TW201540803A - Adhesive sheet - Google Patents

Abstract

The present invention provides an adhesive sheet having proper adhesiveness to a sealing resin, which constitutes the semiconductor encapsulation, and a semiconductor chip, capable of being easily peeled off from the sealing resins and semiconductor chips and preventing residual paste when being peeled off. The adhesive sheet of this invention is provided with an adhesive layer whose surface forms a contact angle 15 degree or more relative to 4-tertiary butyl phenyl glycidyl ether, and the adhesion strength of the adhesive sheet to polyethylene terephthalate under 23 DEG C is 0.5N/20mm or above.

Description

Adhesive sheet

The present invention relates to an adhesive sheet.

In recent years, in order to reduce the size of semiconductor devices, CSP (Chip Size/Scale Package) which forms a semiconductor package having the same size as a built-in semiconductor element has been attracting attention as a semiconductor package technology. A WLP (Wafer Level Package) is known as a semiconductor package technology for forming a small and high-package package in a CSP. The WLP is a technique in which a plurality of semiconductor wafers are collectively sealed by a sealing resin without using a substrate, and thereafter, each semiconductor wafer is cut and separated to obtain a semiconductor package. In general, when a semiconductor wafer is batch-sealed, in order to prevent movement of the semiconductor wafer, a plurality of semiconductor wafers are temporarily fixed by a specific temporary fixing material, and a plurality of semiconductor wafers are collectively sealed on the temporary fixing material. Thereafter, when the semiconductor wafers are subjected to the separation and separation (after the batch sealing, before the separation or the separation, or after the separation), the temporary fixing material is peeled off from the structure including the sealing resin and the semiconductor wafer. As a temporary fixing material used as such, a low-adhesive adhesive sheet is often used.

However, when a conventional adhesive sheet is used, there is a problem that a paste remains in the structure when it is peeled off from the structure including the sealing resin and the semiconductor wafer. In particular, the paste residue in the peripheral portion of the semiconductor wafer becomes remarkable, and the paste residue becomes a cause of a decrease in yield.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-308116

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-313350

The present invention has been made to solve the above problems, and an object thereof is to provide an adhesive sheet which has a moderate adhesiveness to a sealing resin and a semiconductor wafer constituting a semiconductor package, and can be used for the sealing resin and the semiconductor. The wafer is easily peeled off, and paste residue at the time of peeling is less likely to occur.

The adhesive sheet of the present invention is an adhesive sheet having an adhesive layer, and the contact angle of the surface of the adhesive layer with respect to 4-t-butylphenyl glycidyl ether is 15° or more, and the adhesive sheet is at 23° C. The adhesion to polyethylene terephthalate is 0.5 N/20 mm or more.

In one embodiment, the material constituting the adhesive in the adhesive layer has an sp value of 7 (cal/cm ³ ) ^1/2 to 10 (cal/cm ³ ) ^1/2 .

In one embodiment, the adhesive layer of the adhesive layer has a viscosity of 50 N/5 mm. the above.

In one embodiment, the adhesive layer comprises an acrylic adhesive.

In one embodiment, the acrylic pressure-sensitive adhesive contains an acrylic polymer having an alkyl ester having 4 or more carbon atoms in a side chain as a base polymer.

In the above-mentioned acrylic polymer, the content ratio of the structural unit having an alkyl ester having 4 or more carbon atoms in the side chain is 30% by weight or more based on the total structural unit constituting the acrylic polymer. .

In one embodiment, the adhesive layer contains a rubber-based adhesive.

In one embodiment, the adhesive layer comprises a polyoxynoxy adhesive.

In one embodiment, the polyoxynoxy adhesive comprises polyoxyethylene rubber and polyfluorene The oxygen resin is used as the base polymer, and the weight ratio of the polyoxyxene rubber to the polyoxynoxy resin (rubber: resin) is from 100:0 to 100:220.

In one embodiment, the adhesive layer further includes heat-expandable microspheres.

In one embodiment, the pressure-sensitive adhesive layer before the heat-expandable microspheres are heated has an arithmetic surface roughness Ra of 500 nm or less.

In one embodiment, for the adhesive sheet of the present invention, the outer surface of the adhesive layer is applied to a Bakelite plate at an ambient temperature of 23 ° C, and is exposed to an ambient temperature of 40 ° C. After aging for 30 minutes, a load of 1.96 N was applied and held for 2 hours, at which time the offset of the adhesive sheet of the present invention with respect to the electric board was 0.5 mm or less.

In one embodiment, the adhesive sheet of the present invention further includes a base material layer, and the adhesive layer is disposed on one side or both sides of the base material layer.

In one embodiment, the base material layer and the adhesive layer have a gripping force of 6.0 N/19 mm or more.

According to the present invention, an adhesive sheet having a contact angle of 15° or more with respect to 4-t-butylphenyl glycidyl ether can be obtained, which can provide a sealing resin and a semiconductor which constitute a semiconductor package. The wafer has a moderate adhesiveness and can be easily peeled off from the sealing resin and the semiconductor wafer, and the paste residue at the time of peeling is less likely to occur.

1‧‧‧Semiconductor wafer

2‧‧‧ sealing resin

2'‧‧‧Composition

10‧‧‧Adhesive layer

10'‧‧‧Adhesive sheet

20‧‧‧ Structure

30‧‧‧Substrate layer

40‧‧‧Elastic layer

100, 200, 300‧‧‧ adhesive sheets

Fig. 1(a) is a view showing an example in which a conventional adhesive sheet is used for the manufacture of a semiconductor package, and Fig. 1(b) is a view showing an example in which the adhesive sheet of the present invention is used in the manufacture of a semiconductor package. Picture.

2(a) and 2(b) are schematic cross-sectional views showing an adhesive sheet according to an embodiment of the present invention.

Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment of the present invention.

A. Summary of adhesive sheets

The adhesive sheet of the present invention has an adhesive layer. The adhesive sheet of the present invention may be composed only of the adhesive layer, or may have any appropriate layer in addition to the adhesive layer. Examples of the layer other than the pressure-sensitive adhesive layer include a base material layer which can function as a support, a separator which is detachably disposed on the pressure-sensitive adhesive layer, and the like. Further, other adhesive layers may be provided in addition to the above-mentioned adhesive layer. Other adhesive layers may be of a known composition.

The adhesive sheet of the present invention preferably has an adhesion to polyethylene terephthalate at 23 ° C of 0.5 N / 20 mm or more, more preferably 0.5 N / 20 mm to 20 N / 20 mm, and further preferably 0.5 N / 20mm~15N/20mm. In one embodiment, the adhesive layer of the adhesive sheet of the present invention causes a decrease in adhesion due to heating or light irradiation. In this case, the above-mentioned adhesive force before the adhesion is lowered is 2.5 N/20 mm to 20 N/20 mm. In the present specification, the term "adhesion to polyethylene terephthalate" means that an adhesive sheet is attached to a polyethylene terephthalate film (thickness: 25 μm) (width: 20 mm × Adhesive layer of length 100mm) (adhesion condition: 2kg roller, round trip once), after being placed at an ambient temperature of 23 ° C for 30 minutes, the sample was subjected to a tensile test (peeling speed: 300 mm/min, peeling) The angle of 180°) was measured for adhesion.

The adhesive sheet of the present invention preferably has an adhesion force to a germanium wafer (thickness: 500 μm) at 23 ° C of 0.1 N/20 mm to 4 N/20 mm, more preferably 0.15 N/20 mm to 3 N/20 mm, and still more preferably 0.2. N/20mm~2/20mm. If it is such a range, the adhesive sheet which has adhesive force and peeling property with respect to a semiconductor wafer can be obtained. The adhesion to the wafer can also be measured by the same method as the above-mentioned "adhesion to polyethylene terephthalate".

The adhesive sheet of the present invention preferably has an adhesion to the epoxy resin sheet at 23 ° C of 0.1 N / 20 mm to 5 N / 20 mm, more preferably 0.3 N / 20 mm to 4 N / 20 mm, and still more preferably 0.5 N. /20mm~3/20mm. If it is such a range, the paste residue at the time of peeling of a self-sealing resin (details demonstrated later) can be suppressed. The adhesion to the epoxy resin film can also be obtained by the same method as the above "adhesion to polyethylene terephthalate". Line measurement. In addition, as the epoxy resin film, for example, a film composed of a sealing resin described in the evaluation of the "stand off suppression effect" of the example can be used.

The outer surface of the adhesive layer of the adhesive sheet (width 10 mm×length 150 mm) of the present invention was applied to the electric board (width 10 mm×length 125 mm) at an ambient temperature of 23 ° C, and the ambient temperature was 40 ° C. The aging was carried out for 30 minutes, and thereafter a load of 1.96 N was applied and held for 2 hours. At this time, the offset of the adhesive sheet with respect to the electric board was preferably 0.5 mm or less, and more preferably 0.4 mm or less. Here, the term "offset of the adhesive sheet with respect to the electric board" means the amount by which the adhesive sheet is moved from the initial state based on the state before the aging (initial state). The above-mentioned adhesive sheet having a small offset is an adhesive sheet which is less likely to cause cohesive failure of the adhesive layer, and such an adhesive sheet is an adhesive sheet which is substantially incapable of producing a paste residue. In the case of such an adhesive sheet, the effects of the present invention become remarkable. The adhesive layer which is less likely to cause cohesive failure can be formed, for example, by using the above-mentioned acrylic pressure-sensitive adhesive (preferably, an adhesive comprising a crosslinked acrylic polymer as a base polymer) as an adhesive for forming an adhesive layer. Further, as the adhesive, a rubber-based adhesive is used, and more specifically, a base polymer (rubber) constituting a rubber-based adhesive, a polyolefin containing a hydroxyl group, and a hydroxyl group reactive with the hydroxy polyolefin are used. The rubber-based adhesive (Rub1) of the crosslinking agent is appropriately adjusted to adjust the amount of the hydroxyl group-containing polyolefin and the crosslinking agent, whereby an adhesive layer which is less likely to cause aggregation failure can be formed. The details will be explained later.

The thickness of the adhesive sheet of the present invention is preferably from 3 μm to 300 μm, more preferably from 5 μm to 150 μm, still more preferably from 10 μm to 100 μm.

