JPWO2013146617A1 - Easy peelable 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 with ionizing radiation, and an undercoat layer and an easily peelable pressure-sensitive adhesive layer are sequentially laminated 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, and the easily peelable adhesive layer includes an ionizing radiation curable adhesive. The undercoat layer contains an amine-based curing agent and a carboxyl group-containing resin with a specific acid value range to maintain the adhesion between the substrate and the undercoat layer and the adhesion between the undercoat layer and the easily peelable adhesive layer. However, it is possible to provide an easily peelable pressure-sensitive adhesive film that is also excellent in solvent resistance.

Description

  The present invention relates to an easily peelable adhesive film preferably used as a temporary fixing sheet for dicing an adherend such as a silicon wafer or a glass wafer, or as a carrier sheet for etching a metal plate.

  In order to prevent cracking during processing of semiconductor materials such as ceramic capacitors, silicon wafers, and glass wafers, an adhesive film having an easy peelability (hereinafter referred to as an easily peelable adhesive film) is attached to the wafer for temporary fixing. A method is adopted in which a wafer that is attached and temporarily fixed is subjected to processing such as polishing or dicing, and then the adhesive film is peeled off by reducing the adhesive force of the adhesive film by applying external energy such as light or heat.

  Moreover, an easily peelable adhesive film is also used as a carrier sheet for etching a metal plate. For example, an easily peelable adhesive film is affixed to a metal plate such as stainless steel, an etching process is applied to the metal plate so as to have a desired shape, and an undercoat coating solution is applied onto the metal plate as necessary. Transfer the plate to the desired transfer.

  Examples of such an adhesive film include those described in Patent Documents 1 to 3. These prior arts disclose that releasability can be obtained by using an ionizing radiation curable pressure-sensitive adhesive whose adhesive strength is reduced by irradiation with ionizing radiation in the adhesive layer.

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

  Here, in the adhesive film as described in Patent Documents 1 to 3, when applying the undercoat coating liquid on the metal plate in the metal etching application as described above, the solvent component in the coating liquid is on the adhesive film. The adhesive film splatters and erodes the adhesive film, resulting in a decrease in the adhesion between the adhesive layer and the base material, resulting in the peeling of the adhesive layer and the workability when transferring the metal plate to the transferred material may be reduced. is there.

  In order to prevent such peeling of the coating film, it is conceivable to provide an undercoat layer that enhances adhesion between the substrate and the adhesive layer. In that case, as the undercoat layer, it is preferable to use a thermosetting resin so as not to decrease the adhesive strength before adhesion of the ionizing radiation curable pressure-sensitive adhesive used in the adhesive layer, but it is usually used as an undercoat layer. In the thermosetting resin, it is difficult to obtain an adhesive film excellent in solvent resistance while maintaining the adhesion between the base material and the undercoat layer, and between the undercoat layer and the adhesive layer.

  In view of such circumstances, the present invention relates to a pressure-sensitive adhesive film having an undercoat layer and an easily peelable pressure-sensitive adhesive layer containing an ionizing radiation curable pressure-sensitive adhesive in order on the base material, the adhesion between the base material and the undercoat layer, It aims at providing the easily peelable adhesive film which is excellent also in solvent resistance, maintaining the adhesiveness of a drawing layer and an easily peelable adhesive layer.

  In order to solve such problems, the inventor includes a specific resin and a curing agent in the undercoat layer, so that the adhesion between the base material and the undercoat layer and the adhesion between the undercoat layer and the easily peelable adhesive layer are reduced. It has been found that it can be excellent in solvent resistance while maintaining the properties, and has led to the present invention.

  That is, the easily peelable adhesive film of the present invention is formed by laminating an undercoat layer and an easily peelable adhesive layer in order on a transparent resin film, and the undercoat layer comprises an amine-based curing agent and an acid value. Includes 10 to 100 mg KOH / g of a carboxyl group-containing resin, and the easily peelable adhesive layer includes an ionizing radiation curable adhesive.

  In the easily peelable pressure-sensitive adhesive film of the present invention, preferably, the easily peelable pressure-sensitive adhesive layer further contains an isocyanate curing agent.

