KR20140142321A - Easily removable adhesive film and metal plate processing method - Google Patents

Abstract

The peelable pressure-sensitive adhesive film of the present invention is a peelable pressure-sensitive adhesive film whose adhesive force is lowered by irradiation with ionizing radiation, wherein an undercoat layer and a peelable pressure-sensitive adhesive layer are laminated in this order on a transparent resin film, Layer comprises an amine-based curing agent and a carboxyl-containing resin having an acid value of 10 to 100 mgKOH / g, and the peelable pressure-sensitive adhesive layer comprises an ionizing radiation-curable pressure-sensitive adhesive. The undercoat layer contains an amine-based curing agent and a carboxyl group-containing resin having a specific acid value range, so that the adhesive property between the substrate and the undercoat layer and the peelable pressure-sensitive adhesive film having excellent solvent resistance while maintaining the adhesion between the undercoat layer and the peelable pressure- Can be provided.

Description

The present invention relates to a releasable adhesive film and a metal plate processing method,

The present invention relates to a peelable pressure-sensitive adhesive film which is preferably used as a temporarily 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.

(Hereinafter referred to as a releasable pressure-sensitive adhesive film) having a releasability as a temporary fixing agent is applied to a wafer in order to prevent cracking during processing for semiconductor materials such as ceramic capacitors, silicon wafers, and glass wafers A method is employed in which a wafer is subjected to polishing, dicing, or the like, and then the adhesive force of the pressure-sensitive adhesive film is lowered by the addition of external energy such as light or heat to peel off the wafer.

The peelable pressure-sensitive adhesive film is also used as a carrier sheet for metal plate etching. For example, the releasable pressure-sensitive adhesive film is stuck to a metal plate such as stainless steel, and the metal plate is etched so as to have a desired shape, and if necessary, an undercoat coating liquid is coated on the metal plate to form a metal plate It is transferred.

As such adhesive films, those described in, for example, Patent Documents 1 to 3 may be mentioned. These prior arts disclose that re-release properties can be obtained by using an ionizing radiation-curable pressure-sensitive adhesive whose adhesive strength is lowered by ionizing radiation to the pressure-sensitive adhesive layer.

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

In the pressure-sensitive adhesive films exemplified in Patent Documents 1 to 3, when the undercoat coating liquid is coated on the metal plate in the metal etching application as described above, the solvent components in the coating liquid are scattered on the pressure-sensitive adhesive film, And the adhesion between the adhesive layer and the base material deteriorates, resulting in detachment of the coating film of the adhesive layer. Thus, the workability such as the transferring of the metal plate to the transfer material may be deteriorated.

In order to prevent such peeling of the coating film, it is conceivable to provide an undercoat layer for enhancing adhesion between the substrate and the pressure-sensitive adhesive layer. In this case, as the undercoat layer, it is preferable to use a thermosetting resin in order not to lower the adhesion of the ionizing radiation-curable pressure-sensitive adhesive used in the pressure-sensitive adhesive layer. However, in the case of a thermosetting resin used as an undercoat layer, It has been difficult to obtain a pressure-sensitive adhesive film having excellent solvent resistance while maintaining the adhesion between the undercoat layer and the undercoat layer and the pressure-sensitive adhesive layer.

In view of the above circumstances, the present invention provides a pressure-sensitive adhesive film comprising the release-type pressure-sensitive adhesive layer including the undercoat layer and the ionizing radiation-curable pressure-sensitive adhesive on a substrate in order, Sensitive adhesive film which is excellent in solvent resistance while maintaining the adhesion of the pressure-sensitive adhesive layer.

The inventors of the present invention have found that by including a specific resin and a curing agent in the undercoat layer, the present inventor can attain excellent solvent resistance while maintaining the adhesion between the substrate and the undercoat layer and the adhesion between the undercoat layer and the peelable pressure- And has arrived at the present invention.

That is, the peelable pressure-sensitive adhesive film of the present invention is formed by sequentially laminating an undercoat layer and a peelable pressure-sensitive adhesive layer on a transparent resin film, wherein the undercoat layer has an amine-based curing agent and an acid value of 10 to 100 mgKOH / g And the releasable pressure-sensitive adhesive layer comprises an ionizing radiation-curable pressure-sensitive adhesive.