B. Adhesive layer

The contact angle of the surface of the adhesive layer with respect to 4-t-butylphenyl glycidyl ether is 15° or more, more preferably 20° or more, further preferably 30° to 100°, and particularly preferably 40° to 60°. °.

The adhesive layer of the adhesive sheet of the present invention is adjusted for the affinity of the sealing resin (for example, epoxy resin) used for sealing the semiconductor wafer and the monomer component constituting the sealing resin. Specifically, the above adhesive layer can be expressed on a sealing resin (and a semiconductor wafer) Within the range of appropriate adhesion, the affinity is adjusted in such a manner that the affinity is lowered. The contact angle of the appropriately adjusted adhesive layer with respect to 4-t-butylphenyl glycidyl ether showed the above range. By adjusting the affinity between the sealing resin and the monomer component constituting the sealing resin in this manner, an adhesive sheet having less residual resin can be obtained, and more specifically, an adhesive sheet can be obtained which is bonded to a semiconductor containing When the structure (Fig. 1) of the resin (or the resin precursor monomer) for sealing the semiconductor is peeled off, the adhesive layer component adhering to the structure can be reduced. The mechanism for reducing the residue of the paste by using the adhesive sheet of the present invention can be considered as follows.

Fig. 1(a) shows an example in which the previous adhesive sheet 10' is used for the manufacture of a semiconductor package. The adhesive sheet 10' has an adhesive layer, and the outer surface of the adhesive layer is used as a bonding surface. Previously, in the manufacture of a semiconductor package (CSP), first, the semiconductor wafer 1 (a-i) was bonded to the adhesive sheet 10'. Thereafter, the semiconductor wafer 1 is sealed, and a composition 2' (a-ii) containing a monomer which is a precursor of the sealing resin 2 is applied, and thereafter, the composition 2' is cured (a-iii). Further, as the composition, for example, a composition containing a naphthalene type bifunctional epoxy resin (epoxy equivalent: 144) can be used. Then, the adhesive sheet 10' is peeled off from the structure 20 including the semiconductor wafer 1 and the sealing resin 2 before the semiconductor wafer is cut and separated, or after the separation (before the cutting and separation in the illustrated example). -iv). In the case of using the previous adhesive sheet, it is easy to cause paste residue upon peeling. Especially in the peripheral portion of the semiconductor wafer 1, paste residue was observed remarkably. The inventors of the present invention have found that, in the case of using the prior adhesive sheet 10', the adhesive layer of the adhesive sheet 10' at the time of peeling is embossed so as to surround the bottom of the semiconductor wafer 1, and the adhesive sheet is peeled off. A step (hereinafter also referred to as a gap height) due to the bottom edge of the semiconductor wafer 1 is generated in the adhesive layer of 10'. It is considered that since the stress originating from the semiconductor wafer 1 is concentrated on the gap height portion, aggregation failure of the adhesive layer occurs, and as a result, the paste remains.

Fig. 1(b) shows an example in which the adhesive sheet 10 of the present invention is used in the manufacture of a semiconductor package. The adhesive sheet 10 has an adhesive layer, and the outer surface of the adhesive layer is used as a bonding surface. In Fig. 1(b), a structure 20 including a semiconductor wafer 1 and a sealing resin 2 is formed on the adhesive sheet 10 by the same operation as that shown in Fig. 1(a) except that the adhesive sheet is changed. Thereafter, the adhesive sheet 10 is peeled off. In the case of using the adhesive sheet 10 of the present invention, the gap height generated in the adhesive sheet 10 is extremely small (or not generated), and the residue of the paste is suppressed.

In the prior adhesive sheet 10', it is considered that the adhesive layer component is transferred to the composition containing the monomer which is the precursor of the sealing resin 2, or the sealing resin, and as a result, the resin layer of the adhesive sheet 10' is bonded. The gap height is generated by bulging in such a manner as to surround the bottom of the semiconductor wafer 1. Further, the presence or absence of component transfer can be confirmed by spectral analysis using FT-IR or the like. On the other hand, in the invention of the present invention, it is considered that the adhesiveness of the sealing resin used for sealing the semiconductor wafer and the monomer component constituting the sealing resin is adjusted, so that the component transfer as described above is suppressed. The gap height becomes extremely small (or does not occur), and as a result, the paste residue is suppressed. In the present specification, the sealing resin used in sealing the semiconductor wafer and the monomer component constituting the sealing resin are collectively referred to as a sealing material.

The above adhesive layer contains an adhesive. The sp value of the material (polymer) constituting the adhesive is preferably 7 (cal/cm ³ ) ^1/2 to 10 (cal/cm ³ ) ^1/2 , more preferably 7 (cal/cm ³ ) ^1/2 ~9.1 (cal/cm ³ ) ^1/2 , further preferably 7 (cal/cm ³ ) ^1/2 to 8 (cal/cm ³ ) ^1/2 . When it is such a range, it is possible to form an adhesive layer which has an appropriate adhesive property and which has low affinity with a sealing material and is less likely to cause a gap height. The adhesive sheet having such an adhesive layer is less likely to cause paste residue. Further, the term "adhesive" as used herein means a base polymer contained in the adhesive (the base polymer after crosslinking in the case of crosslinking) and rubber (in the case of crosslinking, it is crosslinked) A polymer such as rubber) or an adhesion-imparting agent. In the present invention, it is preferably a base polymer which is at least a main component of the adhesive (a base polymer after crosslinking in the case of crosslinking) or a rubber (a rubber which is crosslinked in the case of crosslinking) The value is the above range.

In one embodiment, the surface of the adhesive layer is brought into contact with 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and allowed to stand in an environment of 50 ° C for 2 hours for the adhesive. When the absorbance of the peak derived from the glycidyl group is measured by FT-IR measurement, the absorbance of the peak derived from the glycidyl group is higher than the absorbance of the peak derived from the peak of the glycidyl group of the initial adhesive layer. It is preferably 1.3 or less, more preferably 1.1 or less, still more preferably 1.05 or less. Further, the "initial adhesive layer" is an adhesive layer before contact with 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane. In another embodiment, the surface of the adhesive layer is brought into contact with 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and allowed to stand in an environment of 50 ° C for 2 hours to carry out the adhesion. In the case of the FT-IR measurement of the surface of the agent (for example, the attenuated total reflection method (ATR method)), the absorbance at the wave number of the peak derived from the glycidyl group (near 850 cm ^-1 ) is from the initial adhesive layer. The amount of increase is preferably 0.3 or less, more preferably 0.1 or less. Here, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is an epoxy compound which can be used as a resin material for sealing a semiconductor wafer. When an adhesive layer which does not easily transfer the epoxy compound as described above even when it is in contact with the epoxy compound is formed, an adhesive sheet which is less likely to have a gap height and a small amount of paste residue can be obtained even when used for manufacturing a semiconductor package. .

The thickness of the above adhesive layer is preferably from 1 μm to 300 μm, more preferably from 3 μm to 300 μm, still more preferably from 5 μm to 150 μm, still more preferably from 10 μm to 100 μm, still more preferably from 10 μm to 50 μm. In the case where the adhesive layer contains heat-expandable microspheres as described below, the thickness of the adhesive layer is preferably from 3 μm to 300 μm, more preferably from 5 μm to 150 μm, still more preferably from 10 μm to 100 μm. When it is such a range, it is possible to form an adhesive layer which is excellent in surface smoothness and excellent in adhesion. In the case where the adhesive layer does not contain the heat-expandable microspheres, the thickness of the adhesive layer is preferably 50 μm or less, more preferably 1 μm to 50 μm, still more preferably 5 μm to 30 μm.

The elastic modulus of the above adhesive layer measured by a nanoindentation method at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, still more preferably 0.1 MPa to 10 MPa. If it is such a range, an adhesive sheet having an adhesive force as an adhesive sheet which can be used for the manufacture of a semiconductor package can be obtained. The so-called nanoindentation method The modulus of elasticity refers to the elastic modulus obtained from the load load-pressing depth curve obtained by continuously measuring the load load and the depth of penetration of the indenter when the indenter is pressed into the sample. number. In this specification, the elastic modulus measured by the nanoindentation method refers to the load: 1 mN, load. Unloading speed: 0.1 mN/s, holding time: 1 s as a measurement condition, and the modulus of elasticity measured as described above.

The tensile modulus of the adhesive layer at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, still more preferably 0.1 MPa to 10 MPa. If it is such a range, an adhesive sheet having an adhesive force as an adhesive sheet which can be used for the manufacture of a semiconductor package can be obtained. Further, the tensile modulus of elasticity can be measured in accordance with JIS K 7161:2008.

The adhesive viscosity value of the above adhesive layer is preferably 50N/5mm Above, more preferably 75N/5mm Above, and further preferably 100N/5mm the above. If it is such a range, the adhesive body is excellent in retention, for example, when the semiconductor wafer is temporarily fixed, unnecessary positional displacement of the semiconductor wafer can be prevented. The method for measuring the viscosity of the probe is as follows.

<adhesive>

As the adhesive constituting the above adhesive layer, any suitable adhesive can be used as long as the effect of the present invention can be obtained. It is preferred to use an adhesive comprising a base polymer having an sp value in the above range. Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a polyoxygen-based pressure-sensitive adhesive. Among them, an acrylic adhesive can be preferably used. Further, an active energy ray-curable adhesive may be used as the adhesive.

(acrylic adhesive)

The acrylic adhesive is exemplified by acrylic acid (homopolymer or copolymer) using one or two or more kinds of alkyl (meth) acrylates as a monomer component as a base polymer. Adhesives, etc.

The acrylic polymer preferably has an alkyl ester having a carbon number of 4 or more in the side chain, more preferably an alkyl ester having a carbon number of 6 or more in the side chain, and further preferably has a carbon number of 8 in the side chain. The alkyl ester is preferably an alkyl ester having a carbon number of 8 to 20 in the side chain, and preferably an alkyl ester having a carbon number of 8 to 18 in the side chain. When an acrylic polymer having a long side chain is used, an adhesive layer having a low affinity with a sealing material can be formed. In the acrylic polymer, the content ratio of the structural unit having an alkyl ester having 4 or more carbon atoms in the side chain is preferably 30% by weight or more, more preferably 30% by weight or more, based on the total structural unit constituting the acrylic polymer. 50% by weight or more, more preferably 70% by weight to 100% by weight, particularly preferably 80% by weight to 100% by weight. If it is such a range, the adhesive layer with low affinity with a sealing material can be formed.