  In the easily peelable pressure-sensitive adhesive film of the present invention, the ratio of the number of moles of the aziridinyl group contained in the amine-based curing agent to the number of moles of the isocyanate group contained in the isocyanate-based curing agent is preferably 1.5 to 15. It is characterized by this.

  Moreover, the easily peelable adhesive film of the present invention is preferably characterized in that the undercoat layer contains 3 to 30 parts by weight of the amine curing agent with respect to 100 parts by weight of the carboxyl group-containing resin. .

  The easily peelable adhesive film of the present invention is preferably characterized in that the amine curing agent is a trifunctional aziridine compound.

  Moreover, the processing method of the metal plate of this invention is A) The process of bonding the surface which has the easily peelable adhesion layer of the easily peelable adhesive film of this invention to a metal plate, B) The easy peelability stuck to the metal plate. A process of irradiating the adhesive film with ionizing radiation and curing the easily peelable adhesive layer, C) forming a mask on the surface of the metal plate opposite to the surface having the easily peelable adhesive film, and immersing the metal plate in an etching solution A step of removing the metal plate in a portion where the mask is not formed, and D) a step of removing the mask from the metal plate and peeling off the easily peelable adhesive film. Either step B) or step C) may precede.

  According to the easily peelable pressure-sensitive adhesive film of the present invention, 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, it is excellent in solvent resistance. Can do. Therefore, the easily peelable adhesive film is suitably used as a temporary fixing sheet for dicing an adherend such as a silicon wafer or a glass wafer, or as a carrier sheet during metal etching.

  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 in order on a transparent resin film, and the undercoat layer comprises an amine-based curing agent and an acid. A carboxyl group-containing resin having a valence of 10 to 100 mg KOH / g (hereinafter sometimes simply referred to as a carboxyl group-containing resin) is included, and the easily peelable adhesive layer contains an ionizing radiation curable adhesive. It is. Hereinafter, embodiments of each component of the easily peelable pressure-sensitive adhesive film will be 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, triacetyl cellulose, acrylic, polyvinyl chloride. And plastic films such as norbornene compounds. Moreover, the polymer film containing the compound which has a carboxyl group as a polymer structural unit, or the laminated body of this and a general purpose polymer film can also be used. The thickness of the transparent resin film is preferably 2 to 300 μm, and more preferably 10 to 125 μm.

  In addition, since the adhesive force of the easily peelable adhesive layer is reduced by irradiation with ionizing radiation as described later, the easily peelable adhesive film of the present invention is transparent so that the mechanism for reducing the adhesive force is not hindered. It is preferable to use a resin film having a total light transmittance of 50% or more, preferably 80% or more based on JIS K7375: 2008.

  Next, the undercoat layer contains an amine curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g. The amine-based curing agent is crosslinked with the carboxyl group-containing resin in the undercoat layer to improve the solvent resistance of the undercoat layer. Further, the carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g also reacts with an ionizing radiation curable adhesive and an isocyanate-based curing agent in the easily peelable adhesive layer described later, whereby the undercoat layer and the easily peelable adhesive layer. This also improves the adhesion. Moreover, adhesiveness with a transparent resin film will also be improved by including carboxyl group-containing resin whose acid value is 10-100 mgKOH / g in an undercoat layer.

  Here, examples of the amine-based curing agent include aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, alicyclic polyamines such as isophoronediamine and 1,3-bisaminomethylcyclohexane, and aromatics such as diaminodiphenylmethane and diaminodiphenylsulfone. Polyamines, linear diamines, tetramethylguanidine, triethanolamine, piperidine, pyridine, secondary amines such as benzyldimethylamine or tertiary amines, dimer acid and polyamines such as diethylenetriamine and triethylenetetramine The aziridine compound having a polyamidoamine, melamine, or aziridine group (ethyleneimine) obtained in the above can be used. An aziridine compound is particularly preferable.

