JPWO2017200103A1 - Release film - Google Patents

Abstract

A support comprising a substrate and an adhesive layer disposed on the substrate, and an electromagnetic wave shielding sheet disposed on the adhesive layer of the support, wherein the adhesive layer and the electromagnetic wave shielding sheet are interposed between The release film whose peeling force is 0.10 N / 50 mm-2.00 N / 50 mm.

Description

  The present invention relates to a release film.

  In recent years, with the progress of miniaturization of electronic devices, further improvement of high density mounting technology on the surface of a semiconductor element is required. Therefore, in recent years, a so-called stack package type semiconductor device in which a plurality of semiconductor elements are stacked in multiple stages is adopted. In such a stacked package type semiconductor device, since semiconductor elements are arranged in an integrated state, a problem due to external noise (electromagnetic wave interference) may occur. The problem of such noise becomes more remarkable as the digitization, speeding up, and higher frequency of electronic devices progress. Then, in order to suppress the influence by noise, the technique which forms the electromagnetic wave shielding sheet for shielding electromagnetic waves on the sealing material which seals a semiconductor element is proposed (for example, refer patent document 1).

  As a method of forming an electromagnetic wave shielding sheet, for example, a method of manufacturing a semiconductor device described in Patent Document 2 is known. In this manufacturing method, an electromagnetic shielding sheet is formed on a release film (carrier film) disposed on the upper mold in the step of sealing the semiconductor element with a sealing material by transfer molding using the upper mold and the lower mold. Material is applied, and the material is transferred onto a sealing material and cured to form an electromagnetic shielding sheet.

Patent No. 4133637 gazette JP 2007-287937 A

  However, in the method described in Patent Document 2, every time the step of sealing the semiconductor device with the sealing material, the work of applying the material for forming the electromagnetic wave shielding sheet on the carrier film every time is required, so production There is room for improvement in terms of efficiency.

  The present invention was made in order to solve the above-mentioned subject, and it aims at providing a mold release film which can aim at improvement of production efficiency of a semiconductor device which has an electromagnetic wave shielding sheet.

Means for solving the above problems include the following embodiments.
<1> A base material and a support including an adhesive layer disposed on the base, and an electromagnetic wave shielding sheet disposed on the adhesive layer of the support, the adhesive layer and the electromagnetic wave shielding sheet A release film, wherein the peeling force between is 0.10 N / 50 mm to 2.00 N / 50 mm.
The release film as described in <1> whose thickness of the <2> above-mentioned electromagnetic wave shielding sheet is 0.01 micrometer-50 micrometers.
The thickness of the <3> above-mentioned adhesion layer is a release film as described in <1> or <2> which is 1 micrometer-20 micrometers.
The release film as described in any one of <1>-<3> in which the <4> above-mentioned adhesion layer contains at least 1 sort (s) selected from the group which consists of a silicone type adhesive and an acrylic adhesive.
The mold release film of any one of Claims 1-4 for manufacture of the semiconductor device containing the process of transcribe | transferring the said electromagnetic wave shielding sheet to the sealing material which seals <5> semiconductor element.

  According to the present invention, there is provided a release film capable of improving the production efficiency of a semiconductor device having an electromagnetic wave shielding sheet.

It is a schematic sectional drawing which shows an example of the structure of the release film of this embodiment. It is a schematic plan view which shows an example of the structure of the release film of this embodiment.

  Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.

In the present specification, the term "step" includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. Be
In the numerical value range indicated by using “to” in the present specification, the numerical values described before and after “to” are included as the minimum value and the maximum value, respectively.
In the numerical ranges that are described stepwise in the present specification, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in the other stepwise Good. In addition, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present specification, the content or content of each component in the composition is the number of the plurality of types present in the composition unless a plurality of substances corresponding to each component are present in the composition. The total content or content of substances is meant.
In the present specification, the particle diameter of each component in the composition is the mixture of the plurality of particles present in the composition unless a plurality of particles corresponding to each component are present in the composition. Means a value about.
In the present specification, the words “layer” or “film” mean, when observing a region in which the layer or film is present, in addition to the case where the region is formed in its entirety, a part of the region Also included if only formed.
As used herein, the term "laminate" refers to stacking layers, two or more layers may be combined, and two or more layers may be removable.
In the present specification, “(meth) acryloyl group” means at least one of acryloyl group and methacryloyl group, “(meth) acryl” means at least one of acrylic and methacryl, “(meth) acrylate” is acrylate and It means at least one of methacrylates.

  The release film of the present embodiment includes a support including a substrate and an adhesive layer disposed on the substrate, and an electromagnetic wave shielding sheet disposed on the adhesive layer of the support, the adhesive The peeling force between the layer and the electromagnetic wave shielding sheet is 0.10 N / 50 mm to 2.00 N / 50 mm.

  By having the above configuration, the release film of the present embodiment can satisfactorily peel the electromagnetic wave shielding sheet from the support even if the electromagnetic wave shielding sheet is disposed on the support in advance before the sealing step. Therefore, since it is not necessary to arrange an electromagnetic wave shielding sheet on a release film every time of a sealing process, and it is not necessary to form an electromagnetic wave shielding layer by another process after sealing, it is advantageous from the viewpoint of production efficiency. Therefore, the release film of this embodiment is a method of manufacturing a semiconductor device having an electromagnetic wave shielding sheet (more specifically, a semiconductor device including a step of transferring the electromagnetic wave shielding sheet to a sealing material for sealing a semiconductor element) Is preferably used in the production method of

  In the present specification, the "peel force between the adhesive layer and the electromagnetic wave shielding sheet" is a value measured at a peel angle of 180 ° and a peel speed of 0.3 m / min under an atmosphere of 170 ° C. (N / 50 mm) It is. Peeling force can be measured, for example, using a Tensilon universal material tester (manufactured by A & D Co., Ltd.).

  When the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 0.10 N / 50 mm or more, peeling of the electromagnetic wave shielding sheet at a high temperature tends to be suppressed. If the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 2.00 N / 50 mm or less, the transferability of the electromagnetic wave shielding sheet from the adhesive layer tends to be sufficiently obtained. The peeling force between the adhesive layer and the electromagnetic wave shielding sheet is preferably 0.20 N / 50 mm or more, and preferably 1.60 N / 50 mm or less.

  Hereinafter, although the release film of this embodiment is demonstrated with reference to drawings, this invention is not limited to this. Further, the sizes of the members in the respective drawings are conceptual, and the relative relationship between the sizes of the members is not limited thereto.

  FIG. 1 is a schematic cross-sectional view showing an example of the structure of the release film of the present embodiment. The release film 10 includes a base 20 and a support 20 including an adhesive layer 40 disposed on the base 50, and an electromagnetic wave shielding sheet 30 disposed on the adhesive layer 40 of the support 20. In the support 2, the pressure-sensitive adhesive layer may be disposed on the entire surface of the substrate 50 or may be disposed on only a part, and the shape thereof is not particularly limited.

  In the release film 10, the position where the electromagnetic wave shielding sheet 30 is disposed is not particularly limited as long as it is on the adhesive layer 40. For example, as shown in the schematic plan view of FIG. 2, the electromagnetic wave shielding sheet 30 may be disposed on only a part of the support 20 or the electromagnetic shielding sheet 30 may be disposed on the entire surface of the support 20. The shape of the electromagnetic wave shielding sheet 30 is not particularly limited, and may be a desired shape such as a square or a circle. The electromagnetic wave shielding sheet 30 may be arranged at intervals in a plurality of areas, and the interval between the areas in this case is not particularly limited.

  The method of disposing the electromagnetic wave shielding sheet 30 on the adhesive layer 40 is not particularly limited. For example, a sputtering method, a vapor deposition method, an ion plating method, a lamination method and the like can be mentioned. From the viewpoint of adhesion to the adhesive layer 40, a vapor deposition method, an ion plating method or a lamination method is preferable. The material of the electromagnetic wave shielding sheet 30 is not particularly limited. For example, metals can be mentioned. From the viewpoint of cost and processability, it is preferable to include at least one metal element selected from the group consisting of copper and aluminum.

  The thickness of the substrate 50 is preferably 20 μm to 200 μm, more preferably 25 μm to 100 μm, and still more preferably 25 μm to 50 μm. When the thickness of the substrate 50 is 20 μm or more, sufficient strength is obtained, and the occurrence of problems such as warpage of the lead frame tends to be suppressed, and when 200 μm or less, the compatibility with the semiconductor manufacturing apparatus tends to be excellent. It is in.