The acrylic pressure-sensitive adhesive may include a plurality of acrylic polymers, and the content ratio of the acrylic polymer having an alkyl ester having 4 or more carbon atoms in the side chain is preferably 100 parts by weight based on 100 parts by weight of the total acrylic polymer. It is 30 parts by weight to 100 parts by weight, more preferably 70 parts by weight to 100 parts by weight.

Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, (A) Isodecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (methyl) Tridecyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate A (meth)acrylic acid C1-20 alkyl ester such as octadecyl (meth)acrylate, nonadecyl (meth)acrylate or eicosyl (meth)acrylate. Among them, an alkyl (meth)acrylate having a linear or branched alkyl group having a carbon number of 4 to 20 (more preferably 6 to 20, particularly preferably 8 to 18) is preferred, and more preferably 2-ethylhexyl (meth)acrylate.

The acrylic polymer may be modified for cohesive force, heat resistance, crosslinkability, etc., and may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate, if necessary. Examples of such a monomer component include carboxyl groups such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Monomer; anhydride monomer such as maleic anhydride or itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyl group (meth)acrylate Hydroxyl monomer such as hexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate ; styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) propylene decylamine-2-methylpropane sulfonic acid, (meth) acrylamide propylene sulfonic acid, sulfopropyl (meth) acrylate, a sulfonic acid group-containing monomer such as (meth)acryloxynaphthalenesulfonic acid; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl (methyl) a (N-substituted) guanamine monomer such as acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide or the like; Ethyl ester, (meth) propylene N,N-dimethylaminoethyl ester, aminoalkylalkyl (meth)acrylate such as tert-butylaminoethyl (meth)acrylate; methoxyethyl (meth)acrylate, (meth)acrylic acid alkoxyalkyl ester monomer such as ethoxyethyl acrylate; N-cyclohexyl maleimide, N-isopropyl maleimide , N-Lauryl maleimide, N-phenyl maleimide, etc., maleimide-based monomer; N-methyl Ikonide, N-ethyl Ikonium imine, N-butyliconazole, N-octylkonkine imine, N-2-ethylhexylkamponium imine, N-cyclohexylkkonium imine, N - Ikonideimine monomer such as lauryl ikonium imine; N-(methyl) propylene oxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyl Amber quinone imine monomer such as hexamethylene succinimide, N-(methyl) propylene decyl-8-oxy octamethylene succinimide; vinyl acetate, vinyl propionate, N -vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper Vinylpyr , vinyl pyrrole, vinyl imidazole, vinyl Azole, vinyl Vinyl, N-vinylcarboxamide, styrene, α -methylstyrene, N-vinyl caprolactam and other vinyl monomers; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile An epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (methyl) a diol-based acrylate monomer such as acrylate or methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, or polyoxymethylene (meth) acrylate An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom such as an ester; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, or (poly)propylene glycol di( Methyl) acrylate, neopentyl glycol di(meth) acrylate, pentaerythritol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, two Polyfunctional monomer such as pentaerythritol hexa(meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; , Butadiene, isobutylene and other olefin-based monomers; vinyl ether, vinyl ether-based monomers. These monomer components can be used individually or in combination of 2 or more types. Among the above, a monomer having a carboxyl group (particularly preferably acrylic acid) or a monomer having a hydroxyl group (particularly, hydroxyethyl (meth)acrylate) is more preferable. The content of the structural unit derived from the monomer having a carboxyl group is preferably from 0.1% by weight to 10% by weight, more preferably from 0.5% by weight to 5% by weight, even more preferably 1%, based on the total structural unit constituting the acrylic polymer. Weight%~4% by weight. Further, the content of the structural unit derived from the monomer having a hydroxyl group is preferably from 0.1% by weight to 20% by weight, more preferably from 0.5% by weight to 10% by weight, based on the total structural unit constituting the acrylic polymer. It is 1% by weight to 7% by weight.

The above acrylic adhesive may contain any appropriate additives as needed. Examples of the additive include a crosslinking agent, an adhesion-imparting agent, and a plasticizer (for example, a trimellitate-based plasticizer or a pyromellitic-based plasticizer), a pigment, a dye, and a filler. Agent, anti-aging agent, conductive material, antistatic agent, ultraviolet absorber, light stabilizer, peeling adjuster, softener, surfactant, flame retardant, antioxidant, etc.

Examples of the crosslinking agent contained in the acrylic pressure-sensitive adhesive include an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, and a peroxide crosslinking agent, and examples thereof include a urea system. a crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, a carbon diimide crosslinking agent, An oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, and the like. Among them, an isocyanate crosslinking agent or an epoxy crosslinking agent is preferred.

Specific examples of the above isocyanate-based crosslinking agent contained in the acrylic pressure-sensitive adhesive include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; and cyclopentyl diisocyanate; An alicyclic isocyanate such as cyclohexyl diisocyanate or isophorone diisocyanate; an aromatic isocyanate such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or benzodimethyl diisocyanate; Trimethylolpropane/toluene diisocyanate trimer adduct (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Nippon) An isocyanate adduct such as an isocyanurate (manufactured by Nippon Pocyurethane Industry Co., Ltd., trade name "CORONATE HX") manufactured by Pocyurethane Industry Co., Ltd., trade name "CORONATE HL"). The content of the isocyanate crosslinking agent can be set to any appropriate amount depending on the desired adhesive strength, and is typically 0.1 parts by weight to 20 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the base polymer. Parts by weight.

Examples of the epoxy-based crosslinking agent contained in the acrylic pressure-sensitive adhesive include N, N, N', N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, and 1, 3-bis(N,N-glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C"), 1,6-hexanediol diglycidyl ether (Kyoeisha) Chemical company, trade name "EPOLIGHT 1600"), neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "EPOLIGHT 1500NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd.) , product name "EPOLIGHT 40E"), propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "EPOLIGHT 70P"), polyethylene glycol diglycidyl Ether (manufactured by Nippon Oil & Fats Co., Ltd., trade name "EPIOL E-400"), polypropylene glycol diglycidyl ether (manufactured by Nippon Oil & Fats Co., Ltd., trade name "EPIOL P-200"), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd.) , product name "DENACOL EX-611"), glycerol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "DENACOL EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd.) Trade name "DENACOL EX-512"), sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl- Tris(2-hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, epoxy resin having two or more epoxy groups in the molecule, and the like. The content of the epoxy-based crosslinking agent can be set to any appropriate amount depending on the desired adhesive strength, and is typically 0.01 parts by weight to 10 parts by weight, more preferably 0.03 parts by weight, per 100 parts by weight of the base polymer. 5 parts by weight.

Any suitable adhesion-imparting agent can be used as the adhesion-imparting agent contained in the acrylic pressure-sensitive adhesive. As the adhesion-imparting agent, for example, an adhesive-imparting resin can be used. Specific examples of the adhesion-imparting resin include a rosin-based adhesion-imparting resin (for example, unmodified rosin, modified rosin, rosin phenol-based resin, rosin-ester resin, etc.) and a terpene-based adhesion-imparting resin (for example, Terpene resin, terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, hydrocarbon-based adhesion-imparting resin (for example, aliphatic hydrocarbon resin, Aliphatic cyclic hydrocarbon resin, aromatic hydrocarbon resin (for example, styrene resin, xylene resin, etc.), aliphatic, aromatic petroleum resin, aliphatic, alicyclic petroleum resin, hydrogenated hydrocarbon resin , a coumarone-based resin, a coumarone-ruthenium resin, etc.), a phenol-based adhesion-imparting resin (for example, an alkylphenol-based resin, a xylene-formaldehyde resin, a resol-formaldehyde resin, a novolak, etc.), and a ketone-based adhesive A resin, a polyamide-based adhesion-imparting resin, an epoxy-based adhesion-imparting resin, an elastic system adhesion-providing resin, and the like are provided. Among them, a rosin-based adhesion-imparting resin, a terpene-based adhesion-imparting resin, or a hydrocarbon-based adhesion-imparting resin (such as a styrene-based resin) is preferable. Adhesive-imparting agents can be used alone or in combination More than one kind. The amount of the adhesion-imparting agent added is preferably from 5 parts by weight to 100 parts by weight, more preferably from 10 parts by weight to 50 parts by weight, per 100 parts by weight of the base polymer.

It is preferred to use a resin having a high softening point or a glass transition temperature (Tg) as the above-mentioned adhesion-imparting resin. When a resin having a high softening point or a glass transition temperature (Tg) is used, an adhesive layer capable of exhibiting high adhesion can be formed even in a high-temperature environment (for example, in a high-temperature environment such as processing during sealing of a semiconductor wafer). . The softening point of the adhesion-imparting agent is preferably from 100 ° C to 180 ° C, more preferably from 110 ° C to 180 ° C, still more preferably from 120 ° C to 180 ° C. The glass transition temperature (Tg) of the adhesion-imparting agent is preferably from 100 ° C to 180 ° C, more preferably from 110 ° C to 180 ° C, still more preferably from 120 ° C to 180 ° C.

It is preferable to use a low-polarity adhesion-imparting resin as the above-mentioned adhesion-imparting resin. When a resin having a low polarity adhesion is used, an adhesive layer having a low affinity with a sealing material can be formed. Examples of the low polarity adhesion-imparting resin include an aliphatic hydrocarbon resin, an aliphatic cyclic hydrocarbon resin, an aromatic hydrocarbon resin (for example, a styrene resin, a xylene resin, etc.), and an aliphatic group. Aromatic petroleum resin, aliphatic. The alicyclic petroleum resin or the hydrogenated hydrocarbon resin is a hydrocarbon-based adhesion-imparting resin. Among them, an adhesion-imparting agent having a carbon number of 5 to 9 is preferred. Such an adhesion-imparting agent has a low polarity and is excellent in compatibility with an acrylic polymer, and does not cause phase separation in a wide temperature range, and can form an adhesive layer excellent in stability.

