure-sensitive adhesive film It is not so good that the handleability is excellent. Therefore, it can be used suitably not only for the carrier of such metal etching, but also for processing uses, such as a semiconductor capacitor, such as a ceramic capacitor, a silicon wafer, and a glass wafer.

Example

The present invention will be described in more detail with reference to the following Examples. In addition, in this Example, "part" and "%" are a basis of weight unless there is particular notice.

1. Preparation of peelable adhesive film

Example 1

As a transparent resin film, the coating liquid for undercoat layers of the following prescription was apply | coated to one side of the polyethylene terephthalate film (Lumirror S10: Toray Corporation) of thickness 100micrometer by the bar coater method, and the undercoat layer of thickness 0.5micrometer was formed. . Subsequently, the coating liquid for peelable adhesion layer of the following prescription is apply | coated by the bar coater method on the said undercoat layer, the easily peelable adhesion layer of thickness 25micrometer is formed, the undercoat layer and the easily peelable adhesion layer are heated, Dried. Subsequently, the release process surface of the separator (thickness 25 micrometers, polyethylene naphthalate film, MRF: Mitsubishi Chemical Polyester film company) was bonded together on the said peelable adhesion layer, and the peelable adhesive film of Example 1 was produced.

<Coating liquid for undercoat layer of Example 1>

100 parts of polyester resin

(UR1700: Toyo Boseki company, acid value: 26 mgKOH / g, solid content 100%)

Amine-based curing agent 29 parts

(TAZO: Sogo medicine construction, solid 30%)

1.1 parts of particles (silicone resin particles, average particle diameter: 3 탆)

(Tospearl 130: Momentive performance materials company)

942 dilution solvents

<Coating liquid for peelable pressure-sensitive adhesive layer of Example 1>

100 parts of ionizing radiation curable pressure sensitive adhesive

(Coponyl N7271: Japanese synthetic chemical company, solid content 40%)

0.55 part isocyanate-based curing agent

(Coronate L45E: Japanese polyurethane company, solid content 45%)

Polymerization initiator 1.4 parts

(Irukacure 184: BASF company, 100% of solid content)

Diluent solvent 38 parts

Example 2

The easily peelable adhesive film of Example 2 was produced like Example 1 except the particle contained in the coating liquid for undercoat layers of Example 1.

Example 3

The easily peelable adhesive film of Example 3 was produced like Example 1 except having set the weight part of the amine-type hardener contained in the coating liquid for undercoat layers of Example 1 except particle | grains.

Example 4

The easily peelable adhesive film of Example 4 was produced like Example 1 except having set the weight part of the amine-type hardener contained in the coating liquid for undercoat layers of Example 1 except particle | grains.

In Examples 1 to 4, the molar ratios of the aziridinyl groups contained in the amine curing agent in the undercoat layer to the isocyanate group contained in the easily peelable pressure-sensitive adhesive layer are all in the range of 1.5 to 15.

Comparative Example 1

An easily peelable pressure-sensitive adhesive film of Comparative Example 1 was produced in the same manner as in Example 1 except that the amine curing agent contained in the coating liquid for undercoat layer of Example 1 was used.

Comparative Example 2

The easily peelable pressure-sensitive adhesive film of Comparative Example 2 was produced in the same manner as in Example 1 except that the coating liquid for undercoat layer of Example 1 was changed to the coating liquid for undercoat layer of the following prescription.

<Coating solution for undercoat layer of Comparative Example 2>

100 parts of polyester resin

(Crete ER20: Daisei Chemical Corporation, acid value: 2mgKOH / g, solid content 40%)

4.9 parts of isocyanate curing agent

(Takenate D110N: Mitsui Chemicals, solid content 60%)

Diluted solvent 225 parts

Comparative Example 3

The same procedure as in Comparative Example 3 was carried out in the same manner as in Comparative Example 2 except that 9 parts by weight of a bifunctional acrylate monomer (Kayarad R-167, Nippon Kayaku Co., Ltd., 100% solids) was added to the coating solution for the undercoat layer of Comparative Example 2. A peelable adhesive film was produced.

[Comparative Example 4]

The easily peelable adhesive film of the comparative example 4 was produced like Example 1 except having changed the coating liquid for undercoat layer of Example 1 into the coating liquid for undercoat layer of the following prescription.

<Coating liquid for undercoat layer of Comparative Example 4>

100 parts of polyester resin

(Bylon 200: Toyo Boseki company, acid value: 2 mgKOH / g, solid content 100%)

29 parts of amine curing agent

(TAZO: Sogo medicine construction, solid 30%)

Diluted solvent, 932 parts

2. Evaluation

(1) adhesion

Separators are peeled from the peelable pressure-sensitive adhesive films of Examples 1 to 4 and Comparative Examples 1 to 4, respectively, to expose the peelable pressure-sensitive adhesive layer, and 400 mJ / cm 2 ultraviolet rays are irradiated with a metal halide lamp from the transparent resin film side. To harden the ionizing radiation curable pressure sensitive adhesive. Then, the said peelable adhesive film was measured and evaluated based on the checkerboard tape method in JIS-K5400 1990. "(Circle)" that the one piece of the checkerboard part was not peeled off was made into "(circle)", and that which the part of the checkerboard part peeled off more than five was made into "x". Table 1 shows the measurement results.

(2) Solvent resistance (droplet evaluation)

Separators are peeled from the peelable pressure-sensitive adhesive films of Examples 1 to 4 and Comparative Examples 1 to 4, respectively, to expose the peelable pressure-sensitive adhesive layer, and 400 mJ / cm 2 ultraviolet rays are irradiated with a metal halide lamp from the transparent resin film side. To harden the ionizing radiation curable pressure sensitive adhesive. Then, several drops of toluene were dripped at the surface of this easily peelable adhesion layer. After dropping, the sample was left for 5 minutes but the peelable adhesive layer was observed and no peeling occurred at the end. The thing which peeled off at the edge part immediately after dripping "△" and what was not made into "x". Table 1 shows the measurement results.

