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WO2018181770A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2018181770A1
WO2018181770A1 PCT/JP2018/013357 JP2018013357W WO2018181770A1 WO 2018181770 A1 WO2018181770 A1 WO 2018181770A1 JP 2018013357 W JP2018013357 W JP 2018013357W WO 2018181770 A1 WO2018181770 A1 WO 2018181770A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
thermally expandable
adhesive sheet
resin
Prior art date
Application number
PCT/JP2018/013357
Other languages
English (en)
Japanese (ja)
Inventor
高志 阿久津
揮一郎 加藤
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201880022432.9A priority Critical patent/CN110494524B/zh
Priority to KR1020197027708A priority patent/KR102511639B1/ko
Priority to JP2019510157A priority patent/JP6764526B2/ja
Publication of WO2018181770A1 publication Critical patent/WO2018181770A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an adhesive sheet.
  • the pressure-sensitive adhesive sheet may be used not only for semi-permanent fixing of members but also for temporary fixing for temporarily fixing building materials, interior materials, electronic parts and the like. Such a pressure-sensitive adhesive sheet for temporarily fixing is required to satisfy both adhesiveness at the time of use and peelability after use.
  • Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing when cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. Yes.
  • This heat-peelable pressure-sensitive adhesive sheet adjusts the maximum particle size of the heat-expandable microspheres with respect to the thickness of the heat-expandable pressure-sensitive adhesive layer, and calculates the center line average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating. It is adjusted to 0.4 ⁇ m or less.
  • the heat-peelable pressure-sensitive adhesive sheet can secure an area of contact with an adherend when cutting an electronic component and can exhibit adhesiveness that can prevent adhesion failure such as chip jumping.
  • the heat-expandable microspheres can be easily peeled off by expanding the thermally expandable microspheres by heating to reduce the contact area with the adherend.
  • FOWLP Fean out Wafer Level Package
  • the FOWLP 50 is provided with a rewiring layer 53 on the surface of the semiconductor chip 51 sealed with the sealing resin layer 52, and the solder balls 54 and the semiconductor chip 51 are interposed via the rewiring layer 53. Is a semiconductor package electrically connected to each other.
  • the FOWLP 50 can be applied to applications where the number of terminals is larger than the area of the semiconductor chip 51 because the terminals that are the solder balls 54 can be expanded to the outside of the semiconductor chip 51 (Fan out). be able to.
  • a semiconductor chip is placed on an adhesive sheet, and a sealing resin in a fluid state heated to around 100 ° C. is used as (1) an adhesive sheet around the semiconductor chip and the semiconductor chip. Or the like.
  • a sealing resin film is laminated on a semiconductor chip and heated and laminated. The sealing step (1) or (2) is performed. Then, after the sealing step, FOWLP is manufactured through a step of removing the adhesive sheet and forming a redistribution layer and solder balls on the exposed surface of the semiconductor chip.
  • the semiconductor chip is not misaligned between the time when the semiconductor chip is placed and the time when the semiconductor chip is sealed with the sealing resin. Adhesiveness to such an extent that the sealing resin does not enter at the adhesive interface is required. On the other hand, after sealing, the peelability which can remove an adhesive sheet easily is calculated
  • the sealing step of the FOWLP manufacturing method for example, it is conceivable to use a heat-peelable pressure-sensitive adhesive sheet provided with a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres.
  • the semiconductor chip placed thereon sinks to the pressure-sensitive adhesive sheet side.
  • the sealing resin is cured while the semiconductor chip is sinking to the adhesive sheet side, the surface on the semiconductor chip side including the sealing resin after removing the adhesive sheet is the surface of the semiconductor chip and the surface of the sealing resin.
  • the level difference is inferior and the flatness is poor.
  • the semiconductor chips may be misaligned, resulting in problems such as the distance between the chips being not constant. Furthermore, when removing the pressure-sensitive adhesive sheet described in Patent Document 1, even if the thermally expandable pressure-sensitive adhesive layer is expanded by heating, the semiconductor chip sinks to the pressure-sensitive adhesive sheet side. It is also possible that peeling is difficult without this external force.
  • the present invention has been made in view of the above-described problems, and when temporarily fixing an object, it is easy to use a slight force at the time of peeling while suppressing sinking of the object during heating. It aims at providing the adhesive sheet which can be peeled.
  • the inventors of the present invention provide a pressure-sensitive adhesive sheet containing a resin and a heat-expandable particle and having a non-adhesive heat-expandable base material and a pressure-sensitive adhesive layer containing a pressure-sensitive resin. It has been found that the above problem can be solved by adjusting the storage elastic modulus E ′ at a predetermined temperature to a specific range.
  • a pressure-sensitive adhesive sheet comprising a resin and heat-expandable particles having an expansion start temperature (t) of 120 to 250 ° C., having a non-adhesive heat-expandable base material, and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive resin Because The pressure-sensitive adhesive sheet, wherein the thermally expandable substrate satisfies the following requirements (1) to (2).
  • Requirement (2) The storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
  • -Requirement (3) The storage elastic modulus E '(100) of the said thermally expansible base material in 100 degreeC is 2.0 * 10 ⁇ 5 > Pa or more.
  • the above [1], wherein the ratio of the thickness of the thermally expandable substrate to the thickness of the adhesive layer (thermally expandable substrate / adhesive layer) at 23 ° C. is 0.2 or more.
  • the thickness of the thermally expandable substrate at 23 ° C. is 10 to 1000 ⁇ m, and the thickness of the pressure-sensitive adhesive layer is 1 to 60 ⁇ m.
  • the adhesive sheet as described.
  • the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer at 23 ° C. is 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 Pa.
  • a thermally expandable substrate comprising a resin and thermally expandable particles having an expansion start temperature (t) of 120 to 250 ° C., non-adhesive, and satisfying the following requirements (1) to (2): -Requirement (1): The storage elastic modulus E '(23) of the said thermally expansible base material in 23 degreeC is 1.0 * 10 ⁇ 6 > Pa or more. Requirement (2): The storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
  • the pressure-sensitive adhesive sheet according to any one of [1] to [9] is attached to an adherend, the pressure-sensitive adhesive sheet is removed from the adherend by a heat treatment at an expansion start temperature (t) or higher. How to use the adhesive sheet to peel off.