  The thickness of the adhesive layer 40 is preferably 1 μm to 20 μm, and more preferably 2 μm to 12 μm. When the thickness of the adhesive layer 40 is 1 μm or more, the transfer of the electromagnetic wave shielding sheet 30 from the adhesive layer 40 to the adherend tends to be favorably performed, and when the thickness is 20 μm or less, the electromagnetic wave shielding sheet 30 during the sealing step. Tend to be difficult to peel off from the adhesive layer 40.

  The thickness of the electromagnetic shielding sheet 30 is preferably 0.01 μm to 50 μm, and more preferably 0.05 μm to 12 μm. When the thickness of the electromagnetic wave shielding sheet 30 is 0.01 μm or more, sufficient electromagnetic wave shielding properties tend to be obtained, and when the thickness is 50 μm or less, the processability tends to be excellent.

  In the present specification, the thicknesses of the substrate 50, the adhesive layer 40, and the electromagnetic wave shielding sheet 30 are taken as a number average value of values obtained by measuring at five points. The measuring method in particular of thickness is not restrict | limited, It can carry out by a well-known method.

  The release film 10 may have members other than the base 50, the adhesive layer 40, and the electromagnetic wave shielding sheet 30 as needed. For example, a protective film may be provided to protect the surface of the release film 10.

<Adhesive layer>
The adhesive layer is not particularly limited as long as the peeling force with the electromagnetic wave shielding sheet falls within the above range. For example, a layer containing a pressure-sensitive adhesive such as a silicone-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a urethane-based pressure-sensitive adhesive can be mentioned. The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer may be one kind alone, or two or more kinds.
The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer in the present invention may be partially or completely reacted or unreacted. Further, it may be in a cured state by heat or the like, or in a non-cured state.

(1) Silicone-Based Pressure-Sensitive Adhesive In the present specification, silicone-based pressure-sensitive adhesives mean pressure-sensitive adhesives in which a silicone polymer is a base polymer (a main component of polymer components, that is, a component that occupies 50% by mass or more of all polymer components). Do.
The silicone-based pressure-sensitive adhesive is advantageous from the viewpoints of relatively low peeling force, the electromagnetic wave shielding sheet being easily peeled from the pressure-sensitive adhesive layer, and the adhesive residue (residue of the pressure-sensitive adhesive) on the electromagnetic wave shielding sheet can be suppressed. is there. Examples of the silicone-based pressure-sensitive adhesive include an addition reaction-type silicone-based pressure-sensitive adhesive, a peroxide-curable silicone-based pressure-sensitive adhesive, and a condensation-type silicone-based pressure-sensitive adhesive. From the viewpoint that no peroxide is used for the curing reaction and no decomposition product is generated, an addition reaction type silicone-based pressure-sensitive adhesive is preferable.

(Addition reaction type silicone pressure sensitive adhesive)
An addition reaction type silicone pressure-sensitive adhesive is a monovalent carbonization of at least two alkenyl groups (vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, etc.) in one molecule. And an addition reaction type silicone resin containing a first polydimethylsiloxane having a hydrogen group, and particularly preferably a vinyl group) and a second polydimethylsiloxane having at least two hydrosilyl groups in one molecule. And a silicone resin.

The content of alkenyl groups (the ratio of the number of alkenyl groups to the number of siloxane bonds) in the first polydimethylsiloxane is preferably 0.01% to 10%, and is 0.1% to 5%. Is more preferred. The alkenyl group is preferably present at least at both ends of the molecular chain, and more preferably at both ends and side chains. The polymerization degree (number of siloxane bonds) of the first polydimethylsiloxane is preferably 200 to 5,000, and more preferably 500 to 3,000.
The weight average molecular weight of the first polydimethylsiloxane is preferably 20,000 to 1,300,000, and more preferably 300,000 to 1,200,000.

  In the present specification, the molecular weight (weight-average molecular weight and number-average molecular weight) of a polymer is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  The content of the hydrosilyl group in the second polydimethylsiloxane is preferably 2 to 300 in one molecule, and more preferably 4 to 200 in one molecule. The degree of polymerization (number of siloxane bonds) of the second polydimethylsiloxane is preferably 50 to 2,000, and more preferably 100 to 1,500.

  In the addition reaction type silicone resin, the ratio of the first polydimethylsiloxane to the second polydimethylsiloxane is, for example, 0.01 mass of the blending ratio of the second polydimethylsiloxane to 100 parts by mass of the first polydimethylsiloxane. It is preferable that it is part-20 mass parts, and it is more preferable that it is 0.1 mass part-10 mass parts.

  The content of the alkenyl group contained in the first polydimethylsiloxane, the content of the hydrosilyl group contained in the second polydimethylsiloxane, and the compounding ratio of the second polydimethylsiloxane to the first polydimethylsiloxane are each as described above. The addition reaction between the first polydimethylsiloxane and the second polydimethylsiloxane tends to proceed well. The first polydimethylsiloxane preferably has no hydrosilyl group, and the second polydimethylsiloxane preferably does not have an alkenyl group.

The silicone resin has a role of imparting tackiness to the silicone pressure sensitive adhesive. As used herein, silicone resin means silicone having a three-dimensional network structure.
As a silicone resin, for example, an MQ resin composed of an M unit which is a monofunctional siloxane unit [(CH ₃ ) ₃ SiO _1/2 ] and a Q unit which is a tetrafunctional siloxane unit [SiO _4/2 ] It can be mentioned. The molar ratio of M units to Q units (M units / Q units) in the MQ resin is preferably 0.6 to 1.7.

  In the addition reaction type silicone pressure sensitive adhesive, the compounding ratio of the silicone resin to 100 parts by mass of the addition reaction type silicone resin is preferably 1 part by mass to 30 parts by mass, and more preferably 3 parts by mass to 20 parts by mass. Preferably, it is 5 parts by mass to 15 parts by mass. By setting the compounding ratio of the silicone resin in such a range, the releasability of the addition reaction type silicone-based pressure-sensitive adhesive can be adjusted to a desired range. That is, the electromagnetic wave shielding sheet is more easily peeled off from the pressure-sensitive adhesive layer obtained using the addition reaction type silicone pressure sensitive adhesive, and the adhesive residue on the electromagnetic wave shielding sheet tends to be less likely to occur.

  The addition reaction type silicone-based pressure-sensitive adhesive preferably contains a catalyst. By containing the catalyst, the curing reaction of the addition reaction type silicone resin can be advanced more efficiently. The catalyst is not particularly limited as long as it is capable of causing an addition reaction of the first polydimethylsiloxane and the second polydimethylsiloxane, and among them, a compound containing a platinum group metal is preferable. Examples of the platinum group metal-containing compound include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium and the like.

  When the addition reaction type silicone pressure-sensitive adhesive contains a catalyst, the compounding amount of the catalyst per 100 parts by mass of the addition reaction type silicone resin (when the catalyst is a compound containing a platinum group metal, an amount corresponding to a platinum group metal) is 0 It is preferable that it is .0001 mass part-0.1 mass part, and it is more preferable that it is 0.001 mass part-0.01 mass part.

(Peroxide curable silicone pressure sensitive adhesive and condensation silicone pressure sensitive adhesive)
The peroxide-curable silicone-based pressure-sensitive adhesive is generally a pressure-sensitive adhesive that cures (crosslinks) an organopolysiloxane with a peroxide to form a silicone-based polymer. In addition, a condensation type silicone-based adhesive is generally an adhesive that forms a silicone-based polymer by dehydration or dealcoholization reaction between polyorganosiloxanes having hydrolyzable silyl groups such as silanol group or alkoxysilyl group at the terminal. .

  In the case of a peroxide-curable silicone pressure-sensitive adhesive, a silicone rubber having at least a methyl group is used, and in the case of a condensation-type silicone pressure-sensitive adhesive, a silicone rubber having a silanol group or a hydrolyzable alkoxysilyl group at the end is used. The weight average molecular weight of the organopolysiloxane in the silicone rubber is usually 150,000 or more, preferably 280,000 to 1,000,000, and more preferably 500,000 to 900,000.

  The silicone-based pressure-sensitive adhesive may contain, in addition to the polymer component, various additives such as a reaction inhibitor and an adhesion improver.

  The method for forming the adhesive layer on the substrate using a silicone-based adhesive is not particularly limited. For example, it can be formed by applying a silicone-based pressure-sensitive adhesive on a substrate, drying it as necessary, and curing it. The application can be performed using, for example, a coating machine such as a bar coater, a die coater, a gravure coater, a roll coater, or a knife coater.

  When the silicone-based pressure-sensitive adhesive contains a diluent, the diluent is not particularly limited. Examples thereof include hydrocarbon compounds such as toluene, hexane and heptane, acetone, ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone. The diluent contained in the silicone-based pressure-sensitive adhesive may be one kind alone or two or more kinds.