The releasable pressure-sensitive adhesive film of the present invention is preferably characterized in that the releasable pressure-sensitive adhesive layer further comprises an isocyanate-based curing agent.

The peelable pressure-sensitive adhesive film of the present invention is preferably 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-based curing agent is 1.5 to 15.

The releasable pressure-sensitive 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 relative to 100 parts by weight of the carboxyl group-containing resin.

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

The method of working a metal plate of the present invention is characterized in that A) a step of bonding a surface of the peelable pressure-sensitive adhesive film of the present invention having the peelable pressure-sensitive adhesive layer to a metal plate, B) (C) a step of forming a mask on the surface opposite to the surface having the peelable pressure-sensitive adhesive film of the metal plate, and immersing the metal plate in an etchant to form a pressure- Removing the metal plate on the portion where no mask is formed; D) removing the mask from the metal plate, and peeling off the peelable pressure-sensitive adhesive film. Any of the steps B) and C) may be preceded.

According to the peelable pressure-sensitive adhesive film of the present invention, the adhesiveness between the substrate and the undercoat layer and the adhesiveness between the undercoat layer and the peelable pressure-sensitive adhesive layer can be maintained, and excellent solvent resistance can be obtained. Therefore, the peelable pressure-sensitive adhesive film is suitably used as a temporary sheet for dicing an adherend such as a silicon wafer or a glass wafer, or as a carrier sheet for metal etching.

The peelable pressure-sensitive adhesive film of the present invention comprises an undercoat layer and a peelable pressure-sensitive adhesive layer laminated in this order on a transparent resin film, wherein the undercoat layer is formed of an amine-based curing agent and an acid value of 10 to 100 mgKOH / g (Hereinafter sometimes simply referred to as a carboxyl group-containing resin), and the peelable pressure-sensitive adhesive layer comprises an ionizing radiation-curable pressure-sensitive adhesive. Hereinafter, embodiments of the respective components of the 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, And plastic films such as triacetylcellulose, acrylic, polyvinyl chloride, and norbornene compounds. It is also possible to use a polymer film containing a compound having a carboxyl group as a polymer structural unit or a laminate of the polymer film and a general polymer film. The thickness of the transparent resin film is preferably 2 to 300 占 퐉, more preferably 10 to 125 占 퐉.

Further, since the peelable pressure-sensitive adhesive film of the present invention deteriorates the adhesive force of the peelable pressure-sensitive adhesive layer by irradiation with ionizing radiation as described later, the transparent resin film of JIS K7375: 2008 Is preferably 50% or more, more preferably 80% or more of the total light transmittance.

Next, the undercoat layer contains an amine-based curing agent and a carboxyl-containing resin having an acid value of 10 to 100 mgKOH / g. The amine-based curing agent crosslinks with the carboxyl group-containing resin in the undercoat layer to improve the solvent resistance of the undercoat layer. The carboxyl-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 the releasable pressure-sensitive adhesive layer to be described later, whereby the adhesion between the undercoat layer and the peelable pressure- . Further, by including a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g in the undercoat layer, adhesion with the transparent resin film is also improved.

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, diaminodiphenylmethane, Aromatic amines such as benzene, toluene and xylene; aromatic polyamines such as benzene, toluene and xylene; aromatic polyamines such as benzene, toluene and xylene; aromatic polyamines such as benzene and toluene; aromatic polyamines such as benzene, A polyamideamine obtained by reacting a polyamine, an aziridine compound having a melamine, an aziridine group (ethyleneimine), and the like can be used. Aziridine compounds are particularly suitable.