  • the ratio of the average particle diameter of the thermally expandable particles at 23 ° C. to the thickness of the thermally expandable substrate at 23 ° C. (average particle diameter / thermally expandable substrate) is more than 0.3 and 1.0
  • the pressure-sensitive adhesive sheet according to any one of [1] to [9] which is less than
  • the pressure-sensitive adhesive sheet using the heat-expandable substrate of the present invention can be easily peeled off with a slight force at the time of peeling while suppressing the sinking of the object during heating when temporarily fixing the object. Is possible.
  • the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
  • the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in the examples.
  • (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
  • the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it includes a resin and heat-expandable particles and has a non-adhesive heat-expandable base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive resin.
  • 1 and 2 are schematic cross-sectional views of a pressure-sensitive adhesive sheet showing the configuration of the pressure-sensitive adhesive sheet of the present invention.
  • a pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 12 on a thermally expandable substrate 11 as shown in FIG.
  • the adhesive sheet of 1 aspect of this invention is good also as a structure which has the peeling material 13 on the adhesive surface of the adhesive layer 12 like the adhesive sheet 1b shown in FIG.1 (b).
  • the pressure-sensitive adhesive sheet of another aspect of the present invention as shown in FIG. It is good also as the double-sided adhesive sheet 2a. Moreover, like the double-sided pressure-sensitive adhesive sheet 2b shown in FIG. A configuration having 132 is also possible.
  • the peeling force when peeling the release material 131 from the first pressure-sensitive adhesive layer 121, and the peeling force when peeling the peeling material 132 from the second pressure-sensitive adhesive layer 122 In the case of the same level, if the two release materials are pulled outward to be peeled off, a phenomenon may occur in which the pressure-sensitive adhesive layer is divided and peeled off along with the two release materials. From the viewpoint of suppressing such a phenomenon, it is preferable to use two types of release materials designed so that the two release materials 131 and 132 have different release forces from the adhesive layer attached to each other.
  • a release material in which release treatment is performed on both surfaces of one pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer 121 and the second pressure-sensitive adhesive layer 122. May be a double-sided pressure-sensitive adhesive sheet having a configuration in which a laminate is wound in a roll shape.
  • the pressure-sensitive adhesive sheet of one embodiment of the present invention may have a configuration having another layer between the thermally expandable base material and the pressure-sensitive adhesive layer.
  • the thermally expandable substrate 11 and the pressure-sensitive adhesive sheets 1a and 1b shown in FIG. 1 and the double-sided pressure-sensitive adhesive sheets 2a and 2b shown in FIG. It is preferable to have a structure in which the pressure-sensitive adhesive layer 12 is directly laminated.
  • the heat-expandable base material of the pressure-sensitive adhesive sheet of the present invention comprises a resin and heat-expandable particles having an expansion start temperature (t) of 120 to 250 ° C., and is a non-adhesive base material.
  • the storage elastic modulus E '(23) of the said thermally expansible base material in 23 degreeC is 1.0 * 10 ⁇ 6 > Pa or more.
  • the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
  • the storage elastic modulus E ′ of the thermally expandable substrate at a predetermined temperature means a value measured by the method described in the examples.
  • a semiconductor chip is pasted on an adhesive sheet at a room temperature of about 23 ° C., and heated to about 100 ° C. from above to form a sealing resin in a fluid state.
  • the semiconductor chip is sealed by a method of filling the top or laminating a sealing resin sheet on the semiconductor chip and laminating by heating. That is, the requirement (1) is that the storage elastic modulus E ′ (23) of the thermally expandable substrate under the temperature environment (23 ° C.) when the object such as the semiconductor chip is stuck on the adhesive sheet in this way. ).
  • a semiconductor chip is usually placed so that its circuit surface is covered with an adhesive surface.
  • a known device such as a flip chip bonder or a die bonder can be used.
  • a force is applied to push the semiconductor chip in the thickness direction of the adhesive sheet. May sink excessively in the direction.
  • a force to move the semiconductor chip in the plane direction of the adhesive sheet is applied, so the semiconductor chip is an adhesive. There is a risk of displacement in the plane direction of the layer.
  • the pressure-sensitive adhesive sheet of the present invention contains a resin and thermally expandable particles, and has a storage elastic modulus E ′ (23) at 23 ° C. of 1 as defined in the requirement (1).
  • the problem is solved by using a thermally expandable base material adjusted to 0.0 ⁇ 10 6 Pa or more.
  • thermally expansible base material that satisfies the above requirement (1), it is possible to prevent misalignment when attaching an object such as a semiconductor chip on an adhesive sheet. Can do. Moreover, when a target object is stuck, excessive sinking into the pressure-sensitive adhesive layer can also be prevented.
  • the storage elastic modulus E ′ (23) of the thermally expandable base material defined by the requirement (1) is preferably 5.0 ⁇ 10 6 to 5.0 ⁇ 10 12 Pa, more preferably 1. 0 ⁇ 10 7 to 1.0 ⁇ 10 12 Pa, more preferably 5.0 ⁇ 10 7 to 1.0 ⁇ 10 11 Pa, still more preferably 1.0 ⁇ 10 8 to 1.0 ⁇ 10 10 Pa is there.
  • the said requirement (2) prescribes
  • the contact area between the adherend (semiconductor chip and cured sealing resin) and the adhesive surface decreases, and the adherend and the adhesive surface By forming a space between them, the pressure-sensitive adhesive sheet can be easily peeled off from the adherend with a slight force.
  • the heat-expandable base material containing the heat-expandable particles in the “base material” contains the heat-expandable particles in the “adhesive layer” as in Patent Document 1.
  • the degree of decrease in the storage elastic modulus E ′ of the thermally expandable substrate due to the temperature rise is small. Therefore, also in the sealing step, it is possible to prevent the positional deviation of the object such as the semiconductor chip and the excessive sinking into the pressure-sensitive adhesive layer.
  • the heat-expandable particles contained in the heat-expandable substrate need to be adjusted so as to easily expand.
  • the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is defined. It can also be said that the index indicates the rigidity of the thermally expandable substrate immediately before expansion. That is, according to the study by the present inventors, the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is more than 1.0 ⁇ 10 7 Pa. Even if an attempt is made to expand the thermally expandable particles by heating to a temperature equal to or higher than the expansion start temperature (t), the expansion is suppressed, and the thermally expandable particles are not sufficiently large. It turned out that the uneven
  • the storage elastic modulus E ′ (t) defined in the requirement (2) of the thermally expandable substrate used in one embodiment of the present invention is preferably 9.0 ⁇ 10 6 Pa or less, more preferably 8. It is 0 ⁇ 10 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and still more preferably 4.0 ⁇ 10 6 Pa or less.