The acid value of the adhesion-imparting resin is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less. If it is such a range, the adhesive layer with low affinity with a sealing material can be formed. The hydroxyl value of the adhesion-imparting resin is preferably 60 or less, more preferably 40 or less, still more preferably 20 or less. If it is such a range, the adhesive layer with low affinity with a sealing material can be formed.

(rubber adhesive)

As the rubber-based pressure-sensitive adhesive, any appropriate adhesive can be used as long as the effects of the present invention can be obtained. As the rubber-based adhesive, for example, it is preferred to use as follows Rubber-based adhesives as a base polymer: natural rubber; polyisoprene rubber, butadiene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, benzene Ethylene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS) rubber, styrene-ethylene-propylene-styrene block copolymer (SEPS) rubber, styrene-ethylene-propylene block copolymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene rubber, or Synthetic rubber such as the modified body. These base polymers (rubbers) have a low sp value, and when the base polymer is used, an adhesive layer having a low affinity with a sealing material can be formed.

As the base polymer constituting the above rubber-based adhesive, it is particularly preferable to use a polyisobutylene rubber, a polyisoprene rubber or a butyl rubber. When these rubbers are used, it is possible to form an adhesive layer which is excellent in semiconductor wafer retention at room temperature and excellent in releasability. Further, it is possible to form an adhesive layer having low affinity with the sealing material.

As the base polymer constituting the rubber-based adhesive, a styrene-ethylene-propylene block copolymer (SEP) rubber or a styrene-ethylene-butylene-styrene block copolymer (SEBS) can also be preferably used. Rubber, styrene-isoprene-styrene block copolymer (SIS) rubber, styrene-butadiene-styrene block copolymer (SBS) rubber, propylene rubber. When these rubbers are used, an adhesive layer capable of exhibiting high adhesion can be formed even in a high-temperature environment (for example, in a high-temperature environment such as processing during sealing of a semiconductor wafer). In the base polymer (rubber) having a structural unit derived from styrene, the content ratio of the structural unit derived from styrene is preferably 15% by weight or more based on the total structural unit in the base polymer.

The above rubber-based adhesive may contain any appropriate additives as needed. Examples of the additive include a crosslinking agent, a vulcanizing agent, an adhesion-imparting agent, a plasticizer, a pigment, a dye, a filler, an anti-aging agent, a conductive material, an antistatic agent, an ultraviolet absorber, a light stabilizer, and a peeling agent. Conditioner, softener, surfactant, flame retardant, antioxidant Agents, etc.

Any suitable adhesion-imparting agent can be used as the adhesion-imparting agent contained in the rubber-based pressure-sensitive adhesive. As the adhesion-imparting agent, for example, an adhesive-imparting resin can be used. Specific examples of the adhesion-imparting resin include a rosin-based adhesion-imparting resin, a rosin-derived resin, a petroleum-based resin, a terpene-based resin, and a ketone-based resin. The amount of the adhesion-imparting agent added is preferably from 5 parts by weight to 100 parts by weight, more preferably from 10 parts by weight to 50 parts by weight, per 100 parts by weight of the base polymer.

Examples of the rosin-based resin contained in the rubber-based pressure-sensitive adhesive include gum rosin, wood rosin, and tall rosin. As the rosin-based resin, a stabilized rosin obtained by disproportionation or hydrogenation treatment of any appropriate rosin can also be used. Further, as the rosin-based resin, any suitable rosin may be modified by using a polymerized rosin which is a polymer of any appropriate rosin (typically a dimer) (for example, modification with an unsaturated acid) ) Modified rosin obtained.

Examples of the rosin derivative resin contained in the rubber-based adhesive include an esterified product of the rosin-based resin, a phenol-modified product of a rosin-based resin, and an esterified product of a phenol-modified rosin-based resin.

Examples of the petroleum-based resin contained in the rubber-based pressure-sensitive adhesive include an aliphatic petroleum resin, an aromatic petroleum resin, a copolymerized petroleum resin, an alicyclic petroleum resin, and the like.

Examples of the terpene-based resin contained in the rubber-based pressure-sensitive adhesive include an α -pinene resin, a β -pinene resin, an aromatic modified terpene resin, and a terpene phenol resin.

The ketone-based resin to be contained in the rubber-based pressure-sensitive adhesive is, for example, a ketone-based resin obtained by condensing a ketone (for example, an aliphatic ketone or an alicyclic ketone) with formaldehyde.

Examples of the crosslinking agent contained in the rubber-based pressure-sensitive adhesive include an isocyanate crosslinking agent. Examples of the vulcanizing agent contained in the rubber-based pressure-sensitive adhesive include, for example, The thiuram is a vulcanizing agent, a bismuth vulcanizing agent, a bismuth disulfide vulcanizing agent, and the like. When a rubber-based adhesive contains a crosslinking agent and/or a vulcanizing agent, it is possible to form an adhesive layer having high cohesiveness and being less likely to cause a paste residue. The total content of the crosslinking agent and the vulcanizing agent is typically from 0.1 part by weight to 20 parts by weight, more preferably from 0.1 part by weight to 10 parts by weight, per 100 parts by weight of the base polymer.

In one embodiment, a rubber-based adhesive (Rub1) comprising the above base polymer (rubber), a hydroxyl group-containing polyolefin, and a crosslinking agent a reactive with a hydroxyl group of the hydroxy polyolefin is used. In the rubber-based adhesive, the base polymer is not directly cross-linked, but the base polymer and the cross-linked polyolefin having a hydroxyl group are intertwined to perform so-called pseudo-crosslinking. As a result, an adhesive layer having high cohesiveness and being less likely to cause a paste residue can be formed. As the base polymer (rubber) used in the embodiment, the above-mentioned synthetic rubber is preferably used. Further, as the crosslinking agent used in the embodiment, an isocyanate crosslinking agent is preferably used.

The amount of the hydroxyl group-containing polyolefin is preferably 0.5 parts by weight or more, more preferably 1.0% by weight based on 100 parts by weight of the total of the base polymer (rubber), the hydroxyl group-containing polyolefin, and the crosslinking agent a. More than one. If it is such a range, the adhesive layer with high cohesiveness can be formed. Moreover, when the adhesive sheet has a base material layer, the adhesion (clawing force) of the base material layer and the adhesive layer can be improved. In other words, when the blending amount of the hydroxyl group-containing polyolefin is in the above range, an adhesive sheet having less paste residue can be obtained.

The amount of the crosslinking agent a is preferably 0.5 parts by weight or more, more preferably 1.0 part by weight, based on 100 parts by weight of the total of the base polymer (rubber), the hydroxyl group-containing polyolefin, and the crosslinking agent a. the above. If it is such a range, the adhesive layer with high cohesiveness can be formed. Moreover, when the adhesive sheet has a base material layer, the adhesion (clawing force) of the base material layer and the adhesive layer can be improved. In other words, when the amount of the crosslinking agent a is in the above range, an adhesive sheet having less residual resin can be obtained.

As the above hydroxyl group-containing polyolefin, it is preferred to use a phase with the above synthetic rubber. A resin with excellent solubility. Examples of the hydroxyl group-containing polyolefin include a polyethylene polyol, a polypropylene polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a polyisoprene polyol, and a hydrogenated polyisoprene. Diene polyols and the like. From the viewpoint of compatibility with the above synthetic rubber, among them, a hydrogenated polyisoprene polyol, a polyisoprene polyol, and a polybutadiene polyol are preferable.

The number average molecular weight (Mn) of the above hydroxyl group-containing polyolefin is preferably from 500 to 500,000, more preferably from 1,000 to 200,000, still more preferably from 1,200 to 150,000. The number average molecular weight can be determined in accordance with ASTM D2503.

The hydroxyl value (mgKOH/g) of the above hydroxyl group-containing polyolefin is preferably from 5 to 95, more preferably from 10 to 80. The hydroxyl value can be measured in accordance with JIS K1557: 1970.

(polyoxygenated adhesive)

As the polyadoxic adhesive, any appropriate adhesive can be used as long as the effects of the present invention can be obtained. As the polyoxynoxy adhesive, for example, a polyoxynoxy adhesive containing a polyoxyxylene rubber or a polyoxyxylene resin containing an organic polyoxyalkylene as a base polymer can be preferably used. As the base polymer constituting the polyoxygen-based adhesive, a base polymer obtained by crosslinking the above-mentioned polyoxyethylene rubber or polyoxynoxy resin can also be used. In the present specification, the term "polyoxyxene rubber" means a polymer in which a diorganosiloxane (D unit) as a main component is connected in a linear form (for example, a viscosity of 1000 Pa.s); "Oxygen resin" means a polymer composed of a triorganohalfoxane (M unit) and a niobate (Q unit) as a main component ("material design and functional imparting of an adhesive (film)") , Technical Information Association, issued on September 30, 2009).

Examples of the polyoxyxylene rubber include an organic polyoxyalkylene containing dimethyl siloxane as a structural unit. A functional group (for example, a vinyl group) may be introduced into the organic polyoxyalkylene as needed. The weight average molecular weight of the organic polyoxyalkylene is preferably from 100,000 to 1,000,000, more preferably from 150,000 to 500,000. The weight average molecular weight can be measured by GPC (solvent: THF).

Examples of the polyfluorene oxide resin include an organic polyfluorene oxide containing at least one structural unit selected from the group consisting of R ₃ SiO _1/2 structural unit, SiO ₂ structural unit, RSiO _3/2 structural unit, and R ₂ SiO structural unit. An alkane (R is a monovalent hydrocarbon group or a hydroxyl group).

The above polyoxyxene rubber and polyfluorene oxide resin may be used in combination. The weight ratio of the polyoxyxene rubber to the polyoxyxylene resin in the polyoxyxylene adhesive (rubber: resin) is preferably from 100:0 to 100:220, more preferably from 100:0 to 100:180, and further preferably 100:10~100:100. The polyoxyxene rubber and the polyoxynoxy resin may be contained in the polyoxynoxy adhesive as a simple mixture, or may be partially condensed in the form of a polyoxyxene rubber and a polyoxyxylene resin. In the agent. The rubber: resin ratio can also be determined from the ratio of the Q unit (resin) to the D unit (rubber) obtained by measuring the composition of the polyoxygen adhesive by ²⁹ Si-NMR.