  When the silicone-based pressure-sensitive adhesive is an addition reaction-type silicone pressure-sensitive adhesive, it is preferable to heat and cure after adding the addition-reaction-type silicone pressure-sensitive adhesive on a substrate. The heating temperature in this case is preferably 80 ° C. to 180 ° C., and the heating time is preferably about 10 seconds to 90 seconds.

(2) Acrylic Pressure-Sensitive Adhesive In the present specification, an acrylic pressure-sensitive adhesive means a pressure-sensitive adhesive containing an acrylic polymer as a base polymer. With an acrylic polymer, a monomer having at least one (meth) acryloyl group in one molecule (hereinafter, this may be referred to as "acrylic monomer") is a main constituent monomer component (acrylic polymer) (A component that accounts for 50% by mass or more of the total amount of monomers). Acrylic pressure-sensitive adhesives are advantageous in terms of transparency, weather resistance, heat resistance, solvent resistance, and the like.

  When designing an acrylic polymer contained in an acrylic pressure-sensitive adhesive, introduction of a glass transition point (adhesion to an adherend, applicable temperature, etc.), crosslinking point (durability, heat resistance, etc.), acrylic monomer It is important to control the kind, molecular weight and the like of the monomer in consideration of the copolymerizability (the molecular structure of the acrylic polymer, uniformity of the crosslinking point, etc.) and the like. In order to introduce a crosslinking point into the molecule, an acrylic polymer is synthesized using a monomer (acrylic acid, hydroxyethyl acrylate, etc.) containing a functional group capable of reacting with the crosslinking agent used in combination.

As an acryl-type polymer, the polymer which has an alkyl (meth) acrylate as a main component monomer component is mentioned. As the alkyl (meth) acrylate, for example, a compound represented by the following formula (1) can be suitably used.
CH ₂ = C (R ¹ ) COOR ² (1)

Here, R ¹ in the above formula (1) represents a hydrogen atom or a methyl group, and R ² is an alkyl group having 1 to 20 carbon atoms (either a linear alkyl group or an alicyclic alkyl group May be

From the viewpoint of obtaining a pressure-sensitive adhesive having excellent adhesion performance, R ² is a linear alkyl group having 2 to 14 (C 2 to 14) carbon atoms (which may be either a linear alkyl group or a branched alkyl group) Is preferred. As a C2-14 chain | strand-shaped alkyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isoamyl group, neopentyl group , N-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group etc. are mentioned. When R ² is an alicyclic alkyl group, examples of the alicyclic alkyl group include a cyclohexyl group and an isobornyl group.

From the viewpoint of obtaining an acrylic polymer excellent in adhesion performance, 50% by mass or more (for example, 50% by mass to 99.9% by mass) of the total amount of monomers used for synthesizing the acrylic polymer, more preferably 70% by mass More (for example, 70% by mass to 99.9% by mass), more preferably 85% by mass or more (for example, 85% by mass to 99.9% by mass), R ² in the above formula (1) is C2-14 (Meth) acrylate which is a linear alkyl group is preferable, more preferably R ² is a C4-10 linear alkyl acrylate, and at least one selected from n-butyl acrylate and 2-ethylhexyl acrylate It is further preferred that

  The acrylic polymer preferably has a hydroxyl group as a crosslinking point. As an acryl-type polymer which has a hydroxyl group, what contains the acryl-type monomer containing a hydroxyl group in a superposition | polymerization component can be used preferably.

  Specific examples of the acrylic monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (Meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, polypropylene glycol mono (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylate ) Acrylamide, and the like. The acrylic monomers containing a hydroxyl group may be used alone or in combination of two or more.

  Among the acrylic monomers containing a hydroxyl group, (meth) acrylates containing a hydroxyl group are preferable. As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Preferred is butyl (meth) acrylate or the like.

  In the acrylic polymer having a hydroxyl group, the proportion of the acrylic monomer having a hydroxyl group in the total amount of monomers used for the synthesis may be, for example, in the range of 0.01 mass% to 20 mass%, 0.05 mass The content is preferably in the range of% to 15% by mass, and more preferably in the range of 0.1% by mass to 10% by mass.

  The acrylic polymer may contain an acrylic monomer having a functional group other than a hydroxyl group and a monomer other than the acrylic monomer (hereinafter, also referred to as another monomer) as a polymerization component. Other monomers can be used, for example, for the purpose of adjusting Tg of an acrylic polymer, adhesion performance, and the like. For example, as a monomer capable of improving the cohesion and heat resistance of the pressure-sensitive adhesive, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester, an aromatic vinyl compound and the like can be mentioned. Further, as a monomer capable of introducing a functional group capable of becoming a crosslinking point into an acrylic polymer, or contributing to the improvement of adhesion, a carboxy group-containing monomer, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, Imide group-containing monomers, epoxy group-containing monomers, (meth) acryloyl morpholine, vinyl ethers and the like can be mentioned. The other monomers may be used alone or in combination of two or more.

As a sulfonic acid group-containing monomer, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, (meth) acrylamidopropane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxy Naphthalene sulfonic acid, sodium vinyl sulfonate and the like can be mentioned.
As a phosphoric acid group containing monomer, 2-hydroxyethyl acryloyl phosphate etc. are mentioned.
Examples of cyano group-containing monomers include acrylonitrile and methacrylonitrile.
As vinyl esters, vinyl acetate, vinyl propionate, vinyl laurate and the like can be mentioned.
Examples of the aromatic vinyl compound include styrene and substituted styrene (chlorostyrene, chloromethylstyrene, α-methylstyrene and the like) and the like.

Examples of carboxy group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
Examples of the acid anhydride group-containing monomer include maleic anhydride, itaconic acid anhydride, and acid anhydrides of the above-mentioned carboxy group-containing monomers.
As the amide group-containing monomer, acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N, N'- methylenebis acrylamide, N, N- dimethylaminopropyl acrylamide, N, N- dimethylaminopropyl methacrylamide, diacetone acrylamide etc. are mentioned.
Examples of amino group-containing monomers include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate.
Examples of imide group-containing monomers include cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaconimide and the like.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether and the like.
Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.

  When the acrylic polymer contains other monomers as a polymerization component, the content of the other monomers is preferably such that the total of the other monomers is 40% by mass or less of the total of the monomers used for the synthesis of the acrylic polymer And 30% by mass or less. Moreover, it is preferable that the sum total of another monomer is 0.001 mass% or more among the total amounts of the monomer used for the synthesis | combination of an acryl-type polymer.

  The acrylic polymer may have only an acrylic monomer as a polymerization component. As an acrylic polymer having only an acrylic monomer as a polymerization component, for example, an acrylic polymer having only an alkyl (meth) acrylate having 6 to 14 carbon atoms as a polymerization component, an alkyl (meth) having 6 to 14 carbon atoms The acrylic polymer etc. which use only an acrylate and a hydroxyl-containing (meth) acrylate as a polymerization component are mentioned.

The acrylic polymer may have a weight average molecular weight (Mw) in terms of standard polystyrene equivalent obtained by gel permeation chromatography (GPC) of, for example, 20 × 10 ⁴ or more, and preferably 30 × 10 ⁴ or more. Further, for example, it may be 90 × 10 ⁴ or less, and preferably 80 × 10 ⁴ or less. When the weight average molecular weight of the acrylic polymer is in the above range, a pressure-sensitive adhesive having a good adhesion performance tends to be obtained.

  The acrylic polymer may be a random copolymer, a block copolymer, or a graft copolymer. From the viewpoint of productivity and the like, it is usually preferable to be a random copolymer.

  The glass transition temperature (Tg) of the acrylic polymer is preferably -15 ° C or less, more preferably -25 ° C or less, and still more preferably -40 ° C or less. Moreover, it is preferable that a glass transition temperature (Tg) is -70 degreeC or more. When the glass transition temperature (Tg) of the acrylic polymer is in the above range, a pressure-sensitive adhesive exhibiting a good adhesion performance tends to be formed.

  In the present specification, the Tg of an acrylic polymer refers to the Tg of a homopolymer (homopolymer) of each monomer constituting the acrylic polymer, and Fox based on the mass fraction of the monomer (the copolymerization ratio on a mass basis). The value obtained from the equation (Fox). Accordingly, the Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the type of the monomer used for the synthesis of the acrylic polymer, the ratio of the amount used, etc.) The value of (Polymer Handbook) (3rd edition, John Wiley & Sons, Inc, 1989) described in the publicly known data shall be adopted. Specifically as the Tg of the above-mentioned homopolymer, the following values It shall be used.