  Examples of the aziridine compound include monofunctional aziridine compounds (for example, aziridine, 2-methylaziridine, 2-ethylaziridine, 2,2-dimethylaziridine, 2,3-dimethylaziridine, 2-phenylaziridine, etc.), bifunctional aziridine compounds (E.g., neopentyl glycol di (β-aziridinylpropionate), 4,4′-isopropylidenediphenoldi (β-aziridinylpropionate), 4,4′-methylenediphenoldi (β -Aziridinylpropionate), etc.), trifunctional aziridine compounds (eg, tetramethylolmethane-tri- (β-aziridinylpropionate), trimethylolpropane tris (β-aziridinylpropionate), Glyceryl tris (β-aziridinyl propionate), etc., tetrafunctional Dilysine compounds (for example, tetraaziridinyl metaxylenediamine, tetraaziridinylmethylparaxylenediamine, tetramethylpropanetetraaziridinylpropionate, etc.), hexafunctional aziridine compounds (for example, described in JP-A No. 2003-104970) For example). Among these, a trifunctional aziridine compound is preferably used from the viewpoint of improving the solvent resistance of the undercoat layer. The above-mentioned amine curing agents can be used alone or in combination of two or more.

  The 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 the molecule, specifically, a (meth) acrylic copolymer, a vinyl copolymer. A coalescence, a polyurethane-based resin, a polyester-based resin, a polycarbonate-based resin, a polyamide resin, a polyimide resin, and the like can be given. These can be used alone or in combination of two or more. Among these, from the viewpoint of adhesion between the transparent resin film and the undercoat layer, a polyester resin is preferably used.

  Examples of the polyester resin having an acid value of 10 to 100 mgKOH / g include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyethylene naphthalate, and ethylene-terephthalate-isophthalate copolymer. These resins may be used alone or in combination of two or more (for example, as a mixture of two or more). The acid value of the polyester resin is preferably 20 to 80 mgKOH / g.

  The content ratio of the carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g and the amine curing agent is preferably 3 to 30 parts by weight of the amine curing agent with respect to 100 parts by weight of the carboxyl group-containing resin. . By containing 3 parts by weight or more of the amine curing agent, the solvent resistance of the easily peelable adhesive film can be improved and the adhesion between the undercoat layer and the easily peelable adhesive layer can be made more satisfactory. . Moreover, by containing 30 weight part or less, it can prevent that the storage stability of a coating material falls and can prevent that the adhesiveness of an undercoat layer and a transparent resin film falls. The content ratio of the above-described carboxyl group-containing resin and amine curing agent is preferably 5 to 20 parts by weight.

  The undercoat layer preferably contains particles. By incorporating particles in the undercoat layer, an uneven shape is formed on the surface of the undercoat layer, and the uneven shape enters the interface of the easily peelable adhesive layer and exhibits an anchoring effect on the adherend. Become. Thereby, the initial adhesive force to the adherend is further improved. Examples of 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, urethane resin particles, silica, clay , Inorganic particles such as talc, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, titanium oxide, synthetic zeolite, alumina, and smectite.

  Although the particle diameter of particle | grains is not limited, 0.3 micrometer-12 micrometers are preferable at an average particle diameter, and 0.7 micrometer-6 micrometers are more preferable. Further, the content of the particles is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin of the undercoat layer. The “particle diameter” refers to a value calculated by converting a particle volume measured by the Coulter counter method into a sphere.

  In addition, the undercoat layer has a crosslinking agent such as an alkyl etherified aminoformaldehyde resin, polyisocyanates, block isocyanates, polyanilines, polythiophenes, polypyrroles, polyfurans, as long as the function of the present invention is not impaired. Anti-static agents such as polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyacenes polythiophene vinylenes, antifoaming agents, anti-slip agents, antiseptics, rust inhibitors, pH adjusters, antioxidants, pigments other than those mentioned above, Dyes, lubricants, and the like can be included as appropriate.

  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 is firmly attached to an adherend such as a metal plate before irradiation with ionizing radiation (ultraviolet light or electron beam), and does not peel off even if immersed in an etching solution after irradiation. It must prevent erosion of the etchant.

  The ionizing radiation curable pressure-sensitive adhesive constituting such an easily peelable pressure-sensitive adhesive layer is mainly formed from an acrylic copolymer and an ionizing radiation polymerizable compound.