Examples of the aziridine compound include monofunctional aziridine compounds such as aziridine, 2-methyl aziridine, 2-ethyl aziridine, 2,2-dimethyl aziridine, 2,3-dimethyl aziridine, 2- Phenyl aziridine and the like), bifunctional aziridine compounds (for example, neopentyl glycol di (? -Aziridinyl propionate), 4,4'-isopropylidenediphenol di (? -Aziridinyl propionate Trifunctional aziridine compounds such as tetramethylolmethane-tri- (? - aziridinyl propionate), and 4,4'-methylene diphenol di (? - aziridinyl propionate) , Trimethylolpropane tris (? - aziridinyl propionate), glyceryl tris (? - aziridinyl propionate), tetrafunctional aziridine compounds (for example, tetraaziridinyl methacrylate Diamine, tetraaziridinylmethylparaxylenediamine, tetramethylpropane tetraaziridinylpropionate, etc.), 6 A functional aziridine compound (for example, those described in Japanese Patent Application Laid-Open No. 2003-104970). Among them, it is preferable to use a trifunctional aziridine compound from the viewpoint of improving the solvent resistance of the undercoat layer. The amine curing agents described above may be used alone or in combination of two or more.

The carboxyl-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 and specifically includes a (meth) acrylic copolymer, a vinyl copolymer, a polyurethane resin, Polycarbonate resins, polyamide resins, and polyimide resins. These resins may be used singly or in combination of two or more. Among them, a polyester resin is suitably used from the viewpoint of adhesion between the transparent resin film and the 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 Based resin. These resins may be used singly 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 of the carboxyl-containing resin having an acid value of 10 to 100 mgKOH / g and the amine-based curing agent is preferably 3 to 30 parts by weight of the amine-based curing agent relative to 100 parts by weight of the carboxyl-containing resin. By containing at least 3 parts by weight of the amine-based curing agent, it is possible to improve the solvent resistance of the peelable pressure-sensitive adhesive film and to make the adhesion of the undercoat layer and the peelable pressure-sensitive adhesive layer more satisfactory. By containing not more than 30 parts by weight, it is possible to prevent the storage stability of the paint from being deteriorated and prevent the adhesion of the undercoat layer and the transparent resin film from being deteriorated. The content ratio of the carboxyl-containing resin and the amine curing agent is preferably 5 to 20 parts by weight.

It is preferable that particles are contained in the undercoat layer. When the particles are contained in the undercoat layer, a concavo-convex shape is formed on the surface of the undercoat layer, and the concavo-convex shape is intertwined with the interface of the peelable pressure-sensitive adhesive layer, so that the anchoring effect to the adherend can be exerted. This further improves the initial adhesion to the adherend. 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 and urethane resin particles, silica, clay, talc, calcium carbonate, Inorganic particles such as calcium sulfate, barium sulfate, aluminum silicate, titanium oxide, synthetic zeolite, alumina, and smectite.

The particle diameter of the particles is not limited, but is preferably from 0.3 mu m to 12 mu m, more preferably from 0.7 mu m to 6 mu m, in terms of the average particle diameter. The content of the particles is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.5 parts by weight to 5 parts by weight, based on 100 parts by weight of the resin in the undercoat layer. The term " particle diameter " refers to a particle volume calculated by the Coulter counter method in terms of spheres.

The undercoat layer may contain, in the range not to impair the function of the present invention, a crosslinking agent such as an alkyl etherified aminoformaldehyde resin, a polyisocyanate and a block isocyanate, a polyaniline, a polythiophene, a polypyrrole, Antistatic agents such as polyacetylene, polyphenylene, polyphenylene vinylene, polyacene and polythiophene vinylene, antifoaming agents, anti-slip agents, preservatives, rust inhibitors, pH adjusting agents, antioxidants, pigments other than the above- , Lubricant, and the like can be appropriately contained.

The thickness of the undercoat layer is not particularly limited, but is preferably from 0.2 m to 10 m, more preferably from 0.5 m to 5 m, in order to improve adhesion between the substrate and the peelable pressure-sensitive adhesive layer.

Next, this peelable pressure-sensitive adhesive layer comprises an ionizing radiation-curable pressure-sensitive adhesive. The ionizing radiation-curable pressure-sensitive adhesive should adhere firmly to an adherend such as a metal plate before irradiation with ionizing radiation (ultraviolet ray or electron beam), and should not be peeled off even after being immersed in the etching solution, and also to prevent erosion of the etching solution.