Homopolymer of 2-ethylhexyl acrylate: -70 ° C
Homopolymer of n-butyl acrylate: -55 ° C
Ethyl acrylate homopolymer: -22 ° C
Methyl acrylate homopolymer: 8 ° C
Methyl methacrylate homopolymer: 105 ° C
Homopolymer of cyclohexyl methacrylate: 66 ° C.
Vinyl acetate homopolymer: 32 ° C.
Styrene homopolymer: 100 ° C
Acrylic acid homopolymer: 106 ° C
Methacrylic acid homopolymer: 130 ° C.

As Tg of the homopolymer which is not described in "Polymer Handbook", a value measured by the following method is used.
100 parts by mass of a monomer, 0.2 parts by mass of azobisisobutyronitrile, and 200 parts by mass of ethyl acetate as a polymerization solvent are charged into a reactor equipped with a thermometer, a stirrer, a nitrogen introducing pipe and a reflux condenser. Stir at room temperature (25 ° C.) for 1 hour while flowing nitrogen gas. After oxygen in the polymerization system is removed in this manner, the temperature is raised to 63 ° C. and reaction is carried out for 10 hours. Then, it is cooled to room temperature (25 ° C.) to obtain a homopolymer solution having a solid content concentration of 33% by mass. Next, this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. This test sample is punched into a disc shape of 7.9 mm in diameter, sandwiched by parallel plates, and subjected to shear strain at a frequency of 1 Hz using a viscoelasticity tester (ARES, Rheometrics), temperature range -70 ° C to 150 ° C. The visco-elasticity is measured by a shear mode at a heating rate of 5 ° C./min, and the peak top temperature of tan δ is taken as the Tg of the homopolymer.

  The method of synthesizing the acrylic polymer is not particularly limited, and generally used methods such as solution polymerization method, emulsion polymerization method, bulk polymerization method and suspension polymerization method can be applied. From the viewpoint of preparation of the solvent-based pressure-sensitive adhesive composition containing the acrylic polymer, the solution polymerization method is preferable. The organic solvent (polymerization solvent) used in the solution polymerization method is not particularly limited, and examples thereof include toluene, ethyl acetate, hexane, cyclohexane and the like. The organic solvent to be used may be one kind alone or two or more kinds.

  In the present specification, the solvent-type pressure-sensitive adhesive composition means a composition in a form including an adhesive component in an organic solvent. The organic solvent is not particularly limited. For example, toluene, xylene, ethyl acetate, hexane, cyclohexane, methylcyclohexane, isopropyl alcohol and the like can be mentioned. The organic solvents may be used alone or in combination of two or more. The solvent-based pressure-sensitive adhesive composition preferably has an NV (nonvolatile content) of 30% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass. The viscosity of the solvent-type pressure-sensitive adhesive composition is preferably 3 Pa · s to 25 Pa · s, and more preferably 5 Pa · s to 15 Pa · s. In addition, the said viscosity says the value measured using a rotational viscometer in a 23 degreeC environment.

  The acrylic adhesive may be designed to crosslink the acrylic polymer. As a specific method of crosslinking the acrylic polymer, a functional group is introduced into the acrylic polymer by including a monomer having a functional group (hydroxyl group, carboxy group, etc.) which can be a crosslinking point in the polymerization component of the acrylic polymer. There may be mentioned a method of adding a compound (crosslinking agent) capable of reacting with this functional group to form a crosslinked structure (crosslinking agent) and reacting it.

  The crosslinking agent is not particularly limited, and may be selected from general compounds used for crosslinking of acrylic polymers. For example, epoxy type crosslinking agent, isocyanate type crosslinking agent, melamine type crosslinking agent, peroxide type crosslinking agent, metal alkoxide type crosslinking agent, metal chelate type crosslinking agent, metal salt type crosslinking agent, carbodiimide type crosslinking agent, oxazoline type crosslinking agent Agents, aziridine type crosslinking agents, amine type crosslinking agents, etc., among which epoxy type crosslinking agents and isocyanate type crosslinking agents are preferable. The crosslinking agent used may be used alone or in combination of two or more.

  As an epoxy type crosslinking agent, N, N, N ', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,6- Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol poly Glycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether Adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol S diglycidyl ether, two or more epoxy groups in the molecule The epoxy resin etc. which it has are mentioned.

  As an isocyanate type crosslinking agent, lower aliphatic polyisocyanate compounds such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogen Aliphatic polyisocyanate compounds such as added tolylene diisocyanate and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate Compounds; and the like.

  The use amount of the crosslinking agent can be, for example, about 0.01 parts by mass to 15 parts by mass with respect to 100 parts by mass of the acrylic polymer, 0.1 parts by mass to 10 parts by mass (for example, 0.2 parts by mass) It is preferable to set it as a part-2 mass parts). When the crosslinking agent is used in such an amount, it tends to be possible to obtain a pressure-sensitive adhesive that exhibits good adhesion performance.

  The acrylic pressure-sensitive adhesive may contain various additives as required. Examples of the additive include surface lubricants, leveling agents, antioxidants, preservatives, light stabilizers, ultraviolet absorbers, polymerization inhibitors, and silane coupling agents.

  The acrylic pressure-sensitive adhesive may contain a tackifying resin as required. The type of tackifying resin is not particularly limited, and rosin-based tackifying resin, terpene-based tackifying resin, hydrocarbon-based tackifying resin, epoxy-based tackifying resin, polyamide-based tackifying resin, elastomer-based Tackifying resins, phenolic tackifying resins, ketone tackifying resins, etc. may be mentioned. The tackifying resin contained in the acrylic pressure-sensitive adhesive may be one kind alone or two or more kinds.

Examples of rosin-based tackifying resins include unmodified rosin (raw rosin) such as gum rosin, wood rosin and tall oil rosin; modified rosin obtained by modifying unmodified rosin by hydrogenation, disproportionation, polymerization, etc. (hydrogenated rosin, Disproportionated rosin, polymerized rosin, other chemically modified rosin, etc.); other various rosin derivatives;
Examples of rosin derivatives include unmodified rosins or those obtained by esterifying modified rosins with alcohols (rosin esters); unmodified rosins or those obtained by modifying modified rosins with unsaturated fatty acids (unsaturated fatty acids modified rosins); Modified with saturated fatty acid (unsaturated fatty acid modified rosin ester); unmodified rosin, modified rosin, unsaturated fatty acid modified rosin or unsaturated fatty acid modified rosin ester with reduction of carboxy group (rosin alcohol); unmodified rosin A modified rosin and a metal salt of the above-described rosin derivative (in particular, rosin ester); unmodified rosin, modified rosin and rosin phenol resin obtained by thermally polymerizing phenol with an acid catalyst to the above rosin derivative; It can be mentioned.

  Terpene-based tackifying resins such as α-pinene polymers, β-pinene polymers, terpene resins such as dipentene polymers; these terpene resins are modified (phenol modification, aromatic modification, hydrogenation modification, carbonization Hydrogen-modified and the like) modified terpene resins; and the like. Examples of the modified terpene resin include terpene-phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin and the like.

Examples of hydrocarbon tackifying resins include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, and aliphatic / aromatic petroleum resins (such as styrene-olefin copolymers). And aliphatic and alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins and the like.
Examples of aliphatic hydrocarbon resins include polymers of one or more aliphatic hydrocarbons selected from olefins and dienes having about 4 to 5 carbon atoms, and the like. As an olefin, 1-butene, isobutylene, 1-pentene etc. are mentioned. Examples of dienes include butadiene, 1,3-pentadiene, isoprene and the like.

  Examples of the aromatic hydrocarbon resin include polymers of vinyl group-containing aromatic hydrocarbon having about 8 to 10 carbon atoms (styrene, vinyl toluene, α-methylstyrene, indene, methyl indene, etc.), etc. Be

  Alicyclic hydrocarbon-based resins obtained by cyclodimerization of a so-called “C4 petroleum fraction” or “C5 petroleum fraction” as an aliphatic cyclic hydrocarbon resin; and a cyclic diene compound (cyclopentadiene) , Polymers of dicyclopentadiene, ethylidene norbornene, dipentene etc.) or hydrogenated products thereof; alicyclic hydrocarbon resins obtained by hydrogenating the aromatic ring of an aromatic hydrocarbon resin or an aliphatic / aromatic petroleum resin; Etc.

  The tackifying resin preferably has a softening point (softening temperature) of 80 ° C. or more (preferably 100 ° C. or more). By using such a tackifying resin, a high-performance (for example, highly adhesive) adhesive tends to be obtained. The upper limit of the softening point of the tackifying resin is not particularly limited, and can be, for example, 200 ° C. or less (preferably, 180 ° C. or less). In addition, let the softening point of the tackifying resin here be the value measured by the softening point test method (ring and ball method) prescribed in either of JIS K 5902: 2006 and JIS K 2207: 2006.