  • the storage elastic modulus E ′ (t) specified in (2) is preferably 1.0 ⁇ 10 3 Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and further preferably 1.0 ⁇ 10 5 Pa or more. It is.
  • the storage elastic modulus E '(100) of the said thermally expansible base material in 100 degreeC is 2.0 * 10 ⁇ 5 > Pa or more.
  • a sealing resin heated to around 100 ° C. and filled with fluidity is filled on the semiconductor chip, or a sealing resin sheet is laminated on the semiconductor chip.
  • the semiconductor chip is sealed by heating and laminating. That is, the above requirement (3) prescribes the storage elastic modulus E ′ of the thermally expandable substrate under the temperature environment in the sealing process, assuming that the temperature environment in the sealing process of the manufacturing process of FOWLP is 100 ° C. Is.
  • the heat-expandable pressure-sensitive adhesive layer as the pressure-sensitive adhesive sheet described in Patent Document 1 contains a pressure-sensitive adhesive resin
  • the degree of decrease in the storage elastic modulus E ′ becomes very large as the temperature rises.
  • the degree of decrease in the storage elastic modulus E ′ of the heat-expandable pressure-sensitive adhesive layer becomes very large, the heat-expandable particles and the pressure-sensitive resin contained in the heat-expandable pressure-sensitive adhesive layer easily flow, and accordingly, The pressure-sensitive adhesive surface of the thermally expandable pressure-sensitive adhesive layer is easily deformed.
  • a target such as a semiconductor chip around 100 ° C.
  • the weight of the sealing resin is increased.
  • the pressure-sensitive adhesive sheet becomes flexible along with the heating and heating, the object can easily sink into the pressure-sensitive adhesive sheet side.
  • the sinking of the object is caused by the occurrence of positional deviation of the object, the occurrence of variation in the distance between the objects, and unevenness on the surface on which the object after sealing is placed, and the flatness is It also causes inferiority.
  • This problem also applies to the sealing method using a laminate using a sealing resin film.
  • the flow of the heat-expandable particles and the pressure-sensitive resin in the heat-expandable pressure-sensitive adhesive layer is the same as described above. Therefore, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer is likely to be deformed, and the above-described problem may occur.
  • the pressure-sensitive adhesive sheet of one embodiment of the present invention contains a resin and thermally expandable particles and, as defined in the above requirement (3), storage elastic modulus E ′ (100) at 100 ° C. Is solved by using a thermally expansible base material adjusted to 2.0 ⁇ 10 5 Pa or more.
  • the flow of thermally expandable particles can be moderately suppressed even in a temperature environment in a sealing process such as a FOWLP manufacturing process.
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer provided on is difficult to deform.
  • the weight of the sealing resin laminated on the object such as a semiconductor chip or the pressure accompanying the lamination using the sealing resin sheet causes the object to sink to the adhesive sheet side, and a flat surface is formed. It is possible to suppress the adverse effects such as difficulty and the occurrence of displacement of the object.
  • the thickness of the thermally expandable substrate at 23 ° C. is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, still more preferably 25 to 400 ⁇ m, and still more preferably 30 to 300 ⁇ m.
  • the thickness of the thermally expansible base material in 23 degreeC means the value measured by the method as described in an Example.
  • the thermally expansible base material which the adhesive sheet of 1 aspect of this invention has is a non-adhesive base material.
  • whether or not the non-adhesive substrate is determined if the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 N / 5 mm ⁇ with respect to the surface of the target substrate.
  • the said base material is judged as a "non-adhesive base material”.
  • the probe tack value on the surface of the thermally expandable substrate used in one embodiment of the present invention is less than 50 mN / 5 mm ⁇ , preferably less than 30 mN / 5 mm ⁇ , more preferably less than 10 mN / 5 mm ⁇ , and even more preferably 5 mN. / 5mm ⁇ or less.
  • the specific measuring method of the probe tack value on the surface of a thermally expansible base material is based on the method as described in an Example.
  • the heat-expandable base material which the adhesive sheet of 1 aspect of this invention has contains resin and heat-expandable particle
  • a thermally expansible base material can be formed from the resin composition (y) containing resin and a thermally expansible particle.
  • each component contained in the resin composition (y) which is a forming material of a thermally expansible base material is demonstrated.
  • the resin contained in the resin composition (y) may be any polymer that can form a thermally expandable substrate that satisfies the above requirements (1) and (2).
  • non-adhesive resin may be sufficient and adhesive resin may be sufficient. That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin undergoes a polymerization reaction with the polymerizable compound in the process of forming the thermally expandable substrate from the resin composition (y). The obtained resin becomes a non-adhesive resin, and the heat-expandable substrate containing the resin may be non-adhesive.
  • the mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer It may be.
  • the content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and still more preferably 65 to 90% with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). It is 70% by mass, more preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y) is selected from acrylic urethane resins and olefin resins. Preferably it contains more than one species.
  • the following resin (U1) is preferable.
  • urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
  • Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols. These polyols may be used independently and may use 2 or more types together.
  • the polyol used in one embodiment of the present invention is preferably a diol, preferably an ester-type diol, an alkylene-type diol, and a carbonate-type diol, more preferably an ester-type diol and a carbonate-type diol, and even more preferably a carbonate-type diol. .
  • ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
  • alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol
  • ethylene glycol, propylene glycol And alkylene glycols such as diethylene glycol and dipropylene glycol
  • Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.
  • polyvalent isocyanate used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyvalent isocyanates may be used alone or in combination of two or more. These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.
  • the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends.
  • a urethane prepolymer is preferred.
  • an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the (meth) acrylic acid ester is preferably one or more selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
  • the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
  • the carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
  • hydroxyalkyl (meth) acrylate the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce
  • vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
  • Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound.
  • the amount is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the acrylic urethane-based resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
  • the polymerization is preferably performed by adding a radical initiator.
  • the content ratio of the structural unit (u11) derived from the urethane prepolymer and the structural unit (u12) derived from the vinyl compound [(u11) / ( u12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, still more preferably 35/65 to mass by mass ratio. 55/45.
  • the olefin resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferable.
  • olefinic resins for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), Medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefinic terpolymers such as-(5-ethylidene-2-norborn
  • the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
  • an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
  • unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride.
  • Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
  • unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.
  • an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain.
  • a polymer is mentioned.
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
  • said alkyl (meth) acrylate the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
  • Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl.
  • Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
  • Such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polystyrene acrylonitrile-butadiene-styren
  • the content of the resin other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is smaller. Is preferred.
  • the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.
  • the heat-expandable particles used in the present invention may be particles whose expansion start temperature (t) is adjusted to 120 to 250 ° C., and are appropriately selected according to the application.
  • the expansion start temperature (t) of the thermally expandable particles means a value measured based on the following method.
  • Measurement method of expansion start temperature (t) of thermally expandable particles To an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured is added, and an aluminum lid (diameter 5.6 mm, thickness 0. 1 mm) is prepared.
  • the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, in a state where a force of 0.01 N is applied by the pressurizer, heating is performed from 20 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min, and the amount of displacement of the pressurizer in the vertical direction is measured.
  • the displacement start temperature be the expansion start temperature (t).
  • the thermally expandable particles are microencapsulated foaming agents composed of an outer shell composed of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature.
  • a thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane.
  • the average particle size (D 50 ) before expansion of the thermally expandable particles at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, and still more.
  • the thickness is preferably 10 to 50 ⁇ m.
  • the average particle diameter before expansion of the thermally expandable particles is the volume-median particle diameter (D 50 ), and is a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion means a particle diameter corresponding to 50%.
  • the ratio of the average particle diameter of the heat-expandable particles at 23 ° C. to the thickness of the heat-expandable substrate at 23 ° C. (average particle diameter / heat-expandable substrate) From the viewpoint of suppression and ease of peeling at the time of peeling of the object, preferably 0.1 or more and less than 1.0, more preferably 0.2 or more and less than 1.0, and further preferably more than 0.3. It is less than 0, more preferably 0.35 to 0.8, still more preferably 0.4 to 0.6, and still more preferably 0.4 to 0.5.
  • the 90% particle diameter (D 90 ) of the thermally expandable particles at 23 ° C. used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 90 ⁇ m, and still more preferably. Is 30 to 80 ⁇ m.
  • the 90% particle size (D 90 ) of the thermally expandable particles is the heat before expansion measured using a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern). In the particle distribution of the expandable particles, it means a particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the thermally expandable particles before expansion.
  • the maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles used in one embodiment of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, Preferably it is 2.5 to 60 times, and more preferably 3 to 40 times.
  • the content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10% with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). To 30% by mass, and more preferably 15 to 25% by mass.
  • the resin composition (y) used in one embodiment of the present invention may contain a base material additive contained in a base material included in a general pressure-sensitive adhesive sheet as long as the effects of the present invention are not impaired.
  • base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants. These base material additives may be used alone or in combination of two or more.
  • the content of each base material additive is preferably 0.0001 to 20 parts by mass with respect to 100 parts by mass of the resin in the resin composition (y). More preferably, it is 0.001 to 10 parts by mass.
  • the resin composition (y) used in one embodiment of the present invention is ethylenic having a mass average molecular weight (Mw) of 50000 or less from the viewpoint of forming a thermally expandable substrate that satisfies the above requirements (1) and (2).
  • Examples include a solventless resin composition (y1), which is obtained by blending an oligomer having an unsaturated group, an energy beam polymerizable monomer, and the above-described thermally expandable particles, and not blending a solvent. In the solventless resin composition (y1), no solvent is blended, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer. By irradiating the coating film formed from the solventless resin composition (y1) with energy rays, it is easy to form a thermally expandable substrate that satisfies the above requirements (1) and (2).
  • the mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 35000. More preferably, it is 4000-30000.
  • oligomer As said oligomer, what is necessary is just to have an ethylenically unsaturated group whose mass mean molecular weight is 50000 or less among resin contained in the above-mentioned resin composition (y), but the above-mentioned urethane prepolymer (UP ) Is preferred.
  • a modified olefin resin having an ethylenically unsaturated group can also be used.
  • the total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 with respect to the total amount (100% by mass) of the solventless resin composition (y1). It is ⁇ 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
  • Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Cycloaliphatic polymerizable compounds such as (meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; Tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy beam polymerizable monomers may be used independently and may use 2 or more types together.
  • the content ratio of the oligomer and the energy beam polymerizable monomer (oligomer / energy beam polymerizable monomer) in the solventless resin composition (y1) is preferably 20/80 to 90 / in mass ratio. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.
  • the solventless resin composition (y1) is further blended with a photopolymerization initiator.
  • a photopolymerization initiator By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer.
  • the amount is preferably 0.02 to 3 parts by mass.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention only needs to contain a pressure-sensitive adhesive resin, and if necessary, for pressure-sensitive adhesives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator. An additive may be contained.
  • the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is non-thermal from the viewpoint of preventing an object such as a mounted semiconductor chip from sinking into the pressure-sensitive adhesive layer due to heating in the sealing step. It is preferable that it is an expandable adhesive layer.
  • the adhesive force on the adhesive surface of the adhesive layer on which an object such as a semiconductor chip is placed at 23 ° C. before expansion of the thermally expandable particles is preferably 0.1 to 10 It is 0.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm. If the adhesive force is 0.1 N / 25 mm or more, the adherend such as a semiconductor chip can be sufficiently fixed to the extent that positional displacement can be prevented in the next step such as a sealing step.
  • said adhesive force means the value measured by the method as described in an Example.
  • the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer on which an object such as a semiconductor chip is placed at 23 ° C. is preferably 1.0 ⁇ 10 4 to It is 1.0 ⁇ 10 8 Pa, more preferably 5.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa, and still more preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa.
  • the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer to which an object such as a semiconductor chip is attached is in the above range.
  • the storage shear modulus G ′ (23) of all the pressure-sensitive adhesive layers on the side to which an object such as a semiconductor chip is attached rather than the material is within the above range. Further, the storage shear elastic modulus G ′ (23) of the pressure-sensitive adhesive layer on the side opposite to the side to which the object such as a semiconductor chip is affixed with respect to the thermally expandable base material may be within the above range. It may be outside. If the storage shear elastic modulus G ′ (23) of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 4 Pa or more, it is possible to prevent positional deviation when attaching an object such as a semiconductor chip, It is possible to prevent excessive sinking into the adhesive layer.
  • the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer is 1.0 ⁇ 10 8 Pa or less, it becomes easy to be deformed by heating to a temperature of the expansion start temperature (t) or more during peeling, Due to the expansion of the thermally expandable particles in the thermally expandable substrate, irregularities are easily formed on the surface of the pressure-sensitive adhesive layer, and as a result, it can be easily peeled off with a slight force.