  Acrylic copolymers include homopolymers mainly composed of esters of acrylic acid or methacrylic acid, acrylic acid or methacrylic acid or esters thereof or acid amides thereof, and other copolymerizable comonomers. It is a copolymer or a mixture of these polymers. Examples of the monomers and comonomers thereof include alkyl esters of acrylic acid or methacrylic acid, such as methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, glycidyl ester, hydroxymethyl ester, 2-hydroxyethyl ester, hydroxypropyl ester And amides of acrylic acid or methacrylic acid and N-substituted amides such as N-hydroxymethylacrylic acid amide or methacrylic acid amide.

  The ionizing radiation polymerizable compound is a compound containing two or more functional groups having a carbon-carbon double bond such as an acrylate group in one molecule. This is because the acrylate group is preferable from the viewpoints of reactivity and workability, such as relatively high reactivity with ionizing radiation, and selection of various acrylic pressure-sensitive adhesives. Examples of the ionizing radiation polymerizable compound containing two or more carbon-carbon double bonds in one molecule include 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) acrylate, 1,6-hexanediol (meth) Acrylate, neopentyl glycol di (meth) acrylate, esterified product of (meth) acrylic acid and polyhydric alcohol, ester acrylate oligomer, 2-propenyl-3-butenyl cyanurate, isocyanurate, Examples include soocyanurate compounds. These ionizing radiation polymerizable compounds can be used alone or in admixture of two or more.

  The blending amount of the ionizing radiation polymerizable compound in the easily peelable pressure-sensitive adhesive layer varies depending on the type of the selected compound, so it cannot be generally stated. For example, 100 weight of acrylic copolymer in the ionizing radiation curable pressure sensitive adhesive The amount is about 0.5 to 200 parts by weight, and more preferably about 1 to 50 parts by weight. If the blending amount of the ionizing radiation polymerizable compound is too large relative to the blending amount of the acrylic copolymer, the content of the low molecular weight substance is increased, and it is difficult to maintain the shape and performance as an easily peelable adhesive layer. There is a tendency to become. Also, 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 applied, the tack of the easily peelable adhesive layer remains and the adhesive film is peeled off. When doing so, there is a possibility that adhesive remains on the adherend such as a metal plate.

  Further, when the easily peelable adhesive layer is used after being cured by irradiation with ultraviolet rays as ionizing radiation, it is preferable to use additives such as a photopolymerization initiator, a photopolymerization accelerator, and an ultraviolet sensitizer.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthone and the like.

  Further, the photopolymerization accelerator can reduce the polymerization obstacle due to air at the time of curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, and the like. can give. Examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.

  Moreover, it is more preferable that an easily peelable adhesive layer contains an isocyanate curing agent. By containing an isocyanate-based curing agent in the easily peelable adhesive layer, not only the coating strength of the easily peelable adhesive layer is improved by crosslinking with the ionizing radiation curable adhesive when forming the easily peelable adhesive layer, Since the carboxyl group-containing resin in the undercoat layer is also cross-linked, the adhesion between the easily peelable adhesive layer and the undercoat layer is also improved.

  The isocyanate curing agent may be a polyfunctional compound having two or more isocyanate groups. For example, diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, 1,5- Aromatic diisocyanates such as naphthylene diisocyanate, xylylene diisocyanate and toluylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate.

  About the content rate of an ionizing radiation curable adhesive and an isocyanate type hardening agent, it is preferable that an isocyanate type hardening agent shall be 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable adhesives. By containing 0.1 part by weight or more of the isocyanate curing agent, the adhesion between the undercoat layer and the easily peelable adhesive layer can be made more satisfactory. Moreover, the adhesive force before ionizing radiation irradiation can be hold | maintained by containing 10 weight part or less.

  Moreover, the ratio (molar ratio) of the number of moles of the aziridinyl group contained in the amine-based curing agent in the undercoat layer to the number of moles of the isocyanate group contained in the isocyanate-based curing agent in the easily peelable adhesive layer is 1. It is preferable that it is 5-15. By setting the molar ratio of the aziridinyl group to the isocyanate group within such a range, the balance between the crosslinking between the isocyanate curing agent and the hydroxyl group-containing resin and the crosslinking between the amine curing agent and the hydroxyl group-containing resin is suitable. Thus, not only the solvent resistance of the undercoat layer can be made particularly excellent, but also the adhesion between the undercoat layer and the easily peelable adhesive layer can be further improved.