The ionizing radiation-curable pressure-sensitive adhesive constituting the releasable pressure-sensitive adhesive layer is mainly composed of an acrylic copolymer and an ionizing radiation polymerizable compound.

As the acrylic copolymer, a homopolymer having an ester of acrylic acid or methacrylic acid as a main constituent unit, a copolymer of acrylic acid or methacrylic acid or an ester thereof or an acid amide thereof with other copolymerizable comonomer, or a mixture of these polymers to be. Examples of the monomer and comonomer thereof include alkyl esters of acrylic acid or methacrylic acid such as methyl esters, ethyl esters, butyl esters, 2-ethylhexyl esters, octyl esters, glycidyl esters, hydroxymethyl esters, 2- Hydroxyethyl esters, hydroxypropyl esters and amides and N-substituted amides of acrylic acid or methacrylic acid, 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 carbon-carbon double bonds such as an acrylate group in one molecule. The acrylate group exhibits relatively high reactivity to ionizing radiation, but is also preferable from the viewpoints of reactivity and workability such as various acrylic pressure-sensitive adhesives can be selected. 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, pentaerythritol tetra Acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol monohydroxy (Meth) acrylate, esters of (meth) acrylic acid and polyhydric alcohols, ester acrylate oligomers, 2-propenyl-3-butenyloxy Isocyanurate, isocyanurate compounds, and the like. These ionizing radiation polymerizable compounds may be used singly or in combination of two or more.

The blending amount of the ionizing radiation-polymerizable compound in the peelable pressure-sensitive adhesive layer can not be uniformly determined because it differs depending on the kind of the compound selected. For example, in the case of 100 parts by weight of the ionic radiation- To about 200 parts by weight, and more preferably about 1 to about 50 parts by weight. If the blending amount of the ionizing radiation-polymerizing compound is excessively large relative to the blending amount of the acrylic copolymer, the content of the low-molecular weight substance becomes large, and it tends to be difficult to maintain the shape and performance as the releasable adhesive layer. If the blending amount of the ionizing radiation-polymerizing compound is too small relative to the blending amount of the acrylic copolymer, even if the ionizing radiation is irradiated, the exfoliating adhesive layer becomes excessively sticky, and when the exfoliating film is peeled, There is a possibility.

When the peelable pressure-sensitive adhesive layer is cured by irradiating ultraviolet rays as ionizing radiation, additives such as a photopolymerization initiator, a photopolymerization accelerator, and an ultraviolet sensitizer can be used.

Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoyl benzoate,? -Acyloxime ester and thioxanthone.

In addition, the photopolymerization accelerator is capable of accelerating the curing rate by alleviating the polymerization trouble caused by air at the time of curing, and examples thereof include p-dimethylaminobenzoyl isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. Examples of ultraviolet sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

It is more preferable that the peelable pressure-sensitive adhesive layer contains an isocyanate-based curing agent. By containing the isocyanate curing agent in the releasable pressure-sensitive adhesive layer, the coating strength of the releasable pressure-sensitive adhesive layer is improved by crosslinking with the ionizing radiation curable pressure-sensitive adhesive at the time of forming the releasable pressure-sensitive adhesive layer, Therefore, the adhesion between the peelable pressure-sensitive adhesive layer and the undercoat layer is also improved.

The isocyanate-based curing agent may be any polyfunctional compound having two or more isocyanate groups, and examples thereof include diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylenediisocyanate, Aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; aromatic diisocyanates such as xylylene diisocyanate, xylylene diisocyanate, and toluylene diisocyanate; .

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 not less than 0.1 part by weight of the isocyanate curing agent, the adhesion between the undercoat layer and the peelable pressure-sensitive adhesive layer can be made more satisfactory. When the content is 10 parts by weight or less, the adhesive strength before irradiation with ionizing radiation can be maintained.