  • the storage shear modulus G '(23) of an adhesive layer means the value measured by the method as described in an Example.
  • the adhesive on which objects, such as a semiconductor chip, are mounted The storage shear modulus G ′ (23) of the layer is preferably within the above range.
  • the storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer on the side to be attached to the support or the like at 23 ° C. has good adhesion to the support or the like. From the viewpoint, it is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 Pa, more preferably 3.0 ⁇ 10 4 to 5.0 ⁇ 10 7 Pa, still more preferably 5.0 ⁇ 10 4 to 1. 0 ⁇ 10 7 Pa.
  • the thickness (23 ° C.) of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is due to the viewpoint of developing excellent pressure-sensitive adhesive force and the expansion of the heat-expandable particles in the heat-expandable base material by heat treatment. From the viewpoint of easily forming irregularities on the surface of the pressure-sensitive adhesive layer to be formed, the thickness is preferably 1 to 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, still more preferably 5 to 30 ⁇ m.
  • the ratio of the thickness of the heat-expandable base material to the thickness of the pressure-sensitive adhesive layer at 23 ° C. heat-expandable base material / pressure-sensitive adhesive layer
  • the sealing step from the viewpoint of flattening the surface on the object side after sealing and preventing positional displacement of the object, it is preferably 0.2 or more, more preferably 0.5 or more, and still more preferably.
  • a pressure-sensitive adhesive sheet that can be easily peeled with a slight force when peeled, preferably 1000 or less, more preferably 200 or less, More preferably, it is 60 or less, More preferably, it is 30 or less.
  • the “thickness of the adhesive layer” at 23 ° C. is It means the thickness of each adhesive layer. That is, for each pressure-sensitive adhesive layer, it is preferable that the thickness and the ratio [thermally expandable substrate / pressure-sensitive adhesive layer] are within the above ranges. Moreover, the thickness of the adhesive layer in 23 degreeC means the value measured by the method as described in an Example.
  • the adhesive layer which the adhesive sheet of 1 aspect of this invention has can be formed from the adhesive composition containing adhesive resin. Moreover, in the adhesive sheet which has several adhesive layers like the double-sided adhesive sheet 2a, 2b shown in FIG. 2, each adhesive layer may be formed from the same adhesive composition, and it mutually differs. You may form from an adhesive composition.
  • each component contained in the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer will be described.
  • any polymer may be used as long as the resin has adhesiveness and has a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably 30,000, from the viewpoint of improving the adhesive strength. ⁇ 1 million.
  • the adhesive resin examples include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. These adhesive resins may be used independently and may use 2 or more types together. In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
  • the adhesive resin used in one embodiment of the present invention may be an energy ray curable adhesive resin in which a polymerizable functional group is introduced into the side chain of the above-mentioned adhesive resin.
  • a polymerizable functional group include a (meth) acryloyl group and a vinyl group.
  • energy rays include ultraviolet rays and electron beams, but ultraviolet rays are preferred.
  • the content of the adhesive resin is preferably 30 to 99.99% by mass, more preferably 40 to 99.95% by mass, still more preferably based on the total amount (100% by mass) of the active ingredients of the adhesive composition. It is 50 to 99.90% by mass, more preferably 55 to 99.80% by mass, still more preferably 60 to 99.50% by mass.
  • “content of each component relative to the total amount of active ingredients of the pressure-sensitive adhesive composition” means “content of each component in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition”. Is synonymous with.
  • the adhesive resin preferably contains an acrylic resin.
  • the content of the acrylic resin in the adhesive resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition. %, More preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • the acrylic resin that can be used as an adhesive resin includes, for example, a polymer including a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, a cyclic structure And a polymer containing a structural unit derived from a (meth) acrylate having a hydrogen atom.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
  • a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) and a functional group-containing monomer (a2).
  • An acrylic copolymer (A1) having a structural unit (a2) derived from ') (hereinafter also referred to as “monomer (a2')") is more preferred.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and still more preferably 4 to 8 from the viewpoint of improving adhesive properties. It is.
  • the alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. These monomers (a1 ′) may be used alone or in combination of two or more. As the monomer (a1 ′), methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable. For example, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, and still more preferably 80 to 95.0% by mass.
  • a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2 ′) may be used alone or in combination of two or more. Among these, as the monomer (a2 ′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
  • Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing compounds as described above.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • the content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight with respect to all the structural units (100% by weight) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, and still more preferably 3.0 to 25% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1).
  • To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • Examples of the monomer (a3 ′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
  • olefins such as ethylene, propylene, and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, iso
  • the acrylic copolymer (A1) may be an energy ray curable acrylic copolymer having a polymerizable functional group introduced in the side chain.
  • the polymerizable functional group and the energy ray are as described above.
  • the polymerizable functional group includes an acrylic copolymer having the above structural units (a1) and (a2), and a substituent that can be bonded to the functional group of the structural unit (a2) of the acrylic copolymer. And a compound having a polymerizable functional group can be reacted. Examples of the compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
  • the pressure-sensitive adhesive composition preferably further contains a cross-linking agent when it contains a pressure-sensitive adhesive resin containing a functional group such as the acrylic copolymer (A1) described above.
  • the said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge
  • crosslinking agent examples include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents may be used independently and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
  • the content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the adhesive resin has, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group, The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is distinguished from a functional resin.
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 5000 to 8000, and still more preferably 800 to 5000.
  • Examples of the tackifier are obtained by copolymerizing C5 fractions such as rosin resin, terpene resin, styrene resin, pentene, isoprene, piperine, 1.3-pentadiene generated by thermal decomposition of petroleum naphtha.
  • C9 petroleum resin obtained by copolymerizing C9 fractions such as indene generated by thermal decomposition of petroleum naphtha and vinyltoluene, and hydrogenated resins obtained by hydrogenating these.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • a tackifier may be used independently and may use 2 or more types from which a softening point and a structure differ. And when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.
  • the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, and still more preferably relative to the total amount (100% by mass) of the active ingredients of the adhesive composition. It is 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, still more preferably 1.0 to 40% by mass.
  • ⁇ Photopolymerization initiator> 1 aspect of this invention WHEREIN: When an adhesive composition contains an energy-beam curable adhesive resin as an adhesive resin, it is preferable to contain a photoinitiator further. By forming an adhesive composition containing an energy ray-curable adhesive resin and a photopolymerization initiator, the adhesive layer formed from the adhesive composition can be irradiated with a relatively low energy energy beam. It is possible to sufficiently advance the curing reaction and adjust the adhesive strength to a desired range.