  Furthermore, such an easily peelable pressure-sensitive adhesive layer may include other crosslinking agents such as alkyl etherified melamine compounds, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins). Etc.), additives such as plasticizers, fillers and anti-aging agents may be included as appropriate.

  The thickness of the easily peelable pressure-sensitive adhesive layer is not particularly limited, but is 5 μm to 100 μm, preferably 7 μm to 50 μm, and more preferably 10 μm to 30 μm, from the viewpoint of appropriate punching processing and prevention of etching solution penetration.

  Moreover, it is preferable that the adhesive film used by this invention is provided with the separator on the surface of the easily peelable adhesive layer from a viewpoint of handleability. Such a separator is not particularly limited. For example, polyethylene laminated paper, polypropylene, polyethylene, polyester, polycarbonate, triacetyl cellulose, polyvinyl chloride, acrylic, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride copolymer. And a plastic film having a release treatment applied to one surface of the plastic film.

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

  As a method for producing the easily peelable pressure-sensitive adhesive film of the present invention as described above, for example, the material constituting the undercoat layer described above is mixed to form an undercoat layer coating solution, and a conventionally known coating method such as a bar After coating on the transparent resin film by coater, die coater, blade coater, spin coater, roll coater, gravure coater, flow coater, spray, screen printing, etc., it is dried as necessary, and then constitutes an easily peelable adhesive layer It can be obtained by mixing the materials to be prepared into an easily peelable adhesive layer coating solution, and similarly applying the coating onto the undercoat layer by a conventionally known coating method, followed by heating and drying as necessary. Moreover, the separator mentioned above is bonded together to the said easily peelable adhesion layer as needed.

  In addition, for example, an undercoat layer is formed on one surface of the transparent resin film in the same manner as described above, and an easily peelable adhesive layer is formed on the separator in the same manner as described above, and then the transparent resin is formed. By bonding the surface on which the undercoat layer of the film is formed and the surface on which the easily peelable adhesive layer of the separator is formed, the easily peelable adhesive film of the present invention can be obtained.

  In addition, in the above description, although an example of the manufacturing method of the easily peelable adhesive film of this invention was demonstrated, this invention is not limited to this, For example, an easily peelable adhesive layer, undercoat layer on a separator, for example The transparent resin film may be formed in order.

  Moreover, regarding the manufacturing method of an easily peelable adhesive film, the carboxyl group-containing resin whose acid value is 10-100 mgKOH / g contained in undercoat layer coating liquid, and the isocyanate type hardening | curing agent contained in easily peelable adhesive layer coating liquid. From the viewpoint of crosslinking and sufficient adhesion between the undercoat layer and the easily peelable adhesive layer, the undercoat layer and the easily peelable adhesive layer contain a carboxyl group in the undercoat layer before they are bonded together. It is preferable that the reaction between the resin and the amine curing agent and the reaction between the ionizing radiation curable resin and the isocyanate curing agent in the easily peelable adhesive layer are not completed.

  The easily peelable pressure-sensitive adhesive film of the present invention can be used as a general pressure-sensitive adhesive film. In particular, it is suitable as an adhesive film for temporary fixing when processing semiconductor materials such as glass and silicon, and as a carrier sheet for etching metal plates. Adhesion with the layer can be maintained, and the workability can be improved.

  Hereinafter, the processing method of the metal plate which is one of the usage aspects of the easily peelable adhesive film of this invention is demonstrated. That is, the processing method of the metal plate of the present invention includes: A) a step of bonding the surface having the easily peelable adhesive layer of the easily peelable adhesive film of the present invention to the metal plate, and B) sticking the easily peelable adhesive film. A step of irradiating the exposed surface with ionizing radiation and curing the easily peelable adhesive layer, C) attaching a mask member to the surface of the metal plate opposite to the surface having the easily peelable adhesive film, and using the metal plate as an etching solution Dipping and removing the unmasked portion of the metal plate of the mask member, and D) peeling the mask member and the easily peelable adhesive film from the metal plate. Either the easily peelable adhesive layer curing step B) or the metal plate removing step C) may precede either.

