JP2015151521A - Adhesive agent laminate and utilization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive agent laminate that has high adhesiveness and heat resistance and can remove residue suitably by cleaning after peeling a photocured adhesion layer from a substrate.SOLUTION: An adhesive agent laminate 10 has a first adhesive agent layer 1 including a first thermoplastic resin, a separation layer 2 including a nanoparticle and being altered by irradiation with lights and a second adhesive agent layer 3 including a second thermoplastic resin laminated in this order. The nanoparticle is a metal, a metal oxide, carbon or an organic pigment and has an average particle size in the range of not less than 5 nm to not more than 100 nm. The first and second adhesive agent layers 1, 3 have the same composition and are a triblock resin or a hydrogenated styrene elastomer.

Description

  The present invention relates to an adhesive laminate and use thereof.

  As mobile phones, digital AV devices, IC cards, etc. have become more sophisticated, the demand for higher integration of silicon in the package has increased by reducing the size and thickness of semiconductor silicon chips (hereinafter referred to as chips). ing. For example, in an integrated circuit that integrates a plurality of chips into one package such as CSP (chip size package) or MCP (multi-chip package), a reduction in thickness is required. In order to achieve high integration of chips in the package, it is necessary to reduce the thickness of the chip to a range of 25 to 150 μm.

  However, since a semiconductor wafer (hereinafter referred to as a wafer) serving as a chip base becomes thin by grinding, its strength is weakened, and the wafer is likely to be cracked or warped. Further, since it is difficult to automatically transport a wafer whose strength has been reduced by making it thinner, it must be transported manually, and the handling is complicated.

  Therefore, a wafer handling system has been developed that maintains the strength of the wafer and prevents the occurrence of cracks and warping of the wafer by bonding a plate made of glass, hard plastic, or the like, to the wafer to be ground. . Since the wafer strength can be maintained by the wafer handling system (WHS), the transport of the thinned semiconductor wafer can be automated.

  As a method for manufacturing a semiconductor chip in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and after the semiconductor wafer is processed, the support side The photothermal conversion layer is decomposed by irradiating radiant energy from the substrate to separate the semiconductor wafer from the support.

JP 2004-64040 A (published February 26, 2004)

  However, in the conventional technique as described above, after separating the substrate and the support, the photocured adhesive layer is peeled off from the substrate by the peel. At this time, the photocurable adhesive and the substrate are in contact with each other. Therefore, there is a problem that the residue of the adhesive layer tends to remain on the substrate.

  Further, since the photothermal conversion layer is decomposed by irradiating radiant energy in order to separate the substrate and the support, there is a concern about an increase in particles generated when the substrate and the support are separated.

  This invention is made | formed in view of said subject, The objective is to provide the adhesive laminated body which is equipped with high adhesiveness and heat resistance, and can remove a residue suitably by washing | cleaning.

  In order to solve the above problems, an adhesive laminate according to the present invention includes a first adhesive layer containing a first thermoplastic resin, a separation layer containing nanoparticles and altered by light irradiation, The second adhesive layer containing the second thermoplastic resin is laminated in this order.

  According to the present invention, there is provided an adhesive laminate that has high adhesiveness and heat resistance, and that can suitably remove a residue by washing.

1 is a schematic cross-sectional view for explaining an adhesive laminate, a substrate laminate, an adhesion method, a separation method, and a cleaning method according to an embodiment of the present invention.

  The adhesive laminate according to the present invention includes a first adhesive layer containing a first thermoplastic resin, a separation layer containing nanoparticles and denatured by light irradiation, and a second thermoplastic resin containing a second thermoplastic resin. The second adhesive layer is laminated in this order.

  According to the said structure, since the separation layer contains the nanoparticles, the adhesive laminate can have high adhesiveness and heat resistance. For this reason, when performing a desired process, it can prevent that a separated layer is damaged, and can prevent that a board | substrate peels from a support body. Further, the separation layer of the adhesive laminate does not contain a thermoplastic resin. For this reason, after separating the substrate and the support, when the substrate is washed with the cleaning liquid, the residue of the separation layer and the adhesive layer attached to the substrate can be suitably removed. In addition, since the separation layer can be suitably altered by visible light, it suppresses the generation of particles that occur when separating the substrate and the support rather than disassembling the separation layer by irradiating radiant energy. can do.