  • mode of this invention the same thing as what is mix
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.001 parts by mass with respect to 100 parts by mass of the energy ray curable adhesive resin. 05 to 2 parts by mass.
  • the pressure-sensitive adhesive composition as a material for forming the pressure-sensitive adhesive layer is a pressure-sensitive adhesive used for general pressure-sensitive adhesives in addition to the above-described additives, as long as the effects of the present invention are not impaired. May contain additives.
  • an adhesive additive include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and the like. These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
  • each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. ⁇ 10 parts by mass.
  • the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer, may contain thermally expandable particles as long as the effects of the present invention are not impaired.
  • the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably a non-thermally expandable pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive composition, which is a material for forming the pressure-sensitive adhesive layer, is more preferable as the content of thermally expandable particles is as small as possible.
  • the content of the heat-expandable particles is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably 0.1% by mass with respect to the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition. Is more preferably less than 0.01% by mass, particularly preferably less than 0.001% by mass.
  • the double-sided adhesive sheet of 1 aspect of this invention has a peeling material further on the sticking surface of an adhesive layer. Also good.
  • the adhesive sheet which has two adhesive layers like the adhesive sheet 2b of FIG.2 (b) the two peeling materials provided on the sticking surface of each adhesive layer differ in the peeling force difference. It is preferable that it is adjusted as described above.
  • the release material a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.
  • Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin.
  • a plastic film such as a resin film;
  • release agent examples include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
  • the thickness of the release material at 23 ° C. is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, and still more preferably 35 to 80 ⁇ m.
  • Step (1a) On the release treatment surface of the release material, the resin composition (y), which is a material for forming the thermally expandable substrate, is applied to form a coating film, and the coating film is dried or irradiated with UV. Forming a thermally expandable substrate.
  • Another method for producing the pressure-sensitive adhesive sheet of the present invention includes a method (b) having the following steps (1b) to (3b).
  • the resin composition (y) and the pressure-sensitive adhesive composition may be further mixed with a diluent solvent to form a solution.
  • a diluent solvent examples include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the expansion of the thermally expandable particles is prevented in the drying process of forming the thermally expandable substrate from the coating film.
  • the drying temperature is preferably less than the expansion start temperature (t) of the thermally expandable particles.
  • the pressure-sensitive adhesive sheet of the present invention When temporarily fixing an object, the pressure-sensitive adhesive sheet of the present invention can be easily peeled off with a slight force while peeling while suppressing the sinking of the object during heating. Therefore, the pressure-sensitive adhesive sheet of the present invention is preferably used in a sealing step with heating using a sealing resin, and specifically, preferably used in a sealing step when manufacturing FOWLP. .
  • the semiconductor chip is placed on the adhesive surface of the adhesive layer of the adhesive sheet of the present invention, and then the upper surface and the adhesive surface of the semiconductor chip are covered with a sealing resin and heated. Sealing is performed by thermosetting the sealing resin.
  • the elastic modulus of each layer constituting the pressure-sensitive adhesive sheet decreases due to heating in the sealing process, and the semiconductor chip placed sinks to the pressure-sensitive adhesive sheet side. Is seen.
  • the pressure-sensitive adhesive sheet of the present invention satisfies the above requirement (1), and thus effectively suppresses the sinking of the semiconductor chip to the pressure-sensitive adhesive sheet side, which may occur in the sealing step, and the semiconductor after sealing.
  • the surface on the chip side can be flattened, and the occurrence of misalignment of the semiconductor chip can be suppressed.
  • the sealing resin an arbitrary one can be appropriately selected from those used as a semiconductor sealing material.
  • a sealing resin containing a thermosetting resin or an energy ray curable resin can be used.
  • a sealing resin containing Further, the sealing resin may be a solid such as a granule or a sheet at room temperature, or a liquid in the form of a composition. From the viewpoint of workability, the sealing resin is in the form of a sheet. Is preferred.
  • a method of covering the semiconductor chip and its peripheral part using the sealing resin it is appropriately selected and applied according to the type of the sealing resin from methods conventionally used in the semiconductor sealing process. For example, a roll laminating method, a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a transfer molding method, a compression molding mold method, or the like can be applied.
  • a sealing process is performed on temperature conditions less than the expansion start temperature (t) of a thermally expansible particle.
  • the sealing resin coating process and the thermosetting process may be performed separately. However, when the sealing resin is heated in the coating process, the sealing resin is cured as it is by the heating, and the coating process is performed. And thermosetting treatment may be performed simultaneously.
  • the pressure-sensitive adhesive sheet can be easily peeled with a slight force by heating to a temperature equal to or higher than the expansion start temperature (t).
  • the “temperature higher than the expansion start temperature (t)” when peeling the adhesive sheet is preferably “expansion start temperature (t) + 10 ° C.” or higher and “expansion start temperature (t) + 60 ° C.” or lower. It is more preferable that the expansion start temperature (t) + 15 ° C. or more and “expansion start temperature (t) + 40 ° C.” or less.
  • this invention can also provide the usage method of the adhesive sheet of following [1].
  • a method for using a pressure-sensitive adhesive sheet wherein the pressure-sensitive adhesive sheet is peeled from the adherend by a heat treatment at a temperature equal to or higher than an expansion start temperature (t) after the pressure-sensitive adhesive sheet of the present invention is attached to the adherend.
  • t expansion start temperature
  • the particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the particle diameters corresponding to 50% and 90% of the cumulative volume frequency calculated from the smaller particle diameter of the particle distribution are expressed as “average particle diameter (D 50 ) of thermally expandable particles” and “thermally expandable particles”, respectively. 90% particle diameter (D 90 ) ”.
  • Torsional shear using a viscoelasticity measuring device manufactured by Anton Paar, device name “MCR300” under the conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a heating rate of 3 ° C./min, and a frequency of 1 Hz
  • MCR300 viscoelasticity measuring device
  • a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N / cm 2 for 1 second, and then the probe is tested at a speed of 10 mm / second. The force required to move away from the surface was measured. And the measured value was made into the probe tack value of the test sample.
  • Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) 80.0 / 20.0 (mass ratio), A solution containing an acrylic copolymer having a Mw of 600,000. Diluting solvent: ethyl acetate, solid content concentration: 40% by mass.
  • Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid 86.0 / 8.0 / 5.0 / 1.
  • first adhesive layer (X-1) The isocyanate-based crosslinking agent (i) 5.0 parts by mass (solid content ratio) is blended with 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, and diluted with toluene.