The above polyoxygenated adhesive may contain any appropriate additives as needed. Examples of the additive include a crosslinking agent, a vulcanizing agent, an adhesion-imparting agent, a plasticizer, a pigment, a dye, a filler, an anti-aging agent, a conductive material, an antistatic agent, an ultraviolet absorber, a light stabilizer, and a peeling agent. Adjusting agent, softener, surfactant, flame retardant, antioxidant, etc.

It is preferred that the polyoxynitride-based adhesive contains a crosslinking agent. Examples of the crosslinking agent include a decane-based crosslinking agent and a peroxide-based crosslinking agent. As the peroxide-based crosslinking agent, any appropriate crosslinking agent can be used. Examples of the peroxide-based crosslinking agent include benzamidine peroxide, tert-butyl peroxybenzoate, and dicumyl peroxide. Examples of the oxirane-based crosslinking agent include polyorganohydroquinones and the like. The polyorganohydroquinone is preferably one having two or more hydrogen atoms bonded to a deuterium atom. Further, the polyorganohydrohalosiloxane preferably has an alkyl group, a phenyl group or a halogenated alkyl group as a functional group bonded to a ruthenium atom.

(active energy ray hardening type adhesive)

As the above-mentioned adhesive, an active energy ray-curable adhesive which can be cured by irradiation with an active energy ray (high elastic modulus) can also be used. If using active energy In the ray-curable adhesive, the following adhesive sheet can be obtained: it has low elasticity at the time of attachment, has high flexibility, and is excellent in handleability, and when it is required to be peeled off, the adhesive force can be lowered by irradiation of an active energy ray. Examples of the active energy ray include gamma rays, ultraviolet rays, visible rays, infrared rays (hot rays), radio frequency waves, alpha rays, beta rays, electron beams, plasma streams, ionizing rays, particle beams, and the like. In the case where the term "adhesive layer" is used in this specification, it means an adhesive layer before the adhesive is hardened and the adhesive force is lowered.

Examples of the resin material constituting the active energy ray-curable adhesive include an ultraviolet curing system (Approved by Kato Qingyu, Integrated Technology Center, (1989)), photo-curing technology (Technical Information Association (2000)), and Japan. A resin material described in JP-A-2003-292916, Japanese Patent No. 4151850, and the like. More specifically, a resin material (R1) containing a polymer as a mother agent and an active energy ray-reactive compound (monomer or oligomer), and a resin material (R2) containing an active energy ray-reactive polymer are mentioned. Wait.

Examples of the polymer to be used as the mother agent include natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, and butyl rubber. A rubber-based polymer such as polyisobutylene rubber or nitrile rubber (NBR); a polyfluorene-based polymer; an acrylic polymer. These polymers may be used singly or in combination of two or more. As the polymer to be used as the mother agent, from the viewpoint of affinity with the sealing material, it is preferred to use a base polymerization as the above-mentioned acrylic adhesive, rubber adhesive or polyoxygen adhesive. a polymer exemplified.

Examples of the active energy ray-reactive compound include a photoreactive monomer having a functional group having a carbon-carbon multiple bond such as an acrylonitrile group, a methacryl group, a vinyl group, an allyl group, or an ethynyl group, or Oligomer. Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, and pentaerythritol tris(methyl). Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. (methyl) a compound of an acrylonitrile group; a bis-pentapolymer of a compound containing a (meth) acrylonitrile group;

Further, as the active energy ray-reactive compound, a monomer such as epoxidized butadiene, glycidyl methacrylate, acrylamide or vinyl siloxane, or an oligomer composed of the monomer may be used. . The resin material (R1) containing these compounds can be hardened by high-energy rays such as ultraviolet rays or electron beams.

Further, as the active energy ray-reactive compound, a mixture of an organic salt such as a phosphonium salt and a compound having a plurality of heterocyclic rings in the molecule may be used. The mixture can be cleaved by irradiation of an active energy ray (for example, ultraviolet rays, electron beams) to generate ions, and the starting species can cause a ring-opening reaction of the hetero ring to obtain a three-dimensional network structure. Examples of the organic salt include a phosphonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, and a borate. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, oxetane, oxolane, ethylene sulfide, and aziridine.

In the resin material (R1) containing the polymer as the mother agent and the active energy ray-reactive compound, the content ratio of the active energy ray-reactive compound is preferably 0.1% by weight based on 100 parts by weight of the polymer to be the mother agent. The portion is preferably 500 parts by weight, more preferably 1 part by weight to 300 parts by weight, still more preferably 10 parts by weight to 200 parts by weight. If it is such a range, the adhesive layer with low affinity with a sealing material can be formed.

The resin material (R1) containing the polymer as the mother agent and the active energy ray-reactive compound may contain any appropriate additives as needed. Examples of the additive include an active energy ray polymerization initiator, an active energy ray polymerization accelerator, a crosslinking agent, a plasticizer, a vulcanizing agent, and the like. As the active energy ray polymerization initiator, any appropriate initiator can be used depending on the kind of active energy ray used. The active energy ray polymerization initiators may be used singly or in combination of two or more. Active energy ray polymerization in a resin material (R1) containing a polymer as a mother agent and an active energy ray-reactive compound The content ratio of the initiator is preferably from 0.1 part by weight to 10 parts by weight, more preferably from 1 part by weight to 5 parts by weight, per 100 parts by weight of the polymer to be the mother agent.

The active energy ray-reactive polymer may, for example, be a polymer having a functional group having a carbon-carbon multiple bond such as an acrylonitrile group, a methacryl group, a vinyl group, an allyl group or an ethynyl group. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate. The polymer composed of a polyfunctional (meth) acrylate preferably has an alkyl ester having 4 or more carbon atoms, more preferably an alkyl ester having 6 or more carbon atoms, and more preferably has a carbon number of The alkyl ester of 8 or more is particularly preferably an alkyl ester having a carbon number of 8 to 20, and most preferably an alkyl ester having a carbon number of 8 to 18. When a polymer having a long side chain is used, an adhesive layer having a low affinity with a sealing material can be formed. In the polymer, the content ratio of the structural unit having an alkyl ester having a carbon number of 4 or more in the side chain is preferably 30% by weight or more, more preferably 50% by weight or more based on the total structural unit constituting the polymer. Further, it is preferably from 70% by weight to 100% by weight, particularly preferably from 80% by weight to 100% by weight. If it is such a range, the adhesive layer with low affinity with a sealing material can be formed.

The resin material (R2) containing the active energy ray-reactive polymer may further contain the above-mentioned active energy ray-reactive compound (monomer or oligomer). Further, the resin material (R2) containing the active energy ray-reactive polymer may contain any appropriate additives as needed. Specific examples of the additive are the same as those which may be contained in the resin material (R1) containing the polymer as the mother agent and the active energy ray-reactive compound. In the resin material (R2) containing the active energy ray-reactive polymer, the content ratio of the active energy ray-polymerization initiator is preferably from 0.1 part by weight to 10 parts by weight per 100 parts by weight of the active energy ray-reactive polymer. More preferably, it is 1 part by weight to 5 parts by weight.

<heat-expandable microspheres>

In one embodiment, the adhesive layer further includes heat-expandable microspheres. An adhesive sheet having an adhesive layer containing heat-expandable microspheres is heated to heat the microspheres The expansion or foaming causes irregularities on the adhesive surface, and as a result, the adhesive force decreases or disappears. Such an adhesive sheet can be easily peeled off by heating.

As the heat-expandable microspheres, any suitable heat-expandable microspheres can be used as long as it is a microsphere which can be expanded or foamed by heating. As the heat-expandable microspheres, for example, a microsphere in which a material which is easily expanded by heating is enclosed in a shell having elasticity can be used. Such heat-expandable microspheres can be produced by any appropriate method, such as coacervation, interfacial polymerization, and the like.

Examples of the substance which is easily swelled by heating include propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, heptane. a low boiling point liquid such as octane, petroleum ether, methane halide or tetraalkyl decane; azodicarboxyguanamine which is vaporized by thermal decomposition.

Examples of the material constituting the shell include a polymer composed of acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, α -ethoxy acrylonitrile, and a nitrile monomer such as fumaronitrile; a carboxylic acid monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid or citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth)acrylate, (a) Ethyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylate Ester, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, β -carboxyethyl acrylate (meth) acrylate; styrene, styrene, α -methyl styrene, chlorostyrene, etc. a phthalamide monomer such as acrylamide, substituted acrylamide, methacrylamide or substituted methacrylamide. The polymer composed of the monomers may be a homopolymer or a copolymer. Examples of the copolymer include a vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, a methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and a methyl methacrylate-acrylonitrile copolymer. , acrylonitrile-methacrylonitrile-iconic acid copolymer, and the like.

As the heat-expandable microspheres, an inorganic foaming agent or an organic foaming agent can also be used. Examples of the inorganic foaming agent include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, and various azides. Further, examples of the organic foaming agent include a chlorofluoroalkane compound such as trichloromonofluoromethane or dichloromonofluoromethane; azobisisobutyronitrile, azobiscarboxyguanamine, and azodicarboxylate; An azo compound such as strontium sulphate; p-toluene sulfonium, diphenyl hydrazine-3,3'-disulfonium, 4,4'-oxybis(phenylsulfonate), allyl bis (sulfonate)肼) an oxime compound; an aminourea-based compound such as p-toluenesulfonyl urea or 4,4'-oxybis(phenylsulfonylaminourea); Triazole compound such as phenyl-1,2,3,4-thiatriazole; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'- An N-nitroso compound such as dinitroso-p-xylyleneamine or the like.

A commercially available product can also be used for the above-mentioned heat-expandable microspheres. Specific examples of the heat-expandable microspheres of the commercially available product include the product name "Matsumoto Microsphere" manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd. (Grade: F-30, F-30D, F-36D, F-36LV, F-50) , F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), the product name of Japan Fillite Co., Ltd. EXPANCEL" (grade: 053-40, 031-40, 920-40, 909-80, 930-120), "DAIFOAM" by Wu Yu Chemical Industry Co., Ltd. (Class: H750, H850, H1100, S2320D, S2640D, M330) , M430, M520), "ADVANCELL" manufactured by Sekisui Chemical Industry Co., Ltd. (grade: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501).