The molar ratio of the aziridinyl group contained in the amine curing agent in the undercoat layer to the number of moles of the isocyanate group contained in the isocyanate curing agent in the peelable pressure-sensitive adhesive layer is preferably 1.5 to 15. When the molar ratio of the aziridinyl group to the isocyanate group is within the above range, the balance between the crosslinking of the isocyanate curing agent and the hydroxyl group-containing resin and the crosslinking of the amine curing agent and the hydroxyl group-containing resin becomes suitable, Is particularly excellent, and adhesion between the undercoat layer and the peelable pressure-sensitive adhesive layer can be further improved.

Further, the peelable pressure-sensitive adhesive layer may further contain other crosslinking agents such as an alkyl etherified melamine compound, a tackifier (e.g., a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, etc.) , An antioxidant, and the like may be appropriately included.

The thickness of the peelable pressure-sensitive adhesive layer is not particularly limited, but is preferably from 5 탆 to 100 탆, preferably from 7 탆 to 50 탆, more preferably from 10 탆 to 30 탆, from the viewpoint of preventing pitting and penetration of the etching solution. to be.

The adhesive film used in the present invention is preferably provided with a separator on the surface of the peelable pressure-sensitive adhesive layer from the viewpoint of handling. Examples of such a separator include, but are not limited to, polyethylene laminates, polypropylene, polyethylene, polyester, polycarbonate, triacetylcellulose, polyvinyl chloride, acrylic, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride A plastic film such as a copolymer, and a film obtained by subjecting one surface of the plastic film to a releasing treatment.

The thickness of the separator is not particularly limited, but from the viewpoint of handling property, a thickness of 10 탆 to 250 탆, preferably 20 탆 to 125 탆, more preferably 30 탆 to 100 탆 is used.

As the method for producing the peelable pressure-sensitive adhesive film of the present invention as described above, for example, a method may be employed in which a material constituting the undercoat layer described above is mixed to form an undercoat layer coating liquid, Is applied 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 spraying, a screen printing or the like, and then dried if necessary, And then applying the releasable pressure-sensitive adhesive layer coating liquid to the releasable pressure-sensitive adhesive layer coating liquid, applying the releasable pressure-sensitive adhesive layer coating liquid on the undercoat layer by the conventionally known coating method, and then heating and drying if necessary. If necessary, the aforementioned separator is applied to the peelable pressure-sensitive adhesive layer.

Further, for example, an undercoat layer is formed on one side of a transparent resin film in the same manner as described above, and the peelable pressure-sensitive adhesive layer is formed on the separator in the same manner as described above, The peelable pressure-sensitive adhesive film of the present invention can be obtained by bonding the surface of the separator with the surface of the separator having the coat layer formed thereon.

In the above description, an example of the method of producing the peelable pressure-sensitive adhesive film of the present invention has been described. However, the present invention is not limited thereto. For example, the peelable pressure-sensitive adhesive layer, the undercoat layer, May be formed in this order.

With respect to the production method of the peelable pressure-sensitive adhesive film, the carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g contained in the undercoat layer coating liquid and the isocyanate curing agent contained in the releasable pressure- The undercoat layer and the peelable pressure-sensitive adhesive layer are preferably formed so that the reaction between the carboxyl group-containing resin and the amine-based curing agent in the undercoat layer and the reaction between the carboxyl group-containing resin and the amine- It is preferable that the reaction between the ionizing radiation curable resin and the isocyanate curing agent in the peelable pressure-sensitive adhesive layer is not completely completed.

The peelable pressure-sensitive adhesive film of the present invention can be used as a general pressure-sensitive adhesive film. It is suitable as a carrier sheet for temporarily fixing an adhesive film for temporarily fixing or a carrier sheet for etching a metal sheet such as glass or silicon and maintains adhesion between the substrate and the peelable pressure-sensitive adhesive layer during processing or during etching, The workability can be improved.