  • the composition (x-1) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by stirring uniformly. Then, on the surface of the release agent layer of the above heavy release film, the prepared composition (x-1) was applied to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to have a thickness of 10 ⁇ m.
  • the first pressure-sensitive adhesive layer (X-1) was formed.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X-1) at 23 ° C. was 2.5 ⁇ 10 5 Pa.
  • Second adhesive layer (X-2) The isocyanate-based crosslinking agent (i) 0.8 parts by mass (solid content ratio) is blended with 100 parts by mass of the acrylic copolymer (ii), which is an adhesive resin, and diluted with toluene, The composition (x-2) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by stirring uniformly. Then, on the surface of the release agent layer of the light release film, the prepared composition (x-2) was applied to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to have a thickness of 10 ⁇ m. The second pressure-sensitive adhesive layer (X-2) was formed. The storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X-2) at 23 ° C. was 9.0 ⁇ 10 4 Pa.
  • the product name “Irgacure 184”) 2.0 parts by mass (solid content ratio) and 0.2 parts by mass (solid content ratio) phthalocyanine pigment as an additive were blended to prepare an energy ray curable composition. . And the said heat-expandable particle
  • thermally expandable substrate (Y-1) The prepared composition (y-1) was applied on the surface of the release agent layer of the light release film to form a coating film. Then, using an ultraviolet irradiation device (product name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.) and a high-pressure mercury lamp (product name “H04-L41” manufactured by Eye Graphics Co., Ltd.), an illuminance of 160 mW / cm 2 and a light amount of 500 mJ / The coating film was cured by irradiating ultraviolet rays under the condition of cm 2 to form a thermally expandable substrate (Y-1) having a thickness of 50 ⁇ m. The above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
  • the isocyanate-based crosslinking agent (i) is 6.3 parts by mass with respect to 100 parts by mass of the solid content of the acrylic urethane-based resin solution obtained in (2) above. Parts (solid content ratio), dioctyltin bis (2-ethylhexanoate) 1.4 parts by mass (solid content ratio) as a catalyst, and the above-mentioned thermally expandable particles (i), and diluted with toluene, The mixture was uniformly stirred to prepare a composition (y-2) having a solid content concentration (active ingredient concentration) of 30% by mass.
  • the content of the heat-expandable particles (i) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-2) was 20% by mass. Then, on the surface of the release agent layer of the light release film, the prepared composition (y-2) was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to have a thickness of 50 ⁇ m. A heat-expandable base material (Y-2) was formed.
  • thermally expandable pressure-sensitive adhesive layer (Y-3) To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 6.3 parts by mass (solid content ratio) of the isocyanate-based crosslinking agent (i) and the thermally expandable particles ( i) was mixed, diluted with toluene, and stirred uniformly to prepare a composition (y-3) having a solid content concentration (active ingredient concentration) of 30% by mass. The content of thermally expandable particles (i) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-3) was 20% by mass.
  • the prepared composition (y-3) was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to have a thickness of 50 ⁇ m.
  • the heat-expandable pressure-sensitive adhesive layer (Y-3) was formed.
  • thermally expandable base material (Y-4)
  • the above isocyanate-based material is used with respect to 100 parts by mass of the solid content of the energy ray-curable acrylic copolymer (iii) obtained in (1) above.
  • 0.5 parts by mass (solid content ratio) of the crosslinking agent (i), 3.0 parts by mass (solid content ratio) of the photopolymerization initiator (i), and the thermally expandable particles (i) are blended, and toluene.
  • the mixture was stirred uniformly to prepare a composition (y-4) having a solid content concentration (active ingredient concentration) of 30% by mass.
  • the content of the heat-expandable particles (1) relative to the total amount (100% by mass) of active ingredients in the obtained composition (y-4) was 20% by mass.
  • the prepared composition (y-4) was applied to form a coating film. After drying the coating film at 100 ° C. for 120 seconds, an illuminance of 160 mW / cm 2. Irradiation with ultraviolet rays under conditions of a light amount of 500 mJ / cm 2 formed a thermally expandable substrate (Y-4) having a thickness of 50 ⁇ m.
  • the above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
  • Thermally expandable substrates (Y-1) to (Y-2) and (Y-4) formed in Production Examples 3 to 4 and 6, and a thermally expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 ),
  • Example 1 The surfaces of the first pressure-sensitive adhesive layer (X-1) formed in Production Example 1 and the heat-expandable base material (Y-1) formed in Production Example 3 were bonded together to form a heat-expandable base material (Y-).
  • the light release film on the 1) side was removed, and the second pressure-sensitive adhesive layer (X-2) formed in Production Example 2 was bonded onto the surface of the exposed thermally expandable substrate (Y-1).
  • the light release film / second pressure-sensitive adhesive layer (X-2) / thermally expandable substrate (Y-1) / first pressure-sensitive adhesive layer (X-1) / heavy release film were laminated in this order.
  • a sheet (1) was produced.
  • Example 2 Lightly peelable film / second adhesive as in Example 1, except that the thermally expandable substrate (Y-1) was replaced with the thermally expandable substrate (Y-2) formed in Production Example 4.
  • a pressure-sensitive adhesive sheet (2) was prepared by laminating layer (X-2) / thermally expandable substrate (Y-2) / first pressure-sensitive adhesive layer (X-1) / heavy release film in this order.
  • Comparative Example 1 The surfaces of the second pressure-sensitive adhesive layer (X-2) formed in Production Example 2 and the thermally expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 were bonded together. Then, the light release film on the side of the heat-expandable pressure-sensitive adhesive layer (Y-3) is removed, and the first pressure-sensitive adhesive formed in Production Example 1 on the surface of the exposed heat-expandable pressure-sensitive adhesive layer (Y-3). The agent layer (X-1) was bonded. Thus, the light release film / second pressure-sensitive adhesive layer (X-2) / thermally expandable pressure-sensitive adhesive layer (Y-3) / first pressure-sensitive adhesive layer (X-1) / heavy release film was laminated in this order. An adhesive sheet (3) was produced.
  • Comparative Example 2 Lightly peelable film / second adhesive as in Example 1, except that the thermally expandable substrate (Y-1) was replaced with the thermally expandable substrate (Y-4) formed in Production Example 6.
  • a pressure-sensitive adhesive sheet (4) was prepared by laminating layer (X-2) / thermally expandable substrate (Y-4) / first pressure-sensitive adhesive layer (X-1) / heavy release film in this order.