  Moreover, according to the said structure, since the adhesive layer of an adhesive laminated body uses the 1st and 2nd thermoplastic resin, a board | substrate and a support body are more than than the case where a photocurable adhesive agent is used. The residue of the adhesive layer after separation can be suitably removed by washing.

<Adhesive laminate>
First, the adhesive laminated body which concerns on one Embodiment of this invention is demonstrated using FIG.

  As shown to (a) of FIG. 1, the adhesive laminated body 10 which concerns on one Embodiment contains the 1st adhesive bond layer 1 containing a 1st thermoplastic resin, a nanoparticle, and a quality change by irradiation of light. The separating layer 2 to be laminated and the second adhesive layer 3 containing the second thermoplastic resin are laminated in this order.

  The adhesive laminate 10 is used for bonding and fixing the substrate 20 and the support plate 30 as shown in FIG.

  As the substrate 20, for example, an arbitrary substrate such as a wafer substrate, a ceramic substrate, a thin film substrate, or a flexible substrate can be used. Moreover, in one Embodiment, the circuit is formed in the surface at the side in which the adhesive bond layer 3 in the board | substrate 20 is formed. Here, when the circuit formed on the substrate 20 is three-dimensional, the substrate 20 has a step due to unevenness.

  The support plate 30 is a support member that supports the substrate 20 and may have a strength necessary to prevent the substrate 20 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 20. . From the above viewpoint, the support plate 30 is made of, for example, glass, silicon, or acrylic resin.

[First adhesive layer]
The first adhesive layer 1 is a layer formed of an adhesive containing a first thermoplastic resin, and is used for bonding and fixing the support plate 30 in the substrate laminate 50 ((c) in FIG. 1). ).

  The thickness of the first adhesive layer 1 may be appropriately set according to the types of the substrate 20 and the support plate 30 to be attached, the treatment applied to the substrate 20 after being attached, and the like. It is preferably in the range of 5 μm or more and 50 μm or less, more preferably in the range of 0.5 μm or more and 20 μm or less, and most preferably in the range of 1 μm or more and 10 μm or less. If the film thickness of the first adhesive layer 1 is in the range of 0.5 μm or more and 50 μm or less, the support plate 30 is suitably bonded and fixed to the adhesive laminate 10 by the first adhesive layer 1. Can do. Further, when the separation layer 2 is irradiated with light, the light can be suitably transmitted through the first adhesive layer 1, and the separation layer 2 can be suitably absorbed with light.

  As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoquinone, hydrocarbon, polyimide, and elastomer constitute the first adhesive layer 1 according to the present invention. It can be used as an adhesive. Hereinafter, the composition of the resin contained in the first adhesive layer 1 in the present embodiment will be described.

  The first thermoplastic resin contained in the first adhesive layer 1 may be any one having adhesiveness, such as a hydrocarbon resin, an acrylic-styrene resin, a maleimide resin, an elastomer resin, etc. Or what combined these etc. are mentioned.

  The glass transition temperature (Tg) of the adhesive varies depending on the type and molecular weight of the resin and a compound such as a plasticizer for the adhesive. The type and molecular weight of the resin contained in the adhesive can be appropriately selected according to the type of the substrate and the support, but the Tg of the resin used for the adhesive is in the range of −60 ° C. or higher and 200 ° C. or lower. The inside is preferable, and the inside of the range of −25 ° C. or higher and 150 ° C. or lower is more preferable. When the Tg of the resin used for the adhesive is in the range of −60 ° C. or higher and 200 ° C. or lower, the adhesive force of the first adhesive layer 1 is preferably reduced without requiring excessive energy for cooling. be able to. Moreover, you may adjust Tg of the 1st adhesive bond layer 1 by mix | blending a plasticizer, resin of a low polymerization degree, etc. suitably.

  The glass transition temperature (Tg) can be measured using, for example, a known differential scanning calorimeter (DSC).

(Elastomer)
The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the “styrene unit” may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. Further, the content of the styrene unit is more preferably in the range of 14% by weight or more and 50% by weight or less. Furthermore, the elastomer preferably has a weight average molecular weight in the range of 10,000 to 200,000.