  The metal plate processing method of the present invention further includes, after the metal plate removing step C), E) applying a subbing coating solution to the metal plate and transferring the metal plate to a desired transfer product. Can do. In this case, the transfer step E) is preferably performed after peeling the mask member in step D) and before peeling the easily peelable adhesive film. In addition, the easily peelable adhesive layer curing step B) may be performed after the transfer step E), before the metal plate removing step C), or before the metal plate removing step C, if it is before peeling the easily peelable adhesive film. ) And transfer step E).

  The metal plate processing method of the present invention is characterized in that the easily peelable adhesive film of the present invention is used as a carrier sheet for etching a metal plate. The material used in each step and the conditions of each step are metal Conventional materials and processing conditions can be employed depending on the purpose and application of processing. For example, the mask member may be a photoresist coating film as well as a sheet-like member, and the etching solution and etching conditions are appropriately changed according to the type and thickness of the target metal.

  Like this invention, it is an easily peelable adhesive film by which an undercoat layer and an easily peelable adhesive layer are laminated | stacked in order on a transparent resin film, Comprising: An amine type hardening | curing agent and an acid value are 10 to an undercoat layer. By including a carboxyl group-containing resin of 100 mg KOH / g and adopting a configuration containing an ionizing radiation curable pressure-sensitive adhesive in the easily peelable pressure-sensitive adhesive layer, for example, it becomes excellent in solvent resistance when used in metal etching applications. There is no coating film peeling of the easily peelable adhesive film, and the handleability is excellent. Therefore, it can be suitably used not only for such a metal etching carrier but also for processing a semiconductor material such as a ceramic capacitor, a silicon wafer, or a glass wafer.

  Hereinafter, the present invention will be described in more detail with reference to examples. In this example, “parts” and “%” are based on weight unless otherwise specified.

1. Preparation of easily peelable protective adhesive film [Example 1]
The undercoat layer coating solution below is applied to one side of a 100 μm thick polyethylene terephthalate film (Lumirror S10: Toray) as a transparent resin film to form an undercoat layer with a thickness of 0.5 μm. did. Next, an easily peelable adhesive layer coating solution having the following formulation is applied onto the undercoat layer by a bar coater method to form a 25 μm thick easily peelable adhesive layer, and the undercoat layer and the easily peelable adhesive layer are heated. , Dried. Subsequently, the release treatment surface of a separator (thickness 25 μm, polyethylene naphthalate film, MRF: Mitsubishi Chemical Polyester Film Co., Ltd.) was bonded onto the easily peelable adhesive layer, and the removable protective adhesive film of Example 1 was produced. .

<Coating liquid for undercoat layer of Example 1>
・ 100 parts of polyester resin (UR1700: Toyobo Co., Ltd., acid value: 26 mgKOH / g, solid content: 100%)
・ Amine-based curing agent 29 parts
・ Particles (silicone resin particles, average particle size: 3 μm) 1.1 parts (Tospearl 130: Momentive Performance Materials)
・ 942 parts diluted solvent

<Coating liquid for easily peelable adhesive layer of Example 1>
・ Ionizing radiation curable adhesive 100 parts (Cooponyl N7271: Nippon Synthetic Chemical Co., Ltd., solid content 40%)
・ Isocyanate-based curing agent 0.55 parts (Coronate L45E: Nippon Polyurethane, solid content 45%)
-Polymerization initiator 1.4 parts (Irgacure 184: BASF Corporation, solid content 100%)
・ 38 parts of diluted solvent

[Example 2]
A releasable pressure-sensitive adhesive film of Example 2 was produced in the same manner as in Example 1 except that the particles contained in the undercoat layer coating solution of Example 1 were removed.

[Example 3]
The releasable adhesive of Example 3 in the same manner as in Example 1 except that the weight part of the amine-based curing agent contained in the coating solution for the undercoat layer of Example 1 was 6.6 parts, and the particles were removed. A film was prepared.