Hereinafter, a method of processing a metal plate, which is one embodiment of the use of the peelable pressure-sensitive adhesive film of the present invention, will be described. That is, the method for working the metal plate of the present invention comprises the steps of A) a step of bonding a metal plate to the surface of the peelable pressure-sensitive adhesive film of the present invention having the peelable pressure-sensitive adhesive layer, and B) ionizing radiation onto the surface to which the releasable pressure- (C) a step of adhering a mask member to a surface of the metal plate opposite to the surface having the peelable pressure-sensitive adhesive film, and immersing the metal plate in an etchant to remove the unmasked (D) a step of peeling the mask member and the peelable pressure-sensitive adhesive film from the metal plate. This peelable pressure-sensitive adhesive layer curing step B) and the metal plate removing step C) may be preceded by either.

Further, the method of working a metal plate of the present invention may further include a step of E) after the metal plate removing step C), and a step of applying an undercoat coating liquid to the metal plate and transferring the metal plate to a desired transfer article. In this case, it is preferable that the transfer step E) is carried out before the release of the peelable pressure-sensitive adhesive film after peeling the mask member in the step D). This peelable pressure-sensitive adhesive layer curing step B) may be carried out after the transfer step E) before the peeling off of the peelable pressure-sensitive adhesive film, or between the metal plate removing step C) and the metal sheet removing step C) and the transferring step E) .

The metal plate processing method of the present invention is characterized in that the peelable pressure-sensitive adhesive film of the present invention is used as a carrier sheet for etching a metal plate. The materials used in each step and the conditions of each step are not limited to the purpose A common material and processing conditions can be adopted. For example, the mask member may be a sheet-like member as well as a coating film of a photoresist, and the etching solution and the etching conditions are appropriately changed depending on the type and thickness of the metal to be treated.

The releasable pressure-sensitive adhesive film in which an undercoat layer and a peelable pressure-sensitive adhesive layer are laminated in this order on a transparent resin film as in the present invention, wherein the undercoat layer is provided with an amine curing agent and a carboxyl group having an acid value of 10 to 100 mgKOH / g Containing resin, and the constitution including the ionizing radiation-curable pressure-sensitive adhesive agent in the releasable pressure-sensitive adhesive layer is used, for example, when it is used for metal etching, the solvent resistance is excellent. Therefore, So that the handling property is excellent. Therefore, the present invention can be suitably used not only as a carrier for such metal etching but also as a processing material for semiconductor capacitors, semiconductor materials such as silicon wafers and glass wafers.

Example

Hereinafter, the present invention will be described in more detail by way of examples. In the present embodiment, " part " and "% " are by weight unless otherwise indicated.

1. Fabrication of this peelable protective adhesive film

[Example 1]

On one side of a polyethylene terephthalate film having a thickness of 100 占 퐉 as a transparent resin film (Lumirror S10: Doreya Co., Ltd.), an undercoat layer coating liquid described below was applied by a bar coater method to form an undercoat layer having a thickness of 0.5 占 퐉 . Subsequently, a coating liquid for a peelable pressure-sensitive adhesive layer of the following formulation was coated on the undercoat layer by a bar coater method to form a peelable pressure-sensitive adhesive layer having a thickness of 25 占 퐉, and the undercoat layer and the releasable pressure- Lt; / RTI > Subsequently, a releasable protective adhesive film of Example 1 was prepared by kneading a releasable surface of a separator (25 탆 thick, polyethylene naphthalate film, MRF: Mitsubishi Chemical Polyester Film Co., Ltd.) on the releasable pressure-sensitive adhesive layer.

≪ Coating liquid for undercoat layer of Example 1 >

Polyester resin 100 parts

(UR1700: Toyoboseki Co., acid value: 26 mgKOH / g, solid content 100%)

· Amine-based curing agent 29 parts

(TAZO: Sogo Pharmaceutical Co., solid content 30%)

Particles (silicone resin particles, average particle diameter: 3 占 퐉) 1.1 parts

(Tospearl 130: Momentive Performance Materials)

Diluent: 942 parts

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

· Ionizing radiation curable adhesive 100 parts

(Coponyl N7271: Nippon Synthetic Chemical Industry Co., Ltd., solid content: 40%)

· Isocyanate curing agent 0.55 part

(Coronate L45E: Japanese polyurethane, 45% solids)

Polymerization initiator 1.4 parts

(Ircacure 184: BASF Co., 100% solids)

Dilution solvent 38 parts

[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 coating liquid for undercoat layer of Example 1 were excluded.