  If the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the hydrocarbon solvent described later Therefore, the first adhesive layer can be removed more easily and quickly. Further, since the content of the styrene unit and the weight average molecular weight are within the above ranges, the resist solvent (eg, PGMEA, PGME, etc.), acid (hydrogen fluoride) exposed when the wafer is subjected to the resist lithography process. Acid) and alkali (TMAH, etc.).

  In addition, you may further mix the (meth) acrylic acid ester mentioned later with an elastomer.

  Further, the content of styrene units is more preferably 17% by weight or more, and more preferably 40% by weight or less.

  A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

  As the elastomer, if the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, various trimethyl monomers are used. A block resin can be used. For example, polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS). And hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolypropylene in which styrene block is reactively crosslinked -(Septon V9461 (manufactured by Kuraray Co., Ltd.)), Styrene block is a reactive cross-linked styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.) Manufactured by Kuraray Co., Ltd.), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group-modified), etc., and the styrene unit content and weight average molecular weight are within the above-mentioned ranges. Things can be used.

  In the adhesive laminate 10 according to one embodiment, the elastomer is more preferably a triblock resin. Here, the triblock resin refers to an elastomer that is a block polymer of styrene at both ends. By using a triblock resin as the first thermoplastic resin, both ends can be blocked with a styrenic polymer having high thermal stability, and high heat resistance can be imparted to the first adhesive layer 1. .

  Moreover, in the adhesive laminated body 10 which concerns on one Embodiment, it is more preferable that the said elastomer is a water addition styrene elastomer. By using a water-added styrene elastomer as the elastomer, the stability of the first adhesive layer 1 to heat is improved, and deterioration such as decomposition and polymerization is unlikely to occur. Moreover, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and conjugated diene. Stability against heat is improved, and alteration such as decomposition and polymerization hardly occurs. Moreover, higher heat resistance is exhibited by blocking both ends with a styrenic polymer having high thermal stability. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Examples of commercially available products that can be used as an elastomer included in the adhesive constituting the first adhesive layer 1 include “Septon (trade name)” manufactured by Kuraray Co., Ltd. and “Hibler (trade name)” manufactured by Kuraray Co., Ltd. Asahi Kasei Co., Ltd. “Tuftec (trade name)”, JSR Corporation “Dynaron (trade name)” and the like.

  The content of the elastomer contained in the adhesive constituting the first adhesive layer 1 is preferably in the range of 50 parts by weight or more and 99 parts by weight or less, with the total amount of the adhesive being 100 parts by weight, for example, More preferably within the range of not less than 99 parts by weight and most preferably not less than 70 parts by weight and not more than 95 parts by weight. By setting it within these ranges, the wafer and the support can be suitably bonded together while maintaining the heat resistance.

  A plurality of types of elastomers may be mixed. That is, the adhesive constituting the first adhesive layer 1 may include a plurality of types of elastomers. It is sufficient that at least one of the plurality of types of elastomers includes a styrene unit as a constituent unit of the main chain. In addition, at least one of the plurality of types of elastomers has a styrene unit content in the range of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less. Is within the scope of the present invention. Moreover, when the adhesive which comprises the 1st adhesive bond layer 1 contains several types of elastomer, you may adjust so that content of a styrene unit may become in said range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight is 1 weight ratio. When mixed in a one-to-one relationship, the styrene content with respect to the total elastomer contained in the adhesive composition is 21 to 22% by weight, and thus 14% by weight or more. For example, when a styrene unit of 10% by weight and 60% by weight are mixed at a weight ratio of 1: 1, it becomes 35% by weight and falls within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers contained in the adhesive composition according to the present invention all contain a styrene unit within the above range and have a weight average molecular weight within the above range.

  In addition, it is preferable to form the 1st adhesive bond layer 1 using resin other than photocurable resin (for example, UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent a residue from remaining around the minute unevenness of the supported substrate after the first adhesive layer 1 is peeled or removed. In particular, the adhesive constituting the first adhesive layer 1 is preferably not soluble in any solvent but soluble in a specific solvent. This is because the first adhesive layer 1 can be removed by dissolving in the solvent without applying physical force to the substrate 20. When removing the first adhesive layer 1, the first adhesive layer 1 can be easily removed without damaging or deforming the substrate 20 even from the substrate 20 with reduced strength. .

(Hydrocarbon resin)
The hydrocarbon resin is a resin that has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. As the hydrocarbon resin, cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (hereinafter referred to as “resin (A)”). Resin (B) ”), and the like, but is not limited thereto.