  • Comparative Example 3 The surface of the second pressure-sensitive adhesive layer (X-2) formed in Production Example 2 and the surface of the heat-expandable pressure-sensitive adhesive layer (Y-3) formed in Production Example 5 are bonded together to form a light release film / second pressure-sensitive adhesive A pressure-sensitive adhesive sheet (5) in which layer (X-2) / heat-expandable pressure-sensitive adhesive layer (Y-3) / light release film was laminated in this order was produced.
  • the heavy release film of the pressure-sensitive adhesive sheets (1) to (4) and the other light release film of the pressure-sensitive adhesive sheet (5) are removed, and the first pressure-sensitive adhesive layer (X-1) or the thermal expansibility that is exposed
  • the adhesive surface of the adhesive layer (Y-3) nine semiconductor chips (each chip size is 6.4 mm ⁇ 6.4 mm, chip thickness is 200 ⁇ m (# 2000)), the adhesive surface and each semiconductor The chips were placed at a necessary interval so as to be in contact with the circuit surface of the chip.
  • the light release film on the heat-expandable pressure-sensitive adhesive layer (Y-3) side of the pressure-sensitive adhesive sheet (5) is removed, and the pressure-sensitive adhesive sheet is placed on the pressure-sensitive adhesive surface of the exposed heat-expandable pressure-sensitive adhesive layer (Y-3).
  • a semiconductor chip was placed.
  • the semiconductor chip on the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer is visually and microscopically observed to check whether the semiconductor chip is misaligned.
  • F A semiconductor chip in which a positional deviation of 25 ⁇ m or more with respect to the place to be placed was confirmed.
  • a sealing resin film is laminated on the adhesive surface and the semiconductor chip, and the semiconductor chip is sealed using a vacuum heating and pressure laminator (“7024HP5” manufactured by ROHM and HAAS) to produce a sealing body.
  • the sealing conditions are as follows. -Preheating temperature: 100 ° C for both table and diaphragm ⁇ Vacuum drawing: 60 seconds ⁇ Dynamic press mode: 30 seconds ⁇ Static press mode: 10 seconds ⁇ Sealing temperature: 180 ° C. (temperature lower than 208 ° C. which is the expansion start temperature of thermally expandable particles) ⁇ Sealing time: x 60 minutes
  • the pressure-sensitive adhesive sheets (1) to (5) are heated for 3 minutes at 240 ° C., which is equal to or higher than the expansion start temperature (208 ° C.) of the thermally expandable particles.
  • the stop body is separated, and the semiconductor chip on the surface of the separated sealing body (the surface on which the adhesive sheet has been attached) is observed visually and with a microscope, and the presence or absence of misalignment of the semiconductor chip is confirmed. evaluated.
  • A A semiconductor chip in which a positional deviation of 25 ⁇ m or more from before sealing was not confirmed.
  • F A semiconductor chip in which a positional deviation of 25 ⁇ m or more occurred before sealing was confirmed.
  • the heavy release film of the pressure-sensitive adhesive sheets (1) to (4) is also removed, and the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X-1) or the heat-expandable pressure-sensitive adhesive layer (Y-3) is exposed.
  • a test sample was prepared by attaching to a stainless steel plate (SUS304 360 polishing) as an adherend and allowing it to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity). Further, the light release film on the heat-expandable pressure-sensitive adhesive layer (Y-3) side of the pressure-sensitive adhesive sheet (5) is removed, and the pressure-sensitive adhesive sheet is applied to the pressure-sensitive adhesive surface of the exposed heat-expandable pressure-sensitive adhesive layer (Y-3).
  • Test samples were prepared in the same procedure as (1) to (4). Then, using the above test sample, in an environment of 23 ° C. and 50% RH (relative humidity), in accordance with JIS Z0237: 2000, by a 180 ° peeling method at a pulling speed of 300 mm / min at 23 ° C. The adhesive strength was measured. In addition, the above test sample is heated on a hot plate for 3 minutes at 240 ° C., which is equal to or higher than the expansion start temperature (208 ° C.) of the thermally expandable particles, and the standard environment (23 ° C., 50% RH (relative humidity)).
  • the adhesive strength after heating at a temperature equal to or higher than the expansion start temperature was also measured at a pulling rate of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000.
  • the adhesive force was set to 0 (N / 25mm).
  • the pressure-sensitive adhesive sheet (3) of Comparative Example 1 and the pressure-sensitive adhesive sheet (5) of Comparative Example 3 have a thermally expandable pressure-sensitive adhesive layer, not a thermally expandable base material.
  • the position shift of the semiconductor chip was observed, and a step was observed on the surface of the semiconductor chip side after the sealing process. Therefore, for example, it is considered that it is not suitable for use in a sealing process when manufacturing FOWLP.
  • the pressure-sensitive adhesive sheet (4) of Comparative Example 2 had a certain pressure-sensitive adhesive force even after heating at a temperature equal to or higher than the expansion start temperature, and could not be said to be peelable by heating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne une feuille adhésive comprenant : un substrat non adhésif thermiquement expansible contenant une résine et des particules thermiquement expansibles qui présentent une température de début d'expansion (t) de 120 à 250 °C ; et une couche adhésive contenant une résine adhésive. Le substrat thermiquement expansible satisfait les exigences (1) et (2) indiquées ci-dessous. Exigence (1) : le module d'élasticité au stockage E'(23) du substrat thermiquement expansible à 23 °C est de 1,0 x 106 Pa ou plus. Exigence (2) : le module d'élasticité au stockage E'(t) du substrat thermiquement expansible à la température de début d'expansion (t) des particules thermiquement expansibles est de 1,0 x 107 Pa ou moins.
PCT/JP2018/013357 2017-03-31 2018-03-29 Feuille adhésive WO2018181770A1 (fr)

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JPWO2020196757A1 (fr) * 2019-03-28 2020-10-01
JPWO2020196755A1 (fr) * 2019-03-28 2020-10-01
JP7530347B2 (ja) 2019-03-15 2024-08-07 リンテック株式会社 粘着シート及び半導体装置の製造方法

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CN113597458B (zh) * 2020-03-27 2023-10-27 株式会社寺冈制作所 热剥离型粘着胶带

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KR20190129053A (ko) 2019-11-19
TWI774745B (zh) 2022-08-21
CN110494524A (zh) 2019-11-22
CN110494524B (zh) 2022-01-18
KR102511639B1 (ko) 2023-03-20

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