  The use amount of the tackifying resin is not particularly limited, and can be appropriately set according to the desired adhesive performance (adhesive strength and the like). For example, 10 parts by mass to 100 parts by mass (preferably 15 parts by mass to 80 parts by mass, more preferably 20 parts by mass to 60 parts by mass) of tackifying resin with respect to 100 parts by mass of acrylic polymer based on solid content It is preferable to use it in the ratio of

(3) Rubber-Based Pressure-Sensitive Adhesive As used herein, a rubber-based pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a rubber-based polymer as a base polymer. The rubber-based polymer is not particularly limited, and may be a natural rubber-based polymer (including a modified natural rubber-based polymer) or a synthetic rubber-based polymer. As a synthetic rubber polymer, a block copolymer of ABA type or AB type (A indicates a thermoplastic block, B indicates a rubber block. Styrene-isoprene-styrene copolymer (SIS), styrene-butadiene-styrene And copolymers (SBS) and the like. The rubber-based polymer may be a combination of a natural rubber-based polymer and a synthetic rubber-based polymer.

  When the rubber-based adhesive contains a synthetic rubber-based polymer, examples of synthetic rubber-based polymers include polybutadiene, polyisoprene, butyl rubber, polyisobutylene, styrene butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), etc. are mentioned.

  When the rubber-based pressure-sensitive adhesive contains a modified natural rubber-based polymer, it is preferable that 50% by mass or more (for example, 60% by mass or more) of the modified natural rubber-based polymer is a structural part derived from natural rubber. Examples of the modified natural rubber polymer include a graft modified natural rubber polymer in which another monomer is grafted to a natural rubber polymer. Examples of the monomer to be grafted onto the natural rubber polymer include acrylic monomers (monomers having an acryloyl group or methacryloyl group), styrene and the like. The monomers to be grafted onto the natural rubber polymer may be used alone or in combination of two or more.

Examples of acrylic monomers to be grafted onto natural rubber polymers include alkyl acrylates (for example, alkyl acrylates having 1 to 16 carbon atoms, such as methyl acrylate, ethyl acrylate, isopropyl acrylate and t-butyl acrylate), alkyl Examples of the methacrylate include alkyl methacrylates having 1 to 16 carbon atoms, such as methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate and t-butyl methacrylate, acrylic acid and methacrylic acid.
As the modified natural rubber polymer, one in which 50% by mass or more of the monomers to be grafted to the natural rubber polymer is an acrylic monomer (acrylic modified natural rubber polymer) is preferable.

When the base polymer of the rubber-based pressure-sensitive adhesive is a natural rubber-based polymer, as a natural rubber-based polymer, for example, MS (1 + 4) 100 ° C. (use of L type rotor, preheating 1 minute, viscosity measurement time 4 minutes, test temperature 100 Those having a Mooney viscosity of about 10 to 60 under the measurement conditions of ° C.) are preferable.
In another embodiment, an acrylic modified natural rubber polymer (NR-MMA graft copolymer) obtained by grafting methyl methacrylate (MMA) to a natural rubber polymer is preferable. Such graft copolymers can be produced by a conventional method, and can also be obtained as commercial products. Graft ratio of MMA in NR-MMA graft copolymer (mass of MMA bound to natural rubber / mass of natural rubber used for grafting x 100 (%), usually NR-MMA graft copolymer Can be, for example, 1% to 120%, preferably 5% to 100%, more preferably 10, which is equivalent to the value calculated from the mass ratio of the natural rubber used in the production and MMA. % To 90%, more preferably 30% to 80%. The grafting rate is preferably 50% to 90%, more preferably 60% to 80%. When the grafting ratio is 1% or more, the adhesion is prevented from becoming too high, and when the grafting ratio is 120% or less, the adhesion to the adherend such as the SUS plate is prevented from being too low. Be done. MMA used for production of the NR-MMA graft copolymer is partially substituted with other monomers (for example, 5% by mass or less, typically 3% by mass or less of the total monomers to be grafted on natural rubber) May be

  The rubber-based pressure-sensitive adhesive may contain, in addition to the base polymer, another polymer (hereinafter also referred to as a subpolymer). Examples of the secondary polymer include acrylic polymers, polyester polymers, polyurethane polymers, silicone polymers, etc. that can be base polymers such as known acrylic adhesives, polyester adhesives, polyurethane adhesives, silicone adhesives, etc. . Alternatively, the rubber-based polymer described above may be other than the base polymer. The auxiliary polymer contained in the rubber-based pressure-sensitive adhesive may be one kind alone or two or more kinds. As a combination of a base polymer and a subpolymer, a combination of a natural rubber-based polymer as a base polymer and an NR-MMA graft copolymer as a subpolymer, an NR-MMA graft copolymer as a base polymer and as a subpolymer Examples include combinations with natural rubber polymers and the like.

  When the rubber-based pressure-sensitive adhesive contains a base polymer and a secondary polymer, the secondary polymer is used in an amount of 100 parts by mass or less based on 100 parts by mass of the base polymer (the total of two or more secondary polymers) Used. In general, the amount of the auxiliary polymer used is suitably 70 parts by mass or less, preferably 50 parts by mass or less, per 100 parts by mass of the base polymer. The rubber-based pressure sensitive adhesive may be substantially free of the secondary polymer (ie, substantially 100% by weight of the polymer component is the base polymer). In addition, a rubber-based pressure-sensitive adhesive that does not substantially contain a polymer component other than a rubber-based polymer (for example, a rubber-based pressure-sensitive adhesive that does not substantially contain a polymer component other than natural rubber and modified natural rubber) may be used.

  The rubber-based pressure-sensitive adhesive may contain a tackifier in addition to the polymer component. In particular, in the case where the polymer component contains a natural rubber-based polymer having low tackiness of itself, the inclusion of the tackifier enables to exhibit high tackiness to many kinds of adherends. When the rubber-based pressure-sensitive adhesive contains a tackifier, examples of the tackifier include those exemplified as the tackifying resin which may be contained in the acrylic pressure-sensitive adhesive.

  When the rubber-based pressure-sensitive adhesive contains a polymer component and a tackifier, the amount of the tackifier used (the total amount of two or more tackifiers) is, for example, 100 parts by mass of the polymer component The amount can be 20 parts by mass to 150 parts by mass (preferably 30 parts by mass to 100 parts by mass). If the amount of the tackifier used is 20 parts by mass or more, adhesion to an adherend such as a lead frame tends to be sufficiently obtained. On the other hand, when the amount of tackifier used is 150 parts by mass or less, adhesion to an adherend such as a lead frame (particularly, adhesion in a low temperature environment) tends to be sufficiently obtained.

  The method for applying the rubber-based pressure-sensitive adhesive on the substrate is not particularly limited. For example, a method of forming a pressure-sensitive adhesive layer directly on a substrate by applying to a substrate a pressure-sensitive adhesive composition in which a component to be a rubber-based pressure-sensitive adhesive is dissolved or dispersed in a suitable medium and drying it A known method such as a method of transferring the pressure-sensitive adhesive layer formed on the surface having a surface to a substrate can be appropriately adopted. The pressure-sensitive adhesive composition can be prepared, for example, by mixing the polymer component, typically a tackifier, other components which are optionally used, and the above-mentioned medium according to a conventional method.

  The rubber pressure-sensitive adhesive may contain a vulcanization accelerator, if necessary. As a vulcanization accelerator, dithiocarbamates (sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, etc.), thiazoles (2-mercaptobenzothiazole, dibenzothiazyl disulfide, etc.), guanidines (Diphenylguanidine, di-o-tolyl guanidine, etc.), Sulfenamides (benzothiazyl-2-diethylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide etc.), Thiurams (Tetramethylthiuram monosulfide, etc.) , Tetramethylthiuram disulfide, etc., xanthogenic acids (sodium isopropyl xanthate, zinc isopropyl xanthate etc.), aldehydes ammonia (aceto) Aldehyde ammonia, hexamethylenetetramine, etc.), aldehydes amines (n- butyraldehyde aniline, butyraldehyde monobutylamine, etc.), thioureas (diethyl thiourea, trimethyl thiourea, etc.) and the like. The vulcanization accelerator contained in the rubber-based pressure-sensitive adhesive may be one kind alone or two or more kinds. For example, dithiocarbamic acids and thiurams may be used in combination. The use amount of the vulcanization accelerator can be, for example, 0.1 parts by mass to 10 parts by mass (preferably 0.5 parts by mass to 5 parts by mass) with respect to 100 parts by mass of the polymer component.