  The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specific examples include a ring-opening (co) polymer of a monomer component containing a cycloolefin monomer, and a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin monomer.

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, and tetracyclododecene. Tetracycles, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or polycyclic alkyl (methyl, ethyl, propyl, butyl, etc.) substituted alkenyls (vinyl, etc.) Substitution, alkylidene (ethylidene, etc.) substitution, aryl (phenyl, tolyl, naphthyl, etc.) substitution, etc. are mentioned. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin-based monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, and α-olefin. The alkene monomer may be linear or branched.

  Moreover, it is preferable from a viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property) to contain a cycloolefin monomer as a monomer component which comprises resin (A). The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, More preferably, it is 70 mol% or less.

  Moreover, you may contain a linear or branched alkene monomer as a monomer component which comprises resin (A). The ratio of the alkene monomer to the whole monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. 30 to 80 mol% is more preferable.

  The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at high temperatures. It is preferable for suppressing generation of gas.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be set as appropriate according to conventional methods.

  Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” and “ZEONEX” manufactured by Zeon Corporation. And “ARTON” manufactured by JSR Corporation.

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition temperature of the resin (A) is 60 ° C. or higher, softening of the first adhesive layer can be further suppressed when the laminate is exposed to a high temperature environment.

  The resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins. Specifically, examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like. Examples of the rosin resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarone-indene petroleum resins, and the like. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 ° C. or higher, the laminate can be suppressed from being softened when exposed to a high temperature environment, and adhesion failure does not occur. On the other hand, when the softening point of the resin (B) is 160 ° C. or less, the peeling rate when peeling the laminate is good.

  Although the weight average molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the peeling rate when peeling the laminate is good. In addition, the weight average molecular weight of resin (B) in one Embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

  In addition, you may use what mixed resin (A) and resin (B) as resin. By mixing, heat resistance and peeling speed are improved. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio). Since it is excellent in tolerance and flexibility, it is preferable.

(Acrylic-styrene resin)
Examples of the acrylic-styrene resin include a resin obtained by polymerization using styrene or a styrene derivative and (meth) acrylic acid ester as monomers.

  Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. . Examples of the (meth) acrylic acid alkyl ester having a chain structure include acrylic long-chain alkyl esters having an alkyl group having 15 to 20 carbon atoms and acrylic alkyl esters having an alkyl group having 1 to 14 carbon atoms. . As acrylic long-chain alkyl esters, acrylic acid or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Examples include alkyl esters. The alkyl group may be branched.

  Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, an alkyl group of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include esters.

  Examples of (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned, and isobornyl methacrylate and dicyclopentanyl (meth) acrylate are more preferable.

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited. Examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthracenyl group. A phenoxymethyl group, a phenoxyethyl group, and the like. The aromatic ring may have a chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Having an aliphatic hydrocarbon group such as maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc. Examples include resins obtained by polymerizing aromatic maleimide having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np-methylphenylmaleimide. It is done.

  For example, a cycloolefin copolymer that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2) can be used as the resin of the adhesive component.

(In chemical formula (2), n is 0 or an integer of 1 to 3)
As such cycloolefin copolymer, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

(Diluted solvent)
As a diluent solvent for forming the first adhesive layer, for example, hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, and other linear hydrocarbons, carbon number 4 to 15 Branched hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and other cyclic hydrocarbons, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4- Terpine, 1,8-terpine, bornin, norbornane, pinan, tsujang, karan, longifolene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol Terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonon, tuyon, camphor, d-limonene, l-limonene, dipentene Terpene solvents such as: Lactones such as γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol Polyhydric alcohols such as dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate Compounds having an ester bond, compounds having an ether bond such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of the polyhydric alcohols or compounds having the ester bond, etc. (In these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL ), Esters such as methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; Saul, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and aromatic organic solvents such as butyl phenyl ether.

(Other ingredients)
The adhesive constituting the first adhesive layer may further contain other miscible materials as long as the essential properties are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors and surfactants for improving the performance of the adhesive may be further used. it can.

(Separation layer)
The separation layer 2 is a layer that contains nanoparticles and is altered by absorbing light irradiated through the support plate 30. The separation layer 2 is provided between the first adhesive layer 1 and the second adhesive layer 3 in the adhesive laminate 10.