The particle diameter of the heat-expandable microspheres before heating is preferably from 0.5 μm to 80 μm, more preferably from 5 μm to 45 μm, still more preferably from 10 μm to 20 μm, still more preferably from 10 μm to 15 μm. Therefore, when the particle size before heating of the heat-expandable microspheres is referred to as an average particle diameter, it is preferably 6 μm to 45 μm, and more preferably 15 μm to 35 μm. The above-mentioned particle diameter and average particle diameter are values obtained by a particle size distribution measurement method in a laser scattering method.

The heat-expandable microspheres preferably have an appropriate strength which does not break before the volume expansion ratio is preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more. When using such a heat-expandable microsphere, it can be treated by heat treatment And the adhesion is lowered efficiently.

The content ratio of the heat-expandable microspheres in the above-mentioned pressure-sensitive adhesive layer can be appropriately set depending on the desired decrease in the adhesive force or the like. The content ratio of the heat-expandable microspheres is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, and more preferably 25 parts by weight, per 100 parts by weight of the base polymer forming the pressure-sensitive adhesive layer. 100 parts by weight.

In the case where the adhesive layer contains heat-expandable microspheres, the arithmetic surface roughness Ra of the adhesive layer before expansion of the heat-expandable microspheres (that is, before heating) is preferably 500 nm or less, more preferably 400 nm or less, and further It is preferably 300 nm or less. If it is such a range, the adhesive sheet excellent in the adhesiveness with respect to an adherend can be obtained. The adhesive layer excellent in surface smoothness can be obtained, for example, by operating the thickness of the adhesive layer to the above range and applying the adhesive layer to the separator when the other adhesive layer is provided. . Further, in the case where the adhesive sheet of the present invention further has another adhesive layer as described in the above item A, the other adhesive layer may further contain heat-expandable microspheres. In the case where the other adhesive layer contains the heat-expandable microspheres, the arithmetic surface roughness Ra of the adhesive layer is also preferably in the above range.

In the case where the adhesive layer contains heat-expandable microspheres, the adhesive layer preferably comprises a base polymerization in a range of 5 kPa to 1 MPa (more preferably 10 kPa to 0.8 MPa) by a dynamic storage elastic modulus at 80 ° C. The adhesive that constitutes the object. In the case of such an adhesive layer, it is possible to form an adhesive sheet which has an appropriate adhesive property before heating and which is easily lowered by heating. Further, the dynamic storage elastic modulus can be measured by a dynamic viscoelasticity measuring apparatus (for example, trade name "ARES" manufactured by Rheometrics Co., Ltd.) at a frequency of 1 Hz and a temperature rising rate of 10 ° C/min.

C. substrate layer

In one embodiment, the adhesive sheet of the present invention comprises an adhesive layer and a substrate layer. Fig. 2 (a) is a schematic cross-sectional view showing an adhesive sheet according to an embodiment of the present invention. The adhesive sheet 100 includes an adhesive layer 10 and a substrate layer 30 disposed on one side of the adhesive layer 10. Figure 2(b) A schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. The adhesive sheet 200 includes an adhesive layer 10 and a base material layer 30, and an adhesive layer 10 is disposed on both sides of the base material layer 30. The adhesive layer of the two layers may be the same adhesive layer or the adhesive layer of different composition. Further, the pressure-sensitive adhesive layer may be provided on one side of the base material layer and the other adhesive layer may be provided on the other surface.

In the case where the adhesive sheet of the present invention has a substrate layer, the gripping force of the base layer and the adhesive layer is preferably 6.0 N/19 mm or more, more preferably 15 N/19 mm or more.

The above grasping force can be measured in the following manner. The above-mentioned gripping force can be obtained as follows: (i) in the case of an adhesive sheet having a width of 20 mm × a length of 150 mm on the opposite side to the adhesive layer (for example, in the case of an adhesive sheet composed of a substrate layer/adhesive layer) The SUS plate is bonded to the entire surface of the outer surface of the substrate layer via a special double-sided tape; (ii) the outer surface of the adhesive layer of the adhesive sheet is attached with a width of 19 mm and a length of 150 mm. A sheet for adhesion evaluation of a polyester resin (a sheet having a peeling force of 10 N/20 mm to 20 N/20 mm for polyethylene terephthalate, for example, a product name "No. 315" manufactured by Nitto Denko Corporation The adhesive surface of Tape") was prepared for evaluation; (iii) The peeling force between the substrate layer of the adhesive sheet and the adhesive layer was measured by a tensile test. Further, the above (i) to (iii) were carried out at an ambient temperature of 23 °C. The conditions of the tensile test when the peeling force was measured: the peeling speed was 50 mm/min, and the peeling angle was 180°.

As described above, the adhesive sheet having a high gripping force of the base material layer and the adhesive layer is an adhesive sheet which is substantially resistant to the residue of the paste, and the effect of the present invention becomes remarkable when it is such an adhesive sheet. In the case of evaluation by the above method, it is more preferable that the interface between the substrate layer and the adhesive layer is not peeled off, for example, an adhesive sheet which is peeled off between the SUS plate and the substrate layer. The adhesive sheet having a high grip strength can be obtained, for example, by using the above-mentioned rubber-based adhesive (Rub 1) as an adhesive and adding an isocyanate-based crosslinking agent to the adhesive.

Examples of the base material layer include a resin sheet, a nonwoven fabric, paper, a metal foil, a woven fabric, a rubber sheet, a foamed sheet, and the like (especially including a resin sheet). Laminates, etc.). Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene ( PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamine (nylon), wholly aromatic polyamine (aromatic polyamide), polypyrene Amine (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine-based resin, polyetheretherketone (PEEK), and the like. Examples of the nonwoven fabric include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics of Manila hemp, synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics, and ester resin nonwoven fabrics. Examples of the metal foil include copper foil, stainless steel foil, and aluminum foil. Examples of the paper include Japanese paper, kraft paper, and the like.

The thickness of the base material layer can be set to any appropriate thickness depending on the desired strength, flexibility, purpose of use, and the like. The thickness of the base material layer is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, still more preferably 3 μm to 300 μm, and most preferably 5 μm to 250 μm.

The base material layer may also be subjected to a surface treatment. Examples of the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment using a primer.

Examples of the organic coating material include materials described in Plastic Hard Coating Material II (CMC Publishing, (2004)). It is preferred to use a urethane-based polymer, more preferably a polyacrylic acid urethane, a polyester urethane or the precursors. The reason is that the coating to the substrate. The coating is simple, and a variety of substances can be selected industrially and can be obtained at low cost. The urethane-based polymer is, for example, a polymer formed of a reaction mixture of an isocyanate monomer and a monomer having an alcoholic hydroxyl group (for example, an acrylic compound containing a hydroxyl group or an ester compound containing a hydroxyl group). The organic coating material may also contain a chain extender such as a polyamine, an anti-aging agent, an oxidation stabilizer or the like as an optional additive. The thickness of the organic coating layer is not particularly limited, and is, for example, about 0.1 μm to 10 μm, preferably about 0.1 μm to 5 μm, and more preferably about 0.5 μm to 5 μm.

D. Elastic layer

The adhesive sheet of the present invention may further comprise an elastic layer. Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment of the present invention. The adhesive sheet 300 further includes an elastic layer 40. The elastic layer 40 can be preferably disposed in the case where the adhesive layer 10 contains the above-described heat-expandable microspheres. Moreover, when the adhesive sheet 300 is provided with the base material layer 30, the elastic layer 40 may be disposed between the adhesive layer 10 and the base material layer 30 as shown in the example, or may be disposed on the base material layer and the adhesive. One side of the opposite side of the layer. The elastic layer 40 may also be provided in two or more layers. Further, FIG. 3 shows an example in which one elastic layer 40 is provided and the elastic layer 40 is disposed between the adhesive layer 10 and the base material layer 30. By providing the elastic layer 40, the followability to the adherend is improved. Further, when the adhesive sheet having the elastic layer 40 is heated at the time of peeling, deformation (expansion) in the surface direction of the adhesive layer is restricted, and deformation in the thickness direction is prioritized. As a result, the peelability is improved.

The elastic layer contains a base polymer, and as the base polymer, a polymer exemplified as a base polymer constituting the above adhesive layer can be used. Further, the elastic layer may contain natural rubber, synthetic rubber, synthetic resin or the like. Examples of the synthetic rubber and the synthetic resin include a nitrile-based, diene-based, and acrylic-based synthetic rubber; a thermoplastic elastomer such as a polyolefin-based or polyester-based; an ethylene-vinyl acetate copolymer; and a polyurethane. Polybutadiene; soft polyvinyl chloride, etc. The base polymer constituting the above elastic layer may be the same as or different from the base polymer forming the above adhesive layer. The elastic layer may also be a foamed film formed of the above base polymer. The foamed film can be obtained by any suitable method. Further, the elastic layer and the adhesive layer can be distinguished by the difference of the base polymer and/or the presence or absence of the heat-expandable microspheres (the elastic layer does not contain the heat-expandable microspheres).

The above elastic layer may contain any appropriate additives as needed. Examples of the additive include a crosslinking agent, a vulcanizing agent, an adhesion-imparting agent, a plasticizer, a softening agent, a filler, and an anti-aging agent. When a hard resin such as polyvinyl chloride is used as the base polymer, it is preferred to use a plasticizer and/or a softener in combination to form an elastic layer having a desired elasticity.

The thickness of the elastic layer is preferably from 3 μm to 200 μm, more preferably from 5 μm to 100 μm. If it is such a range, an elastic layer can fully exhibit the said function.

The tensile modulus of the elastic layer at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, still more preferably 0.1 MPa to 10 MPa. If it is such a range, an elastic layer can fully exhibit the said function.

E. Isolation

The adhesive sheet of the present invention may further comprise a separator as needed. At least one surface of the separator is a peeling surface and can be provided to protect the adhesive layer. The spacer can be constructed of any suitable material.