  The rubber-based pressure-sensitive adhesive may optionally contain a crosslinking agent. As a crosslinking agent, an isocyanate compound, sulfur, a sulfur-containing compound, a phenol resin, an organic metal compound etc. are mentioned. As a crosslinking agent, an isocyanate compound is preferable, and a bifunctional or more functional isocyanate compound is more preferable. As the bifunctional or higher isocyanate compounds, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylenediocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Corronate L"), trimethylolpropane / Hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HL), hexamethylene diisocyanate Isocyanurate body (Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HX") isocyanate adducts of the like; and the like. The crosslinking agent contained in the rubber-based pressure-sensitive adhesive may be one kind alone, or two or more kinds. The amount of the crosslinking agent used (in the case of the isocyanate compound) is preferably 0.3 parts by mass to 10 parts by mass (for example, 0.5 parts by mass to 5 parts by mass) with respect to 100 parts by mass of the polymer component.

  The rubber-based pressure-sensitive adhesive may contain a vulcanization acceleration auxiliary, if necessary. Examples of the vulcanization acceleration assistant include zinc stearate and the like. By using a vulcanization acceleration auxiliary, the vulcanization accelerator can be activated to accelerate the vulcanization efficiency. When the vulcanization accelerating auxiliary is contained, the amount used may be, for example, 0.1 parts by mass to 10 parts by mass (preferably 0.5 parts by mass to 5 parts by mass) with respect to 100 parts by mass of the polymer component. it can.

  The rubber-based pressure-sensitive adhesive may contain an additive as required. Examples of the additive include a softener, a flame retardant, an antistatic agent, a light stabilizer (a radical scavenger, an ultraviolet absorber and the like), an antioxidant and the like.

(4) Urethane-Based Pressure-Sensitive Adhesive As used herein, a urethane-based pressure-sensitive adhesive means a pressure-sensitive adhesive having a urethane polymer as a base polymer. Examples of the urethane polymer include polymers obtained by reacting a polyol and a polyisocyanate compound, and a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyol and an excess amount of a polyisocyanate compound (hereinafter referred to as “terminal NCO” Preferred are "prepolymers". The terminal NCO prepolymer is such that, for example, the equivalent ratio of OH to NCO (number of OH / number of NCO) becomes 1 / 1.2-3.5, with various polyols and excess polyisocyanate compound. Can be synthesized by reacting with The reaction may be carried out using an appropriate reaction catalyst (organotin-based catalyst such as dibutyltin dilaurate, bismuth-based catalyst such as bismuth octylate), or tertiary amine-based catalyst such as 1,4-diaza [2.2.2] bicyclooctane. And the like, for example, at 20 ° C. to 90 ° C. (preferably 60 ° C. to 90 ° C.) for 1 hour to 7 hours.

  The content of terminal isocyanate group (NCO) in the terminal NCO prepolymer is preferably 0.2% by mass to 15.0% by mass from the viewpoint of storage stability of the prepolymer and flexibility of a cured product, and 0 It is more preferable that it is 0.5 mass%-3.5 mass%. The number average molecular weight of the terminal NCO prepolymer is usually 3,000 to 50,000, and preferably 4,000 to 30,000 from the viewpoint of handling.

  As a polyol, a polyether obtained by addition polymerizing propylene oxide or propylene oxide and an alkylene oxide such as ethylene oxide to a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol or sucrose Polyols; ethylene glycol, propylene glycol and their oligoglycols; butylene glycol, hexylene glycol, and polytetramethylene ether glycol; polycaprolactone polyol; polyester polyols such as polyethylene adipate; polybutadiene polyols; hydroxy such as castor oil Group fatty acid esters; polyether polyols or polyester polyols Polymer polyols grafted vinyl monomer; and the like. The polyols used for the synthesis of the urethane polymer may be one kind alone or two or more kinds.

The polyol may be a polymer. When the polyol is a polymer, the number average molecular weight is preferably 500 to 20,000, and more preferably 1,000 to 20,000, from the viewpoint of reactivity and workability.
From the viewpoint of obtaining an excellent balance of these properties when combined with a specific curing catalyst described later, from the viewpoint of foam suppression, workability, curability and stability of physical properties, the polyol is a propylene oxide It is preferable that it is a polyoxyalkylene polyol as an adduct or a polyoxyalkylene polyol as an adduct of propylene oxide and ethylene oxide. From the viewpoint of practicability, polyoxyalkylene polyols (that is, polypropylene polyols) as adducts of propylene oxide are more preferable, and polypropylene glycols are more preferable.

The polyol may be a rosin diol. By using a rosin diol, the tackiness of the pressure sensitive adhesive becomes better. The rosin diol is a diol having two rosin skeleton and two hydroxyl groups in the molecule.
Examples of rosin diols include rosin esters obtained by reacting rosin with polyhydric alcohol, and reaction products of rosin with bisphenol A diglycidyl ether and the like. These rosin diols can be produced by conventionally known methods.
Among the rosin diols, those having a polyoxyalkylene skeleton are preferable from the viewpoint of compatibility with the NCO-terminated prepolymer. As a commercial item of the rosin diol which has polyoxyalkylene frame | skeleton, pine crystal D-6011, KE-615-3, D-6250 (all are Arakawa Chemical Industry Co., Ltd.) etc. are mentioned.

  The rosin diol is preferably used in combination with other polyols. Polypropylene glycol is preferred as the other polyol. When using rosin diol and another polyol in combination, the amount of rosin diol used is preferably 50% by mass or less of the total amount of the polyol, and 2% by mass to 30% by mass from the viewpoint of the properties after curing. Is more preferable, and 3% by mass to 15% by mass is more preferable.

  The polyol may be a multifunctional polyol. For example, by using a tetrafunctional or higher (preferably tetrafunctional to 8-functional) polyfunctional polyol, the adhesive strength (peel strength) after curing of the pressure-sensitive adhesive becomes more excellent.

  Examples of polyfunctional polyols include tetraols (pentaerythritol, diglycerin, etc.), pentaols (triglycerin, galactose, etc.), hexaols (dipentaerythritol, sorbitol, etc.), heptaols, octaols (tripentaerythritol, sucrose, etc. And those obtained by adding ethylene oxide, propylene oxide or the like to these polyfunctional polyols. From the viewpoint of versatility and effects, alkoxide adducts of pentaerythritol are preferred. These polyfunctional polyols can be produced by conventionally known methods, and can also be obtained as commercial products. Examples of commercially available polyfunctional polyols include EL-410NE (Asahi Glass Co., Ltd.) and POLYPL 4525 (Perstorp Specialty Chemicals AB).

  The multifunctional polyol may be a polymer. When the polyfunctional polyol is a polymer, the number average molecular weight thereof is usually 100 to 2,000, and preferably 300 to 700 from the viewpoints of properties and reactivity.

  The polyfunctional polyol is preferably used in combination with other polyols. As another polyol, polypropylene glycol is preferable, and a combination of polypropylene glycol and rosin diol is more preferable. When a polyfunctional polyol is used in combination with other polyols, the amount of the polyfunctional polyol used is such that the number of hydroxyl groups of the polyfunctional polyol is 60 of the number of hydroxyl groups of the entire polyol from the viewpoint of the flexibility of the cured product (adhesive). The amount is preferably at most%, and more preferably at 5% to 20%.

  The polyisocyanate compound is not particularly limited, and may be any of aromatic, aliphatic or alicyclic. Specifically, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, Naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, polymethylene polyphenyl isocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, etc. may be mentioned. In addition, it may be isocyanurate, carbodiimide, biuret, etc. of these polyisocyanate compounds. The polyisocyanate compound used for the synthesis of the urethane polymer may be one kind alone or two or more kinds. Among them, IPDI is preferred in view of the properties of the prepolymer, flexibility after curing, non-yellowing and safety.

The polyisocyanate compound preferably contains a trifunctional or higher (preferably trifunctional to hexafunctional) polyfunctional polyisocyanate. By using a trifunctional or higher polyfunctional polyisocyanate, the adhesive strength (peel strength) after curing becomes more excellent.
Commercially available polyfunctional polyisocyanates include Coronate HX (alicyclic polyisocyanate, Nippon Polyurethane Industry Co., Ltd.), Takenate D-170N (alicyclic polyisocyanate, Takeda Pharmaceutical Co., Ltd.), Semidur N-3500 (fat Family polyisocyanates, Sumika Bayer Urethane Co., Ltd., Sumidul N-3200 (aliphatic polyisocyanate, Sumika Bayer Urethane Co., Ltd.), Duranate 24A-100, Duranate E-405-80T (Asahi Kasei Chemicals Co., Ltd.), etc. It can be mentioned.

  The multifunctional polyisocyanate compound is preferably used in combination with another polyisocyanate compound. IPDI is preferable as another polyisocyanate compound. When using a polyfunctional polyisocyanate compound and another polyisocyanate compound in combination, the amount of the polyfunctional polyisocyanate compound used is the total number of NCO groups in the polyfunctional polyisocyanate compound from the viewpoint of the properties after the reaction. The amount is preferably 60% or less of the number of NCO groups, and more preferably 5% to 20%.