  In one embodiment, the separation layer is a layer containing nanoparticles that are altered by absorbing light irradiated through the support. In this specification, the “deterioration” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer is reduced. As a result of the alteration of the separation layer caused by absorbing light, the separation layer loses its strength or adhesion prior to light irradiation.

  In addition, the alteration of the separation layer includes dissociation of aggregation of nanoparticles due to absorbed light energy, decomposition (exothermic or non-exothermic), cross-linking, change in configuration or dissociation of functional groups (and separation accompanying these). Layer hardening, degassing, shrinking or expansion) and the like. The alteration of the separation layer occurs as a result of absorption of light by the material constituting the separation layer. Therefore, the type of alteration of the separation layer can vary depending on the type of material constituting the separation layer.

  The separation layer 2 is preferably formed only from nanoparticles, but may contain an additive such as a surfactant as long as the essential characteristics of the present invention are not impaired.

[Nanoparticles]
In the present invention, the nanoparticle means a finely divided pigment, and in the present specification, means a particle having an average particle diameter smaller than 500 nm. In the adhesive laminate 10 according to one embodiment, the nanoparticles preferably have an average particle diameter in the range of 5 nm to 100 nm, and the average particle diameter in the range of 5 nm to 90 nm. The average particle size is most preferably in the range of 10 nm or more and 80 nm or less. If the average particle diameter of the nanoparticles is within the range of 5 nm or more and 100 nm or less, the substrate laminate 50 provided with the adhesive laminate 10 can be used even if a desired treatment is performed on the substrate 20. It is possible to prevent stress from concentrating on the constituent separation layer 2 and damaging the separation layer 2. For this reason, in the board | substrate laminated body 50, it can prevent that the board | substrate 20 peels from the support plate 30. FIG. Moreover, if the separation layer 2 is formed of nanoparticles, the separation layer can be suitably formed even if the separation layer does not contain a thermoplastic resin.

  The thickness of the separation layer 2 is, for example, preferably in the range of 0.3 μm or more and 20 μm or less, more preferably in the range of 0.5 μm or more and 15 μm or less, and in the range of 1 μm or more and 10 μm or less. Most preferably. If the thickness of the separation layer 2 is within a range of 0.3 μm or more, desired alteration can be caused in the separation layer 2 by irradiation with light for a short time and irradiation with low energy light. Moreover, if the thickness of the separation layer 2 is within the range of 20 μm or less, the separation layer of the adhesive laminate 10 can be used even when a desired treatment is performed on the substrate bonded using the adhesive laminate 10. It is possible to prevent stress from being concentrated on 2, and to prevent the separation layer 2 from being damaged. Moreover, even if the adhesive laminate 10 is formed on a film, the separation layer 2 can be prevented from being damaged due to the bending of the film.

  In addition, the nanoparticles preferably have a thermal decomposition temperature of 300 ° C. or higher, and more preferably 350 ° C. or higher. If the thermal decomposition temperature of the nanoparticles is 300 ° C. or higher, the separation layer 2 can have high heat resistance. Therefore, it is possible to prevent the separation layer 2 from being damaged when the substrate laminate 50 is subjected to plasma treatment or heat treatment, and the substrate 20 from being peeled off from the support plate 30.

  The nanoparticles absorb light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the organic nanoparticles used in the separation layer 2, the organic nanoparticles can be suitably altered. In addition, it is more preferable to select nanoparticles that can be altered by light having a wavelength in the range of visible light.

  Examples of the nanoparticles included in the separation layer 2 include inorganic nanoparticles and organic nanoparticles. Here, examples of inorganic nanoparticles include nanoparticles such as metals, metal oxides, metal nitrides, metal carbides, metal sulfides, and carbon. Examples of organic nanoparticles include nanoparticles such as organic pigments.

(Inorganic nanoparticles)
Examples of the nanoparticles used in the separation layer include inorganic nanoparticles. Here, in the adhesive laminated body 10 which concerns on one Embodiment, it is preferable that the said nanoparticle is a metal, a metal oxide, a metal nitride, a metal carbide, a metal sulfide, or carbon. When the separation layer 2 contains nanoparticles such as metal, metal oxide, metal nitride, metal carbide, metal sulfide, or carbon, it can be suitably altered by absorbing light. As a result, the separation layer 2 loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 20 or the like), the separation layer 2 is broken, and the support plate 30 and the substrate 20 can be easily separated.