[Example 3]

The releasable pressure-sensitive adhesive film of Example 3 was prepared in the same manner as in Example 1 except that the amount of the amine-based curing agent contained in the coating liquid for undercoat layer of Example 1 was changed to 6.6 parts by weight.

[Example 4]

The releasable pressure-sensitive adhesive film of Example 4 was produced in the same manner as in Example 1 except that the amount of the amine-based curing agent contained in the coating liquid for undercoat layer of Example 1 was changed to 107 parts by weight.

Further, in Examples 1 to 4, the molar ratio of the aziridinyl group contained in the amine curing agent in the undercoat layer to the isocyanate group contained in the isocyanate curing agent in the peelable pressure-sensitive adhesive layer was all within the range of 1.5 to 15.

[Comparative Example 1]

A releasable 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 the undercoat layer of Example 1 was excluded.

[Comparative Example 2]

The 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 described below.

≪ Coating solution for undercoat layer of Comparative Example 2 >

Polyester resin 100 parts

(Acryt ER20: Daisai Corporation, acid value: 2 mgKOH / g, solid content 40%)

· Isocyanate curing agent 4.9 parts

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

Diluent 225 parts

[Comparative Example 3]

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

[Comparative Example 4]

The peelable pressure-sensitive adhesive film of Comparative Example 4 was produced in the same manner as in Example 1 except that the coating liquid for undercoat layer in Example 1 was changed to the coating liquid for undercoat layer in the following formulation.

≪ Coating liquid for undercoat layer of Comparative Example 4 >

Polyester resin 100 parts

(Bairon 200: Toyoboseki, acid value: 2 mgKOH / g, solid content: 100%)

· Amine-based curing agent 29 parts

(TAZO: Sogo Pharmaceutical Co., solid content 30%)

Diluent 932 parts

2. Evaluation

(1) Adhesiveness

Separators were peeled from the peelable pressure-sensitive adhesive films of Examples 1 to 4 and Comparative Examples 1 to 4 to expose the peelable pressure-sensitive adhesive layer, and ultraviolet rays of 400 mJ / cm 2 were irradiated from the transparent resin film side with a metal halide lamp To thereby cure the ionizing radiation curable pressure sensitive adhesive. Thereafter, the peelable pressure-sensitive adhesive film was measured and evaluated based on the checkerboard tape method in JIS-K5400 1990. &Quot; ", " x ", " x ", " x ", and " x " The measurement results are shown in Table 1.

(2) Solvent resistance (droplet evaluation)

Separators were peeled from the peelable pressure-sensitive adhesive films of Examples 1 to 4 and Comparative Examples 1 to 4 to expose the peelable pressure-sensitive adhesive layer, and ultraviolet rays of 400 mJ / cm 2 were irradiated from the transparent resin film side with a metal halide lamp To thereby cure the ionizing radiation curable pressure sensitive adhesive. Thereafter, a few drops of toluene was added to the surface of the peelable pressure-sensitive adhesive layer. After leaving for 5 minutes after dropwise addition, the peelable pressure-sensitive adhesive layer was observed, and the product in which no peeling occurred at the end was left as "? &Quot; for less than 5 minutes but not peeled &Quot;, and " x " when peeling occurred at the end immediately after dropping. The measurement results are shown in Table 1.

(3) Solvent resistance (rubbing evaluation)

After the ionizing radiation-curable pressure-sensitive adhesive was cured in parallel with (2) above, the surface of the releasable pressure-sensitive adhesive layer was rubbed 10 times by rubbing with toluene impregnated, and the releasable pressure-sensitive adhesive layer was observed. The samples in which peeling did not occur at the edge of the peelable pressure-sensitive adhesive layer were evaluated as "? &Quot; The evaluation results are shown in Table 1.

As is apparent from the results of Table 1, the peelable pressure-sensitive adhesive films of Examples 1 to 4 had 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, And the peelable pressure-sensitive adhesive layer including the ionizing radiation-curable pressure-sensitive adhesive in this order, the evaluation of checkerboard peeling was good and the adhesion between the substrate and the undercoat layer and the adhesion between the undercoat layer and the peelable pressure-sensitive adhesive layer were excellent. Also, the solvent resistance test using toluene was also excellent.