F. Method for manufacturing adhesive sheet

The adhesive sheet of the present invention can be produced by any suitable method. The adhesive sheet of the present invention may, for example, be a method of directly applying a composition containing an adhesive to a substrate layer (any suitable substrate in the case where an adhesive sheet containing no substrate layer is obtained). Or a method of transferring a coating layer formed by coating a composition containing an adhesive to a substrate layer on any suitable substrate. The composition comprising the adhesive may comprise any suitable solvent.

In the case of forming an adhesive layer containing heat-expandable microspheres, a composition comprising heat-expandable microspheres, an adhesive, and any suitable solvent may be applied to the substrate layer to form the adhesive layer. Alternatively, the heat-expandable microspheres may be sprinkled on the adhesive coating layer, and the heat-expandable microspheres may be embedded in an adhesive using a laminator or the like to form an adhesive layer containing the heat-expandable microspheres.

In the case where the adhesive layer has the above elastic layer, the elastic layer can be formed, for example, by coating a composition for forming an elastic layer on a substrate layer or an adhesive layer.

As the above-mentioned adhesive and the coating method of each composition, any appropriate coating method can be employed. For example, it can be dried after coating to form each layer. Examples of the coating method include a multi-coater, a die coater, and gravure coating. Coating method of machine, applicator, etc. Examples of the drying method include natural drying, heat drying, and the like. The heating temperature at the time of heat drying can be set to any appropriate temperature depending on the characteristics of the substance to be dried.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. The evaluation methods in the examples are as follows. Further, in the examples, "parts" and "%" are based on weight unless otherwise specified.

(1) Contact angle

The adhesive sheet was placed on a glass slide with the adhesive layer facing upward, and the contact angle of the surface of the adhesive layer with respect to 4-t-butylphenyl glycidyl ether was measured.

2 μl of 4-t-butylphenyl glycidyl ether was added dropwise to the surface of the adhesive layer, and the contact angle (N=5) after 5 seconds was measured. The measurement of the contact angle was carried out in an atmosphere of 23 ° C and 50% RH using a contact angle meter (trade name "CX-A type" manufactured by Kyowa Interface Co., Ltd.).

(2) sp value

The sp value of the polymer in the adhesive layer after the adhesive sheet is formed according to the method of Fedors (Yamamoto Hideyuki, "sp value basis. Application and calculation method", published by Information Agency Co., Ltd., April 3, 2006 Issued, 66~67 pages) and calculated. Specifically, the sp value is the evaporation energy Δe(cal) at 25 ° C of each atom or group of atoms forming the polymer, and the molar volume ΔV at 25 ° C of each atom or group forming the polymer ( Cm ³ ), calculated according to the following formula.

Sp value = (Σ△e/Σ△V) ^1/2

Further, when the polymer is a copolymer, the Sp value is calculated by calculating the Sp value of each of the homopolymers constituting each structural unit of the copolymer, and multiplying the Sp values by each The molar fraction of the structural unit is summed with the values obtained.

In the above case, regarding the analysis method of each structural unit (composition analysis of the polymer), only the adhesive layer can be appropriately taken from the adhesive sheet, and it is immersed in dimethyl group. The solvent-soluble portion obtained by the organic solvent such as meglumine (DMF), acetone, methanol or tetrahydrofuran (THF) is recovered by gel filtration chromatography (GPC), nuclear magnetic resonance spectroscopy (NMR), infrared It is obtained by analytical methods of spectroscopic method (IR) and mass analysis.

(3) Adhesion

The entire surface of the adhesive sheet (width: 20 mm × length: 140 mm) on the side opposite to the adhesive layer was attached to a double-sided adhesive tape (manufactured by Nitto Denko Corporation under the trade name "No. 531") using a 2 kg hand roller. SUS304 board.

Then, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "Lumirror S-10", thickness: 25 μm, width: 30 mm) was attached to the entire surface of the pressure-sensitive adhesive layer (temperature: 23 ° C, Humidity: 65%, 2kg roller round trip 1).

The sample for evaluation obtained in the above manner was subjected to a tensile test. As a tensile tester, the product name "Shimadzu Autograph AG-120kN" manufactured by Shimadzu Corporation was used. After the evaluation sample was placed in a tensile tester, it was allowed to stand at an ambient temperature of 23 ° C for 30 minutes, and thereafter the tensile test was started. The conditions of the tensile test were set to a peeling angle: 180°, and a peeling speed (tensile speed): 300 mm/min. The load at the time of peeling off the adhesive sheet from the PET film was measured, and the maximum load at this time was used as the adhesive force of the adhesive sheet.

(4) Grasping force

The entire surface of the adhesive sheet (width: 20 mm × length: 140 mm) on the opposite side to the adhesive layer was applied by a double-sided tape (manufactured by Nitto Denko Corporation, trade name "No. 531"), using 2 kg of hand pressure. The roller was attached to a SUS304 plate (width 40 mm x length 120 mm).

Then, the sheet for evaluation (manufactured by Nitto Denko Corporation, trade name "No. 315 Tape", width 19 mm × length 150 mm) (temperature: 23 ° C, humidity: 65%, 2 kg roller reciprocating once) was attached.

The sample for evaluation obtained in the above manner was subjected to a tensile test. As a tensile tester, the product name "Shimadzu Autograph AG-" manufactured by Shimadzu Corporation was used. 120kN". The conditions of the tensile test were set to a peeling angle: 180°, and a peeling speed (tensile speed): 50 mm/min. The sheet for evaluation was gripped, and the load to be peeled off from the base layer of the adhesive sheet was measured, and the maximum load at this time was used as the gripping force of the base layer and the adhesive layer.

(5) Adhesion value

The entire surface of the adhesive sheet (width: 20 mm × length: 50 mm) on the side opposite to the adhesive layer was applied by a double-sided tape (manufactured by Nitto Denko Corporation, trade name "No. 531"), using 2 kg of hand pressure. The roller was attached to a slide glass (made by Songlang Glass Industrial Co., Ltd., 26 mm × 76 mm).

The probe viscosity value of the outer surface of the adhesive layer in the sample for evaluation obtained in the above manner was measured using a probe viscosity measuring machine (manufactured by RHESCA, trade name "TACKINESS Model TAC-II"). The measurement conditions were set to: Immersion speed: 30 mm/min, test speed: 30 mm/min, adhesion load (Prelod): 100 gf, press time: 1 second, probe Area (Probe Area): 5mm SUS.

(6) Retention test

The outer surface of the adhesive layer of the adhesive sheet (width: 10 mm × length: 150 mm) was applied to the electric board at a temperature of 23 ° C at an ambient temperature of 23 ° C (made by Futamura Chemical Co., Ltd., trade name "TAIKOLITE FL-102". The central portion of the width 25 mm × length 125 mm × thickness 2 mm).

The sample for evaluation obtained in the above manner was placed at an ambient temperature of 40 ° C for 30 minutes for aging, and then a tape creep tester (manufactured by Ida Seisakusho Co., Ltd., type/model "12-weight hammer type / 041") was used. A load of 1.96 N was applied and maintained in this state for 2 hours.

The moving distance (offset) of the adhesive sheet due to pressurization was measured using the position on the electric board before pressurization as a reference. The shorter the moving distance, the higher the holding force.

(7) Surface roughness

The arithmetic surface roughness Ra of the surface of the adhesive layer of the adhesive sheet was measured in accordance with JIS B0601. As the measuring machine, an optical surface roughness meter (manufactured by Veeco Metrogy Group Co., Ltd., trade name "Wyko NT9100") was used.

(8) clearance height suppression effect

100 parts by weight of a naphthalene type bifunctional epoxy resin (trade name "HP4032D", epoxide equivalent: 144), and phenoxy resin (manufactured by Mitsui Chemicals, Inc., trade name "EP4250"), 40 parts by weight, phenol system 129 parts by weight of spheroidal cerium oxide (product name "SO-25R" manufactured by Admatech Co., Ltd.), and a dye (manufactured by Orient Chemical Industries Co., Ltd.), 129 parts by weight of a resin (manufactured by Megumi Kasei Co., Ltd., trade name "MEH-8000") 14 parts by weight of a "OIL BLACK BS", 1 part by weight of a curing catalyst (manufactured by Shikoku Kasei Co., Ltd., trade name "2PHZ-PW"), and 30 parts by weight of methyl ethyl ketone were mixed to prepare a resin solution A ( Solid content concentration: 23.6% by weight).

A Si wafer (1 cm × 1 cm, thickness: 500 μm) was placed on the adhesive layer of the adhesive sheet, and the resin solution A was applied to the adhesive layer so as to cover the Si wafer (coating size: 3 cm × 3 cm), the resin solution was cured by heating at 170 ° C for 10 minutes to form a structure including a Si wafer and a sealing resin on the adhesive layer of the adhesive sheet.

After cooling, the adhesive sheet was peeled off from the structure. For the adhesive sheet after peeling, the difference between the thickness of the adhesive layer which is not in contact with the Si wafer and the thickness of the adhesive layer which is in contact with the Si wafer is taken as the gap height.

(9) Paste residue

As in the above (8), a structure including a Si wafer and a sealing resin is formed on the adhesive sheet, and after cooling, the adhesive sheet is peeled off from the structure. After the peeling, the bonding surface of the above-mentioned structure was observed with a microscope (manufactured by Keyence Corporation, "VHX-100", magnification: 150 times), and the presence or absence of the adhesive layer component adhering to the structure was confirmed. in FIG. 1, When the particle diameter is 100 μm (in the case of an amorphous shape, the length of the longest side is 100 μm), the number of adhering substances is less than five, and the case where five or more are used is referred to as ×.

[Example 1]

Acrylic copolymer as a base polymer (copolymer of 2-ethylhexyl acrylate and hydroxyethyl acrylate, and 2-ethylhexyl acrylate structural unit: hydroxyethyl acrylate structural unit = 100:5 (weight (1) parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE L"), and a terpene phenol-based adhesion-imparting resin (manufactured by YASUHARA CHEMICAL Co., Ltd., trade name "YS POLYSTAR S145" 10 parts by weight and 100 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.

The composition for forming an adhesive layer was applied to one side of a polytetrafluoroethylene film (manufactured by Toray Industries, Inc., trade name "Lumirror S10", thickness: 38 μm) as a base material layer to obtain a substrate layer and adhesion. The adhesive layer (thickness 10 μm) constitutes an adhesive sheet.