The said metal or metal oxide should just be the structure which changes in quality by absorbing light. Examples of the metal include gold, silver, copper, iron, palladium, platinum, nickel, aluminum, titanium, and chromium. Examples of the metal oxide include nickel oxide (NiO), cobalt oxide (Co ₂ O ₃ ), manganese oxide (Mn ₂ O ₃ and Mn ₃ O ₄ ), aluminum oxide, copper oxide, iron oxide, zinc oxide, and oxidation. such as cerium and SiO ₂ can be mentioned. Examples of the metal nitride include titanium nitride and gallium nitride. Examples of the metal sulfide include zinc sulfide and cadmium sulfide. By including inorganic nanoparticles in the separation layer, it is possible to form a separation layer that is suitably altered by irradiation with light in the range of 380 nm to 750 nm, which is visible light.

  When a metal is used for the separation layer 2, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 2, the type of laser light source, and laser output. Therefore, it is preferable to take measures against these problems by providing an antireflection film or an antistatic film on the upper or lower side of the separation layer 2 or one of them.

(carbon)
The nanoparticles included in the separation layer 2 may be nanoparticles including carbon, for example. Here, carbon is a concept that may include an allotrope of carbon, and may be, for example, carbon black, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like. In the adhesive laminate 10 according to one embodiment, the carbon nanoparticles used in the separation layer 2 are more preferably carbon nanotubes. If the nanoparticles used in the separation layer 2 are carbon nanotubes, an adhesive laminate with high separation properties can be formed (organic nanoparticles)
Examples of the nanoparticles used in the separation layer include organic nanoparticles. In the adhesive laminated body 10 which concerns on one Embodiment, it is preferable that the said nanoparticle is an organic pigment. Here, the organic pigment only needs to have a structure that is altered by absorbing light. For example, an azo pigment, a phthalocyanine pigment, a quinacridone pigment, an indoline pigment, a cyanine pigment, a merocyanine pigment, and a fullerene pigment. Pigments, polycyclic aromatic pigments, and polydiacetylene pigments can be used. Also, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo , Isoindoline, isoindolinone, pyranthrone, and isoviolanthrone compound pigments. By including organic nanoparticles in the separation layer, it is possible to form a separation layer that is preferably altered by irradiation with light in the range of 380 nm or more and 750 nm or less, which is visible light.

[Second adhesive layer]
The second adhesive layer 3 is a layer containing a second thermoplastic resin, and is used for bonding and fixing the substrate 20 in the substrate laminate 50 ((c) in FIG. 1).

  The kind of the second thermoplastic resin used for the second adhesive layer 3 is the same as that described for the first adhesive layer 1 described above. These items may be different from each other between the first adhesive layer 1 and the second adhesive layer 3, but should not be limited. Here, in the adhesive laminate 10 according to one embodiment, it is more preferable that the first adhesive layer 1 and the second adhesive layer 3 have the same composition.

  Thereby, the structure of an adhesive laminated body can be simplified, and manufacture of the adhesive laminated body 10 can be simplified. Moreover, the temperature conditions at the time of bonding a board | substrate and a support plate etc. can be set similarly to the adhesive film which consists of a single adhesive bond layer.

  In the adhesive laminate 10 according to one embodiment, the film thickness of the second adhesive layer 3 is preferably in the range of 10 μm to 200 μm, and in the range of 15 μm to 150 μm. Is more preferable, and most preferably in the range of 20 μm or more and 130 μm or less. If the film thickness of the second adhesive layer 3 is in the range of 10 μm or more and 200 μm or less, even if a step due to the circuit is formed on the substrate 20, the step due to the circuit of the substrate 20 is changed to the second adhesive. The substrate 20 and the support plate 30 can be bonded and fixed by the adhesive laminate 10 so as to be embedded by the layer 3.

<Adhesive film>
The adhesive film which concerns on one Embodiment of this invention may be equipped with the adhesive laminated body 10 which concerns on one Embodiment of this invention on the film. That is, in the adhesive film according to one embodiment, after any one of the above-mentioned adhesive laminates is formed on a film such as a flexible film in advance, this film (adhesive film) is attached to a workpiece and used. A method (adhesive film method) may be used.