Particularly, in the peelable pressure-sensitive adhesive films of Examples 1 and 2, since the amine-based curing agent was contained in a proportion of 2 to 30 parts by weight based on 100 parts by weight of the carboxyl-containing resin, the adhesive strength of the undercoat layer and the peelable pressure- Adhesion and solvent resistance.

In comparison between Example 1 and Example 2, since the peelable pressure-sensitive adhesive film of Example 1 includes the particles in the undercoat layer, the surface relief shape formed by the particles exerts an embossing effect on the pressure-sensitive adhesive layer , The adhesion between the undercoat layer and the peelable pressure-sensitive adhesive layer and the initial tackiness were also superior to those in Example 2.

On the other hand, in this peelable pressure-sensitive adhesive film of Comparative Example 1, the amine-based curing agent was not included in the undercoat layer, so the adhesiveness between the substrate and the undercoat layer and the adhesiveness between the undercoat layer and the peelable pressure- Was also inferior to the solvent resistance test using.

The peelable pressure-sensitive adhesive film of Comparative Example 2 was prepared by using an isocyanate-based curing agent instead of the amine-based curing agent in the undercoat layer. In Comparative Example 1, the adhesion between the base and the undercoat layer and the adhesion between the undercoat layer and the peelable pressure- The adhesion could not be improved.

The peelable pressure-sensitive adhesive film of Comparative Example 3 was prepared by using a bifunctional acrylate monomer instead of an amine-based curing agent in order to improve the adhesion between the substrate and the undercoat layer and the adhesion between the undercoat layer and the peelable pressure- The adhesion between the substrate and the undercoat layer and the adhesion between the undercoat layer and the peelable pressure-sensitive adhesive layer were inferior to those of the examples using the pressure-sensitive adhesive layer, and the test was also inferior to the solvent resistance test using toluene.

The peelable pressure-sensitive adhesive film of Comparative Example 4 had an amine curing agent and a carboxyl group-containing resin. However, since the acid value of the carboxyl group-containing resin was less than 10 mgKOH / g, the adhesion between the undercoat layer and the peelable pressure- And it was inferior to the solvent resistance test using toluene.

Claims (8)

A releasable pressure-sensitive adhesive film comprising an undercoat layer and a releasable pressure-sensitive adhesive layer laminated in this order on a transparent resin film,
Wherein the undercoat layer comprises an amine-based curing agent and a carboxyl group-containing resin having an acid value of 10 to 100 mgKOH / g,
Wherein the peelable pressure-sensitive adhesive layer comprises an ionizing radiation-curable pressure-sensitive adhesive. The method according to claim 1,
Wherein the peelable pressure-sensitive adhesive layer further comprises an isocyanate-based curing agent. 3. The method of claim 2,
Wherein 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. 4. The method according to any one of claims 1 to 3,
Wherein 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. 5. The method according to any one of claims 1 to 4,
Wherein the amine-based curing agent is a trifunctional aziridine compound. A) a step of adhering a surface of the peelable pressure-sensitive adhesive film described in any one of claims 1 to 5 having a peelable pressure-sensitive adhesive layer to a metal plate,
B) a step of irradiating the releaseable pressure-sensitive adhesive film adhered to the metal plate to cure the releaseable pressure-sensitive adhesive layer,
C) a step of forming a mask on a surface of the metal plate opposite to the surface having the peelable pressure-sensitive adhesive film, and dipping the metal plate in an etching solution to remove the metal plate on the portion where the mask is not formed;
D) removing the mask from the metal plate, and peeling off the peelable pressure-sensitive adhesive film
Wherein the metal plate is a metal plate. The method according to claim 6,
B) is carried out after the step of C). 8. The method according to claim 6 or 7,
D), after removing the mask from the metal plate, before peeling the peelable pressure-sensitive adhesive film,
E) transferring the metal plate to a transfer object.