[Example 4]
The releasable pressure-sensitive adhesive film of Example 4 was prepared in the same manner as in Example 1 except that 107 parts by weight of the amine-based curing agent contained in the coating solution for the undercoat layer of Example 1 and excluding the particles. Produced.
In Examples 1 to 4, the molar ratio of the aziridinyl group contained in the amine-based curing agent in the undercoat layer to the isocyanate group contained in the isocyanate-based curing agent in the easily peelable pressure-sensitive adhesive layer was 1.5. Within the range of -15.

[Comparative Example 1]
A re-peelable pressure-sensitive adhesive film of Comparative Example 1 was produced in the same manner as in Example 1 except that the amine-based curing agent contained in the coating liquid for the undercoat layer of Example 1 was removed.

[Comparative Example 2]
An easily peelable adhesive film of Comparative Example 2 was produced in the same manner as in Example 1 except that the undercoat layer coating solution of Example 1 was changed to the undercoat layer coating solution described below.

<Coating liquid for undercoat layer of Comparative Example 2>
・ 100 parts of polyester resin (Acryt ER20: Taisei Kako Co., Ltd., acid value: 2 mgKOH / g, solid content 40%)
・ Isocyanate curing agent 4.9 parts (Takenate D110N: Mitsui Chemicals, solid content 60%)
・ Diluted solvent 225 parts

[Comparative Example 3]
Comparative Example 2 was the same as Comparative Example 2 except that 9 parts by weight of bifunctional acrylate monomer (Kayarad R-167, Nippon Kayaku Co., Ltd., solid content 100%) was added to the undercoat layer coating solution. The removable adhesive film of Comparative Example 3 was produced.

[Comparative Example 4]
An easily peelable adhesive film of Comparative Example 4 was produced in the same manner as in Example 1, except that the undercoat layer coating solution of Example 1 was changed to the undercoat layer coating solution described below.

<Coating liquid for undercoat layer of Comparative Example 4>
・ 100 parts of polyester resin (Byron 200: Toyobo Co., Ltd., acid value: 2 mgKOH / g, solid content: 100%)
・ Amine-based curing agent 29 parts (TAZO: Mutual Pharmaceutical Company, solid content 30%)
・ Dilution solvent 932 parts

2. Evaluation (1) Adhesiveness The separator was peeled off from each of the easily peelable adhesive films of Examples 1 to 4 and Comparative Examples 1 to 4 to expose the easily peelable adhesive layer, and 400 mJ / cm by a metal halide lamp from the transparent resin film side. The ultraviolet ray of ² was irradiated to cure the ionizing radiation curable pressure-sensitive adhesive. Then, it measured and evaluated based on the cross cut tape method in JIS-K5400 1990 about the said easily peelable adhesive film. “○” indicates that none of the cross section was peeled off, “△” indicates that the cross section was peeled off with less than 5 pieces, and the cross section was peeled off over 5 pieces. The thing was made into "x". The measurement results are shown in Table 1.

(2) Solvent resistance (droplet evaluation)
Examples 1-4 and Comparative Examples 1-4 Each separator was peeled from the easily peelable adhesive film to expose the easily peelable adhesive layer, and ultraviolet rays of 400 mJ / cm ² were irradiated from the transparent resin film side by a metal halide lamp. The ionizing radiation curable adhesive was cured. Thereafter, several drops of toluene were dropped on the surface of the easily peelable adhesive layer. Although it was allowed to stand for 5 minutes after the dropping, the easily peelable adhesive layer was observed, and “○” indicates that no peeling occurred at the end, but it was allowed to stand for 2 minutes or more but less than 5 minutes, but the easily peelable adhesive layer was observed. Then, the case where peeling did not occur at the end portion was designated as “Δ”, and the case where peeling occurred at the end portion immediately after the dropping was designated as “x”. The measurement results are shown in Table 1.

(3) Solvent resistance (rubbing evaluation)
In parallel with (2), after the ionizing radiation curable pressure-sensitive adhesive is cured as described above, the surface of the easily peelable adhesive layer is rubbed 10 times with a waste soaked in toluene, and the easily peelable The adhesive layer was observed. The case where peeling did not occur at the end of the easily peelable pressure-sensitive adhesive layer was “◯”, and the case where peeling occurred was “x”. The evaluation results are shown in Table 1.