  According to the said structure, the board | substrate laminated body 50 can be formed by affixing the adhesive laminated body 10 formed in the film on the board | substrate 20 or the support plate 30. FIG. In other words, the substrate laminate 50 including the separation layer 2 and the first and second adhesive layers can be manufactured by a simple process. Therefore, if the adhesive film according to one embodiment is used, the substrate laminate 50 including the adhesive laminate 10 having high adhesiveness and heat resistance can be manufactured by a simple process.

  The adhesive film may be used by further covering the adhesive laminate 10 with a protective film. In this case, the protective film on the adhesive laminate 10 is peeled off, the exposed adhesive layer is overlaid on the workpiece, and then the above film is peeled off from the adhesive layer on the workpiece. The adhesive laminate 10 can be easily provided.

  Therefore, when this adhesive film is used, the film thickness is uniform compared to the case where the first and second adhesive layers and the separation layer are applied directly on the workpiece to form an adhesive laminate. An adhesive layer having good properties and surface smoothness can be formed.

  As said film used for manufacture of an adhesive film, the adhesive laminated body 10 formed on the film can be peeled from the said film, and the adhesive laminated body 10 is on a to-be-processed surface, such as a support plate and a wafer. There is no particular limitation as long as it is a release film that can be transferred to the film. For example, the flexible film which consists of synthetic resin films, such as a polyethylene terephthalate with a film thickness of 15-125 micrometers, polyethylene, a polypropylene, a polycarbonate, and a polyvinyl chloride, is mentioned. It is preferable that a release treatment is performed on the film as necessary to facilitate transfer.

  Moreover, when using a protective film, as a protective film, although not limited as long as it can peel from an adhesive bond layer, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable, for example. Each protective film is preferably coated or baked with silicon. This is because peeling from the adhesive layer is facilitated. Although the thickness of a protective film is not specifically limited, 15-125 micrometers is preferable. It is because the softness | flexibility of the adhesive film provided with the protective film can be ensured.

<Method for producing adhesive film>
The manufacturing method of the adhesive film which concerns on one Embodiment of this invention is a method of manufacturing the adhesive film which concerns on this invention, Comprising: Said 1st adhesive bond layer 1 containing said 1st thermoplastic resin is laminated | stacked. A first adhesive layer laminating step, a separating layer laminating step for laminating the separating layer 2 containing the nanoparticles, and a second laminating layer for laminating the second adhesive layer 3 containing the second thermoplastic resin. Two adhesive layer laminating steps, and laminating the first adhesive layer 1, the separating layer 2 and the second adhesive layer 3 in this order on the film.

  Here, the 1st adhesive bond layer 1, the separation layer 2, and the 2nd adhesive bond layer 3 should just be laminated | stacked in this order. That is, any of the first adhesive layer forming step and the second adhesive layer forming step may be performed first. As one embodiment, a second adhesive layer 3 is laminated by a second adhesive layer forming step on a film having releasability, and a separation layer 2 is laminated by a separation layer laminating step. The first adhesive layer 1 may be laminated by a layer lamination process, and then the first adhesive layer 1 may be protected by a protective film. In this order, if the adhesive laminate 10 is formed on the film, after the protective film of the adhesive film is peeled off, the first adhesive layer 1 is attached to the support plate 30 ((b) in FIG. 1), Then, the board | substrate 20 can be adhere | attached on the 2nd adhesive bond layer 3 by peeling the film provided with mold release property, and the board | substrate laminated body 50 can be formed ((c) of FIG. 1).

[First adhesive layer lamination process]
In the first adhesive layer laminating step, the first adhesive layer 1 containing the first thermoplastic resin is laminated. Here, the first adhesive layer 1 can be formed by applying an adhesive containing the first thermoplastic resin by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like. it can. Moreover, after apply | coating the 1st adhesive bond layer 1, it is preferable to remove a solvent from the 1st adhesive bond layer 1 by heating a 1st adhesive bond layer. In addition, what is necessary is just to adjust suitably the conditions which heat the 1st adhesive bond layer 1 according to the kind of solvent which melt | dissolves a 1st thermoplastic resin.