  The terminal NCO prepolymer can be obtained, as required, by reacting a polyol, an excess amount of a polyisocyanate compound and a monool. In this case, the adhesive strength (peel strength) after curing of the adhesive is more excellent.

  Examples of monools include polyoxyalkylene monools, polyester monools, polyether / ester monools, higher saturated monools, monools having an ethylenically unsaturated double bond, and the like. When monool is used, it may be one kind alone or two or more kinds.

As a polyoxyalkylene monool, ring-opening addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or the like using an alkyl compound containing one active hydrogen as an initiator, hydroxyl group in the molecule And high molecular weight polyoxyalkylene monools containing one.
Examples of polyester monools include alkylated modified products of terminal hydroxyl groups of known polyester polyols, and lactone-based polyester mono-esters obtained by subjecting a cyclic lactone compound to ring-opening addition copolymerization reaction or esterification reaction using a monohydroxy compound as an initiator. Carols, polyalcohols, and carboxylic acids having an ethylenically unsaturated double bond such as saturated fatty acid or (meth) acrylic acid, cinnamic acid, oleic acid which is a higher unsaturated fatty acid having 10 or more carbon atoms, linoleic acid, linolenic acid, etc. And esters and monools obtained from acids and the like.
Examples of the polyether / ester monool include polyoxyalkylene fatty acid ester monool obtained by addition-polymerizing the (mono) alkylene oxide to fatty acid ester monool.
Examples of higher saturated monools include linear, monovalent, higher saturated alcohols having 10 or more carbon atoms such as lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol.
Examples of monools having an ethylenically unsaturated double bond include linear and monovalent higher unsaturated alcohols having 10 or more carbon atoms such as oleyl alcohol, linoleyl alcohol and linolenyl alcohol, allyl alcohol and the like .
Among them, from the viewpoint of general purpose and safety, polyoxyalkylene monools are preferable, and polyoxypropylene alkyl ether is more preferable.
The monool may be a polymer. When the monool is a polymer, its number average molecular weight may be, for example, 100 to 10,000, and preferably 500 to 10,000 from the viewpoint of versatility and handling.
As a commercial item of monool which is a polymer, PML-S1004F (Asahi Glass Co., Ltd.) etc. are mentioned.
When monool as a polymer is used, the amount used is preferably 5% by mass to 50% by mass, and 5% by mass to 30% by mass, with respect to the total amount of the polyol, from the viewpoint of performance after curing. Is more preferred.

  The urethane-based pressure-sensitive adhesive may contain a tackifier, if necessary. The tackifier is not particularly limited as long as it can impart tackiness to the urethane-based pressure-sensitive adhesive or can improve the tackiness. Examples of the tackifier include those described above as the tackifying resin which may be contained in the acrylic pressure-sensitive adhesive.

  When the urethane-based pressure-sensitive adhesive contains a tackifier, the content thereof is preferably 10% by mass to 60% by mass of the total amount of the pressure-sensitive adhesive composition, from the viewpoint of the balance between physical properties after curing and performance. It is more preferable that it is mass%-50 mass%.

  The urethane-based pressure-sensitive adhesive may contain a reactive monofunctional compound as required. By including the reactive monofunctional compound, the adhesive strength (peel strength) after curing becomes more excellent.

  The reactive monofunctional compound is not particularly limited as long as it is a monofunctional compound having reactivity in a urethane reaction and can improve the adhesive strength (peel strength) after curing of the pressure-sensitive adhesive. Specifically, monools mentioned above as monools which may be used for synthesis of terminal NCO prepolymers, monofunctional isocyanate compounds (reactants of monools and diisocyanates, etc.), and other monofunctional compositions capable of urethane reaction (Amine, amide, thiol, carboxylic acid, etc.) and the like. The reactive monofunctional compounds used may be used alone or in combination of two or more. From the viewpoint of safety and versatility, monofunctional isocyanate compounds are preferable, and a reactant of monool and diisocyanate is more preferable. As a reaction product of monool and diisocyanate, the trade name "Additive TI" of Bayer AG and the like can be mentioned.

  When the urethane-based pressure-sensitive adhesive contains a reactive monofunctional compound, the amount used is preferably 5% by mass to 50% by mass, and 5% by mass to 30% by mass from the viewpoint of the performance after curing. More preferably, it is%.

  The urethane-based pressure-sensitive adhesive may optionally contain an additive. Additives include urethane catalysts, plasticizers (acrylic acid ester plasticizers, phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, alkylbenzenes, etc.), fillers (heavy calcium carbonate Fatty acid-treated calcium carbonate, fumed silica, precipitated silica, carbon black, talc, titanium oxide, balloon, beads, etc., antioxidant (hindered phenols etc.), flame retardant, thixotropic agent (colloidal silica, Organic bentonite, fatty acid amide, polyamide wax, hydrogenated castor oil, etc., UV absorber (benzotriazoles, hindered amines etc.), anti-aging agent (hindered phenols, mercaptans, sulfides, dithiocarboxylic acid salts, thiourea Species, thiophosphate DOO acids, thio-aldehydes, etc.), adhesion agent (an epoxy compound, a silane coupling agent, etc.), and the like dehydrating agent.

  Examples of the urethane catalyst include DBU catalysts, amine catalysts, organic carboxylic acid metal salts, and imidazole catalysts. Examples of DBU catalysts include DBU [1,8-diazabicyclo (5.4.0) undecene-7], DBU phenol salt, DBU octylate, DBU formate and the like. Examples of amine catalysts include monoamines (such as triethylamine), diamines (such as N, N, N ', N'- tetramethylethylenediamine), triamines (such as tetramethylguanidine), cyclic amines (such as triethylenediamine), and alcohol amines (such as dimethylamine). Amino methanol etc., ether amine (bis (2-dimethylaminoethyl) ether etc.) etc. are mentioned. Examples of the organic carboxylic acid metal salt include Sn (such as dibutyltin dilaurate and tin octylate), Pb (such as lead octylate), and Zn (such as zinc octylate). Examples of the imidazole-based catalyst include 2-methylimidazole, 1,2-dimethylimidazole and the like.

  The method for producing the urethane-based pressure-sensitive adhesive is not particularly limited. For example, it may be produced as a one-component urethane adhesive by mixing the polymer component contained in the urethane adhesive and other components contained as necessary. The urethane-based pressure-sensitive adhesive may be a solvent-free pressure-sensitive adhesive substantially free of solvent. When the urethane-based pressure-sensitive adhesive does not substantially contain a solvent, when the pressure-sensitive adhesive is cured by heat, environmental pollution due to generation of odor, volatile organic compound (VOC) or the like can be suppressed.

(Filler)
The adhesive layer may contain a filler. When the adhesive layer contains a filler, an effect such as roughening the outer surface (surface opposite to the substrate side) of the adhesive layer can be obtained.
The material of the filler is not particularly limited, and may be an organic substance such as a resin, an inorganic substance such as a metal or a metal oxide, or a combination of an organic substance and an inorganic substance. The filler contained in the adhesive layer may be one kind alone or two or more kinds.

  The volume average particle size of the filler is not particularly limited. For example, it can be selected from the range of 1 μm to 20 μm. In the present specification, the volume average particle size of the filler is the particle size (D50) at which the accumulation from the small diameter side is 50% in the volume-based particle size distribution measured by the laser diffraction method.

  From the viewpoint of the affinity to the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer, the filler is preferably a resin particle. As resin which comprises a resin particle, an acrylic resin, an olefin resin, a styrene resin, an acrylonitrile resin, a silicone resin etc. are mentioned. An acrylic resin is preferable from the viewpoint of suppressing the residue on the package after molding.

<Base material>
The material of the substrate is not particularly limited. From the viewpoint of mold followability, resins are preferred. Examples of the resin include polyesters such as polyethylene terephthalate (PET), polyimides, polyamides, polyester ethers, polyamide imides, and fluorine-containing resins. When using resin, it is preferable to have sufficient heat resistance with respect to the heating temperature in a sealing process.

  As needed, the surface for the side in which the adhesion layer of a base material is provided may be processed in order to improve the adhesiveness between a base material and an adhesion layer. Examples of the method of treatment include surface treatment such as corona treatment and plasma treatment, and application of a primer (primer).

  As needed, the back surface processing agent for adjusting the unwindability from the roll of an adhesive film may be provided to the back surface (surface opposite to the adhesive layer side) of a base material. As a back surface processing agent, single-piece | units, such as a silicone resin, fluorine-containing resin, polyvinyl alcohol, resin which has an alkyl group, a modified body, a mixture, etc. are mentioned.