(3) solvent resistance (rubbing evaluation)

Moreover, after hardening an ionizing radiation curable adhesive as mentioned above in parallel with (2), the said peelable adhesive layer surface was rubbed 10 round trips with the cloth which infiltrated with toluene, and the said peelable adhesive layer was observed. "(Circle)" and the thing where peeling generate | occur | produced it as "x" that the peeling did not generate | occur | produce in the edge part of the said peelable adhesion layer. The evaluation results are shown in Table 1.

As is clear from the results of Table 1, the easily peelable pressure-sensitive adhesive films of Examples 1 to 4 include an undercoat layer containing an amine-based curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g on a transparent resin film; Since it has an easily peelable adhesion layer containing an ionizing radiation hardening-type adhesive in order, the board | substrate peeling evaluation was favorable and it was excellent in the adhesiveness of a base material and an undercoat layer, and the adhesiveness of an undercoat layer and an easily peelable adhesive layer. The solvent resistance test using toluene was also excellent.

In particular, since the peelable pressure-sensitive adhesive films of Examples 1 and 2 contained 2 to 30 parts by weight of an amine-based curing agent relative to 100 parts by weight of the carboxyl group-containing resin, the undercoat layer and the easily peelable pressure-sensitive adhesive layer It was excellent in adhesiveness and solvent resistance.

In addition, compared with Example 1 and Example 2, since the undercoat layer contains particles in the easily peelable pressure-sensitive adhesive film of Example 1, the surface irregularities formed by the particles exhibit the anchoring effect to the pressure-sensitive adhesive layer It was also excellent in the adhesiveness and initial stage adhesiveness of an undercoat layer and an easily peelable adhesion layer than Example 2.

On the other hand, since the peelable pressure-sensitive adhesive film of Comparative Example 1 did not contain an amine curing agent in the undercoat layer, the adhesion between the base material and the undercoat layer and the undercoat layer and the peelable pressure-sensitive adhesive layer were inferior, and toluene It was also inferior to the solvent resistance test using.

In addition, the easily peelable pressure-sensitive adhesive film of Comparative Example 2 uses an isocyanate-based curing agent in place of the amine-based curing agent in the undercoat layer, but in Comparative Example 1, the adhesion between the base material and the undercoat layer and the undercoat layer and the easily peelable pressure-sensitive adhesive layer The adhesion could not be improved.

The easily peelable pressure-sensitive adhesive film of Comparative Example 3 uses a bifunctional acrylate monomer instead of an amine curing agent to improve the adhesion between the base material and the undercoat layer and the adhesion between the undercoat layer and the easily peelable pressure-sensitive adhesive layer. Compared with the Example which used, the adhesiveness of a base material and an undercoat layer, and the adhesiveness of an undercoat layer and an easily peelable adhesion layer were inferior, and also the solvent resistance test using toluene was inferior.

In addition, although the easily peelable adhesive film of the comparative example 4 had an amine-type hardening | curing agent and carboxyl group-containing resin, since the acid value of carboxyl group-containing resin was less than 10 mgKOH / g, the adhesiveness of an undercoat layer and an easily peelable adhesive layer was carried out. It was inferior to the solvent resistance test using toluene.

Claims (8)

As an easily peelable adhesive film in which an undercoat layer and an easily peelable adhesion layer are laminated | stacked in order on a transparent resin film,
The undercoat layer includes an amine curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g,
The peelable pressure-sensitive adhesive layer includes an ionizing radiation curable pressure sensitive adhesive and an isocyanate curing agent,
The said carboxyl group-containing resin is bridge | crosslinked by the said isocyanate type hardening | curing agent and the said amine type hardening | curing agent, The easily peelable adhesive film characterized by the above-mentioned. The method of claim 1,
The ratio of the number-of-moles of the aziridinyl group contained in the said amine-type hardener with respect to the number-of-moles of the isocyanate group contained in the said isocyanate-type hardener is 1.5-15, The easily peelable adhesive film characterized by the above-mentioned. The method according to claim 1 or 2,
The undercoat layer contains 1.98 to 3.21 parts by weight of the amine-based curing agent based on 100 parts by weight of the carboxyl group-containing resin. The method of claim 1,
The undercoat layer is an easily peelable pressure-sensitive adhesive film, characterized in that it further comprises particles. The method of claim 1,
The amine-based curing agent is a tri-functional aziridine compound, the peelable pressure-sensitive adhesive film, characterized in that. A) bonding the surface which has the easily peelable adhesion layer of the easily peelable adhesion film of Claim 1 to a metal plate,
B) a step of curing the peelable pressure-sensitive adhesive layer by irradiating ionizing radiation to the peelable pressure-sensitive adhesive film stuck to the metal plate,
C) forming a mask on the surface opposite to the surface having an easily peelable pressure-sensitive adhesive film of the metal plate, and immersing the metal plate in an etching solution to remove the metal plate of the portion where the mask is not formed;
D) The process of removing a mask from a metal plate and peeling an easily peelable adhesive film
Metal plate processing method comprising a. The method of claim 6,
The process of B) is performed after the process of C). The method according to claim 6 or 7,
After removing the mask from the metal plate in the step of D), before peeling off the peelable pressure-sensitive adhesive film,
E) A method for processing a metal plate, comprising the step of transferring the metal plate to the transfer object.