  As is clear from the results in Table 1, the easily peelable adhesive films of Examples 1 to 4 include an amine-based curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g on the transparent resin film. Since it has an undercoat layer and an easily peelable adhesive layer containing an ionizing radiation curable adhesive in order, the cross-cut peel evaluation is good, the adhesion between the substrate and the undercoat layer, and the undercoat layer The adhesiveness with the peelable adhesive layer was excellent. Moreover, it was excellent also in the solvent resistance test using toluene.

  In particular, since the easily peelable adhesive films of Example 1 and Example 2 contained 2 to 30 parts by weight of the amine-based curing agent with respect to 100 parts by weight of the carboxyl group-containing resin, It was excellent in adhesion to the easily peelable adhesive layer and solvent resistance.

  Moreover, when Example 1 is compared with Example 2, since the easily peelable adhesive film of Example 1 contains particles in the undercoat layer, the surface unevenness formed by the particles has an anchoring effect on the adhesive layer. As a result, the adhesion between the undercoat layer and the easily peelable adhesive layer and the initial adhesiveness were superior to those of Example 2.

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

Moreover, although the easily peelable adhesive film of the comparative example 2 uses an isocyanate hardening agent instead of an amine hardening agent for the undercoat layer, the substrate and the undercoat layer are different from the comparative example 1. The adhesion and the adhesion between the undercoat layer and the easily peelable adhesive layer could not be improved.
The easy-peelable adhesive film of Comparative Example 3 is not an amine-based curing agent in order to improve the adhesion between the base material and the undercoat layer and the adhesion between the undercoat layer and the easily peelable adhesive layer. Although it uses a functional group acrylate monomer, compared to the examples using an amine curing agent, the adhesion between the substrate and the undercoat layer, and the adhesion between the undercoat layer and the easily peelable adhesive layer In addition, it was inferior to the solvent resistance test using toluene.

Moreover, although the easily peelable adhesive film of Comparative Example 4 had an amine-based curing agent and a carboxyl group-containing resin, the acid value of the carboxyl group-containing resin was less than 10 mgKOH / g. It was inferior in the adhesiveness with an easily peelable adhesion layer, and inferior also in the solvent-resistance test using toluene.

Claims (8)

An easily peelable adhesive film in which an undercoat layer and an easily peelable adhesive layer are laminated 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 easy-peelable adhesive layer contains an ionizing radiation curable pressure-sensitive adhesive.   The easily peelable adhesive film according to claim 1, wherein the easily peelable adhesive layer further contains an isocyanate curing agent.   The ratio of the number of moles of the aziridinyl group contained in the amine-based curing agent to the number of moles of the isocyanate group contained in the isocyanate-based curing agent is 1.5 to 15. Easy peelable adhesive film.   The easily peelable film according to any one of claims 1 to 3, wherein the undercoat layer contains 3 to 30 parts by weight of the amine-based curing agent with respect to 100 parts by weight of the carboxyl group-containing resin. Adhesive film.   The easily peelable adhesive film according to any one of claims 1 to 4, wherein the amine curing agent is a trifunctional aziridine compound. A) The process of bonding the surface which has the easily peelable adhesive layer of the easily peelable adhesive film of any one of Claims 1-5 to a metal plate,
B) The process of irradiating the easily peelable adhesive film stuck to the metal plate with ionizing radiation and curing the easily peelable adhesive layer,
C) forming a mask on the surface of the metal plate opposite to the surface having the easily peelable adhesive film, immersing the metal plate in an etching solution, and removing the portion of the metal plate where the mask is not formed;
D) A process of removing the mask from the metal plate and peeling the easily peelable adhesive film,
The metal plate processing method characterized by including.   The method for processing a metal plate according to claim 6, wherein the step B) is performed after the step C). In step D), after removing the mask from the metal plate, before peeling the easily peelable adhesive film,
E) The method of processing a metal plate according to claim 6 or 7, further comprising a step of transferring the metal plate to a transfer object.