  If necessary, an antistatic agent is applied to the back surface of the substrate or the surface on which the adhesive layer is provided in order to suppress the generation of static electricity during unwinding of the adhesive film, peeling from the adherend, etc. May be Examples of the antistatic agent include cationic antistatic agents having a cationic group such as quaternary ammonium salt, pyridinium salt, and primary to tertiary amino groups, and anions such as sulfonic acid base, sulfuric acid ester base and phosphoric acid ester base. Anionic antistatic agent having a hydrophobic group, amphoteric antistatic agent such as amino acid type and amino acid sulfate ester type, nonionic antistatic agent having nonionic group such as amino alcohol type, glycerin type and polyethylene glycol type and the like A high molecular weight type of antistatic agent may be mentioned. These antistatic agents are also preferable in terms of good transparency.

  Below, the release film of this embodiment is demonstrated based on an Example. However, the present embodiment is not limited to the following examples.

Example 1
100 parts by mass of the adhesive A, 0.5 parts by mass of the catalyst, and 275 parts by mass of a solvent (a mixture of toluene and methyl isobutyl ketone, mass ratio 1: 1) Prepared. The composition for forming an adhesive layer is coated on the entire surface of one side of a substrate (PET film with a thickness of 50 μm) so that the thickness of the adhesive layer is 3 μm, and heated at 120 ° C. for 1 minute to form an adhesive layer. To produce a support. Next, a copper foil (“F2-WS”, Furukawa Electric Co., Ltd.) with a length of 232 mm, a width of 67 mm and a thickness of 9 μm is laminated to the adhesive layer of the support as shown in FIG. An electromagnetic wave shielding sheet was formed and punched into a predetermined shape to produce a release film.

Example 2
100 parts by mass of the adhesive B, 10 parts by mass of the crosslinking agent A, and 227 parts by mass of a solvent (a mixture of toluene and methyl ethyl ketone, mass ratio 8: 2) are mixed and stirred by a disper to prepare a composition for forming an adhesive layer did. The composition for forming an adhesive layer is coated on the entire surface of one side of a substrate (PET film having a thickness of 38 μm) so that the thickness of the adhesive layer is 3 μm, and heated at 100 ° C. for 1 minute to form an adhesive layer. To produce a support. Next, an aluminum layer was formed to a thickness of 1 μm by an ion plating method on the entire surface of the adhesive layer to form an electromagnetic wave shielding sheet, and it was punched into a predetermined shape to prepare a release film.

Example 3
100 parts by mass of the adhesive C, 17.4 parts by mass of the crosslinking agent B, 10 parts by mass of the filler, and 87 parts by mass of a solvent (a mixture of toluene and methyl ethyl ketone, mass ratio 8: 2) are stirred by a disper, The composition for adhesive layer formation was prepared. A release film was produced in the same manner as in Example 2 except that this composition for forming an adhesive layer was used.

Comparative Example 1
A pressure-sensitive adhesive layer was formed on a substrate using the composition for forming a pressure-sensitive adhesive layer prepared as in Example 2 in the same manner as in Example 2 to prepare a support. Then, an electromagnetic wave shielding sheet was formed on the adhesive layer in the same manner as in Example 1 to prepare a release film.

The detail of each material used for preparation of a mold release film is as follows.
(Adhesive)
· Adhesive A: Addition reaction type silicone adhesive, trade name "LTC 755", solid content 30 mass%, Toray Dow Corning Co., Ltd. · Adhesive B: acrylic adhesive, trade name "S-43", solid Min. 24% by mass, Soken Chemical Co., Ltd., a mixed monomer of butyl acrylate (BA) and 4-hydroxybutyl acrylate (4HBA) ・ Adhesive C: Acrylic adhesive, trade name “FS-1208”, solid content 45 %, Lion Special Chemicals Co., Ltd., composed of multiple mixed monomers of methacrylic acid ester (catalyst)
・ Platinum catalyst (brand name "NC-25", Toray Dow Corning Co., Ltd.)
(Crosslinking agent)
Crosslinking agent A: trade name "Coronato HL", solid content 75% by mass, Tosoh Corp., 75% ethyl acetate solution of trimethylolpropane / hexamethylene diisocyanate trimer adduct, number of isocyanate groups in one molecule: 3 -Crosslinking agent B: trade name "Duranate E405-80T", solid content 80% by mass, Asahi Kasei Chemicals Co., Ltd., polyisocyanate based crosslinking agent (hexamethylene diisocyanate crosslinking agent (HMDI)), number of isocyanate groups in one molecule: 2 Filler: Crosslinked acrylic dispersed particles, trade name "MZ-10HN", volume average particle diameter 10 μm, Soken Chemical Co., Ltd.

<Evaluation test>
The following evaluation test was done using the produced release film.

(1) Peeling Force Between Adhesive Layer-Electromagnetic Wave Shielding Sheet In Example 1 and Comparative Example 1 in which the electromagnetic wave shielding sheet was formed by laminating method, the prepared release film was put into an atmosphere at 170 ° C., and after a predetermined time elapsed, Peeling force (N / 50 mm) was measured using a Tensilon universal material tester (manufactured by A & D Co., Ltd.) under a peeling angle of 180 ° and a peeling speed of 0.3 m / min. The results are shown in Table 1.
In Example 2 and Example 3 in which the electromagnetic wave shielding sheet was formed by the ion plating method, the prepared release film was cut into a predetermined size, and placed on a 170 ° C. hot plate with the adhesive layer on top A predetermined amount of a sealing material (trade name "CEL-9750", Hitachi Chemical Co., Ltd.) was sprayed on the adhesive layer, and a PET film having a thickness of 100 μm was placed thereon. A 4 kg weight was then placed on the PET film and left for 3 minutes until the encapsulant was cured. Thereafter, the release film was cut to a width of 50 mm, and was put into an atmosphere of 170 ° C. After 1 minute, the peel strength was measured with a TENSILON universal material tester (manufactured by A & D Co., Ltd.) under a peel angle of 180 ° and a peel speed of 0.3 m / min. The results are shown in Table 1.

(2) Transferability of Electromagnetic Wave Shielding Sheet The release films prepared in Example 1 and Comparative Example 1 are cut to a predetermined size, placed on a 170 ° C. hot plate with the adhesive layer on top, and sealed. A predetermined amount of a material (trade name “CEL-9750”, Hitachi Chemical Co., Ltd.) was dispersed on the adhesive layer, and a PET film having a thickness of 100 μm was placed thereon. A 4 kg weight was then placed on the PET film and left for 3 minutes until the encapsulant was cured. Then, the electromagnetic wave shielding sheet was peeled from the support (base material and adhesive layer), and the transferability of the electromagnetic wave shielding sheet was visually confirmed.
In Example 2 and Example 3, the electromagnetic wave shielding sheet is peeled off from the support (the base material and the adhesive layer) in a state where the sealing material is cured in the same manner as in the evaluation of the peeling force between the adhesive layer and the electromagnetic wave shielding sheet. The transferability of the shielding sheet was visually confirmed.

  The transferability of the electromagnetic wave shielding sheet is "OK" if the electromagnetic wave shielding sheet can be peeled off from the support without generation of wrinkles, breakage, tears, etc., the electromagnetic shielding sheets generate wrinkles, breakage, tears, etc. When it was not able to peel from the support, it was evaluated as "not good". The results are shown in Table 1.

  As shown in the results of Table 1, the release sheet of the example in which the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 0.10 N / 50 mm to 2.00 N / 50 mm has good transferability of the electromagnetic wave shielding sheet. Met. On the other hand, in the release sheet of the comparative example in which the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is less than 0.10 N / 50 mm, wrinkles are generated in the peeled electromagnetic wave shielding sheet, and the transferability of the electromagnetic wave shielding sheet is an example. It was inferior.

  The disclosure of Japanese Patent Application No. 2016-091947 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims (5)

  A support comprising a substrate and an adhesive layer disposed on the substrate, and an electromagnetic wave shielding sheet disposed on the adhesive layer of the support, wherein the adhesive layer and the electromagnetic wave shielding sheet are interposed between The release film whose peeling force is 0.10 N / 50 mm-2.00 N / 50 mm.   The release film according to claim 1, wherein a thickness of the electromagnetic wave shielding sheet is 0.01 μm to 50 μm.   The release film according to claim 1, wherein a thickness of the adhesive layer is 1 μm to 20 μm.   The release film according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer contains at least one selected from the group consisting of silicone pressure-sensitive adhesives and acrylic pressure-sensitive adhesives.   The release film according to any one of claims 1 to 4 for manufacturing a semiconductor device including a step of transferring the electromagnetic wave shielding sheet to a sealing material for sealing a semiconductor element.