[Embodiment 2]

Acrylic copolymer as a base polymer (copolymer of 2-ethylhexyl acrylate with acrylic acid and trimethylolpropane acrylate, and 2-ethylhexyl acrylate structural unit: acrylic structural unit: trishydroxyl Base propane acrylate structural unit = 100:3:0.03 (by weight)) 100 parts by weight, an epoxy-based crosslinking agent (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.), 0.5 part by weight, a terpene phenol system 10 parts by weight of an adhesive-bonding resin (trade name "YS POLYSTAR S145", manufactured by YASUHARA CHEMICAL CORPORATION) and 100 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.

The composition for forming an adhesive layer was applied to one side of a polytetrafluoroethylene film (manufactured by Toray Industries, Inc., trade name "Lumirror S10", thickness: 38 μm) as a base material layer to obtain a substrate layer and adhesion. The adhesive layer (thickness 10 μm) constitutes an adhesive sheet.

[Example 3]

Addition-reactive polyoxynene adhesive (manufactured by Toray Industries, Inc., trade name "Silicone" Rubber SD-4580L", polyoxyxene rubber: polyoxyl resin = 60:40 (weight ratio)) 100 parts by weight, platinum-based catalyst (manufactured by Toray Industries, Inc., trade name "SRX-212") 0.5 parts by weight And 100 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.

The adhesive layer-forming composition was applied to one side of a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name "KAPTON 200H", thickness: 50 μm) as a base material layer to obtain a substrate layer and Adhesive sheet composed of an adhesive layer (10 μm).

[Example 4]

100 parts by weight of a polyisobutylene-based rubber (manufactured by BASF JAPAN Co., Ltd., trade name "Oppanol B80"), 1.5 parts by weight of a hydroxyl group-containing polyolefin (trade name "EPOL", manufactured by Idemitsu Kosan Co., Ltd.), and an isocyanate crosslinking agent ( 4 parts by weight of the product name "CORONATE L" manufactured by Nippon Polyurethane Industry Co., Ltd. and 200 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.

The composition for forming an adhesive layer was applied to one side of a polytetrafluoroethylene film (manufactured by Toray Industries, Inc., trade name "Lumirror S10", thickness: 38 μm) as a base material layer to obtain a substrate layer and adhesion. The adhesive layer (thickness 10 μm) constitutes an adhesive sheet.

[Example 5]

In addition, 30 parts by weight of heat-expandable microspheres (product name "Matsumoto Microsphere F-50", manufactured by Matsumoto Oil & Fats Co., Ltd.) was added to the composition for forming an adhesive layer, and the thickness of the adhesive layer was 40 μm. An adhesive sheet was obtained in the same manner as in Example 1.

[Embodiment 6]

In addition, 30 parts by weight of heat-expandable microspheres (product name "Matsumoto Microsphere F-50", manufactured by Matsumoto Oil & Fats Co., Ltd.) was added to the composition for forming an adhesive layer, and the thickness of the adhesive layer was 40 μm. An adhesive sheet was obtained in the same manner as in Example 2.

[Embodiment 7]

In addition, 30 parts by weight of heat-expandable microspheres (product name "Matsumoto Microsphere F-50", manufactured by Matsumoto Oil & Fats Co., Ltd.) was added to the composition for forming an adhesive layer, and the thickness of the adhesive layer was 40 μm. An adhesive sheet was obtained in the same manner as in Example 3.

[Embodiment 8]

In addition, 30 parts by weight of heat-expandable microspheres (product name "Matsumoto Microsphere F-50", manufactured by Matsumoto Oil & Fats Co., Ltd.) was added to the composition for forming an adhesive layer, and the thickness of the adhesive layer was 40 μm. An adhesive sheet was obtained in the same manner as in Example 4.

[Embodiment 9]

A composition for forming an adhesive layer was prepared in the same manner as in Example 1.

Acrylic copolymer (copolymer of ethyl acrylate and 2-ethylhexyl acrylate and hydroxyethyl acrylate), and ethyl acrylate structural unit: 2-ethylhexyl acrylate structural unit: hydroxyethyl acrylate structural unit = 70:30:5:6 (weight ratio)) 100 parts by weight, an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE L"), 2 parts by weight, and 100 parts by weight of toluene were mixed to prepare an elastic layer. A composition for forming.

Acrylic copolymer (copolymer of ethyl acrylate and 2-ethylhexyl acrylate and hydroxyethyl acrylate), and ethyl acrylate structural unit: 2-ethylhexyl acrylate structural unit: hydroxyethyl acrylate structural unit = 70:30:5:6 (weight ratio)) 100 parts by weight, an isocyanate-based crosslinking agent (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry Co., Ltd.), 2 parts by weight, and a rosin-based adhesion-imparting resin (manufactured by Sumitomo Bakelite Co., Ltd.) 15 parts by weight, 35 parts by weight of heat-expandable microspheres (product name "Matsumoto Microsphere F-50", manufactured by Matsumoto Oil & Fats Co., Ltd.), and 100 parts by weight of toluene were mixed to prepare other products. A composition for forming an adhesive layer.

The adhesive layer-forming composition was applied to one side of a PET film (manufactured by Toray Industries, Inc., trade name "Lumirror S10", thickness: 38 μm) as a base material layer, and an adhesive layer was formed on the base material layer ( Thickness 10 μm). Further, an elastic layer forming composition was applied to the other surface of the PET film, and an elastic layer (thickness: 10 μm) was formed on the base material layer.

Further, the other adhesive layer-forming composition was applied onto another PET film to form another adhesive layer (thickness: 35 μm). The other adhesive layer is transferred onto the above elastic layer to obtain an adhesive sheet composed of an adhesive layer/substrate layer/elastic layer/other adhesive layer.

[Embodiment 10]

An adhesive sheet was obtained in the same manner as in Example 9 except that the composition for forming an adhesive layer obtained in Example 2 was used as the composition for forming an adhesive layer.

[Example 11]

An adhesive sheet was obtained in the same manner as in Example 9 except that the composition for forming an adhesive layer obtained in Example 3 was used as the composition for forming an adhesive layer.

[Embodiment 12]

An adhesive sheet was obtained in the same manner as in Example 9 except that the composition for forming an adhesive layer obtained in Example 4 was used as the composition for forming an adhesive layer.

[Comparative Example 1]

Acrylic copolymer (copolymer of methyl acrylate and 2-ethylhexyl acrylate and acrylic acid, and methyl acrylate structural unit: 2-ethylhexyl acrylate structural unit: acrylic structural unit = 15:85:8 ( 3 parts by weight of an epoxy-based crosslinking agent (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a terpene-based adhesion-imparting resin (manufactured by YASUHARA CHEMICAL Co., Ltd., trade name "YS" 10 parts by weight of POLYSTAR S145") and 100 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.

The adhesive layer forming composition is applied to a polytetrafluoroethylene film as a substrate layer An adhesive sheet composed of a base material layer and an adhesive layer (thickness: 10 μm) was obtained on one side of a product (manufactured by Toray Industries, "Lumirror S10", thickness: 38 μm).

As is apparent from Table 1, the adhesive sheet of the present invention has an adhesive layer having a contact angle of 15 or more with respect to 4-t-butylphenyl glycidyl ether, that is, having a low affinity for the sealing resin. In the agent layer, an adhesive sheet in which the gap height is less generated and the paste residue is less likely to be obtained can be obtained.

1‧‧‧Semiconductor wafer

2‧‧‧ sealing resin

2'‧‧‧Composition

10‧‧‧Adhesive layer

10'‧‧‧Adhesive sheet

20‧‧‧ Structure

Claims (14)

An adhesive sheet which is an adhesive sheet having an adhesive layer, and a contact angle of the surface of the adhesive layer with respect to 4-t-butylphenyl glycidyl ether is 15° or more, and the adhesive sheet is at 23° C. The adhesion to polyethylene terephthalate is 0.5 N/20 mm or more. The adhesive sheet of claim 1, wherein the material constituting the adhesive in the adhesive layer has an sp value of 7 (cal/cm ³ ) ^1/2 to 10 (cal/cm ³ ) ^1/2 . The adhesive sheet of claim 1 or 2, wherein the adhesive layer of the adhesive layer has a viscosity of 50 N/5 mm the above. The adhesive sheet of claim 1 or 2, wherein the adhesive layer comprises an acrylic adhesive. The adhesive sheet according to claim 4, wherein the acrylic adhesive comprises an acrylic polymer having an alkyl ester having 4 or more carbon atoms in a side chain as a base polymer. The adhesive sheet according to claim 5, wherein the content ratio of the structural unit having an alkyl ester having 4 or more carbon atoms in the side chain in the acrylic polymer is relative to the total structure constituting the acrylic polymer The unit is 30% by weight or more. The adhesive sheet of claim 1 or 2, wherein the adhesive layer comprises a rubber-based adhesive. The adhesive sheet of claim 1 or 2, wherein the adhesive layer comprises a polyoxynoxy adhesive. The adhesive sheet according to claim 8, wherein the polyoxynoxy adhesive comprises a polyoxyxene rubber and a polyoxyxylene resin as a base polymer, and a weight ratio of the polyoxyxene rubber to the polyoxyxylene resin (rubber: resin) It is 100:0~100:220. The adhesive sheet of claim 1 or 2, wherein the above adhesive layer further comprises heat-expandable microspheres. The adhesive sheet according to claim 10, wherein the above-mentioned adhesive layer before heating the heat-expandable microspheres has an arithmetic surface roughness Ra of 500 nm or less. The adhesive sheet of claim 1 or 2, wherein the outer surface of the adhesive layer is applied to the electric board at an ambient temperature of 23 ° C, and is aged at an ambient temperature of 40 ° C for 30 minutes, thereafter A load of 1.96 N was applied and held for 2 hours, at which time the offset with respect to the bakelite was 0.5 mm or less. The adhesive sheet according to claim 1 or 2, further comprising a base material layer, wherein the adhesive layer is disposed on one side or both sides of the base material layer. The adhesive sheet of claim 13, wherein the substrate layer and the adhesive layer have a gripping force of 6.0 N/19 mm or more.