  The film thickness of the first adhesive layer 1 may be appropriately set according to the type of the substrate 20 and the support plate 30 to be attached, the treatment applied to the substrate 20 after being attached, etc. What is necessary is just to form so that it may exist in the range of 0.5 micrometer or more and 50 micrometers or less as described in the term of the [first adhesive layer].

[Separation layer lamination process]
In the separation layer lamination step, the separation layer 2 containing the nanoparticles is laminated.

  The separation layer 2 containing nanoparticles may be formed by applying a dispersion in which nanoparticles are dispersed. Here, the dispersion medium used for the nanoparticle dispersion may be water and an organic solvent. Examples of the organic solvent include p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tujang, kalan, longifolene, geraniol, nerol, linalool, Citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1, Terpene solvents such as 8-cineole, borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH) Ketones such as methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol mono Compounds having an ester bond such as acetate or dipropylene glycol monoacetate, monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl of the polyhydric alcohols or compounds having the ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as ether (in these, propylene glycol monomer Tilether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, Esters such as methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; aromatic organics such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether A solvent etc. are mentioned. Moreover, polar solvents, such as PM and N-methyl-2-pyrrolidone (NMP), can also be used. The nanoparticles may be dispersed in a dispersion medium using a surface-treated nanoparticle. Further, in order to improve the dispersibility of the nanoparticles, it may be dispersed using a dispersant or the like. In addition, as long as the average particle diameter is in the range of 5 nm or more and 100 nm or less, the separation layer 2 may use a commercially available dispersion.

  If necessary, a surfactant or the like may be added to the nanoparticle dispersion. Thereby, the dispersibility of a nanoparticle can be improved. In addition, the above-mentioned polar solvent, for example, a propylene glycol solvent such as PGME may be added to the nanoparticle dispersion as an additive. Thereby, the wettability of the nanoparticle dispersion liquid to the first or second adhesive layer may be improved.

  Examples of the method for forming the separation layer 2 include dipping, roller blades, spray coating, and slit coating. In addition, it is preferable to remove the dispersion medium by applying a nanoparticle dispersion onto the first or second adhesive layer and then heating the nanoparticle dispersion.

[Second adhesive layer lamination process]
In the second adhesive layer laminating step, the second adhesive layer 3 containing the second thermoplastic resin is laminated. Here, the second adhesive layer 3 can be formed by applying an adhesive containing the second thermoplastic resin by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like. it can. Moreover, it is preferable to remove the solvent from the second adhesive layer 3 by applying the second adhesive layer 3 and then heating the second adhesive layer 3. In addition, what is necessary is just to adjust suitably the conditions which heat the 2nd adhesive bond layer 3 according to the kind of solvent and quantity of a solvent which melt | dissolve a 2nd thermoplastic resin.

  The film thickness of the second adhesive layer 3 may be appropriately set according to the type of the substrate 20 and the support plate 30 to be pasted, the treatment applied to the substrate 20 after pasting, etc. What is necessary is just to form so that it may exist in the range of 10 micrometers or more and 200 micrometers or less as described in the term of [the 2nd adhesive bond layer].

  In addition, when using the adhesive agent containing the same thermoplastic resin in the 1st adhesive bond layer 1 and the 2nd adhesive bond layer 3, first, the adhesive agent used for a 1st adhesive bond layer and a 2nd adhesive bond layer And then the concentration of the adhesive may be adjusted by dilution. Thereby, the process for laminating the adhesive layers in the first and second adhesive laminating steps can be simplified.

<Adhesion method>
The bonding method according to one embodiment of the present invention will be described in more detail with reference to FIG.

  As shown in FIG. 1B, the bonding method according to an embodiment is a bonding method of bonding a substrate 20 and a support plate (support) 30 that transmits light, which is an embodiment of the present invention. The first adhesive step of adhering the support plate 30 to the first adhesive layer 1 of the adhesive laminate 10 according to the embodiment; the second adhesive layer 3 of the adhesive laminate 10; A second bonding step of bonding the substrate 20.

  As an example, the bonding method according to the present invention can be implemented by using the adhesive film according to the present invention.

[First bonding process]
As shown in FIG. 1B, in the bonding method according to one embodiment, a support plate 30 is bonded to the first adhesive layer 1 in the adhesive laminate 10. Thus, in the subsequent separation step, the separation layer 2 can be irradiated with light through the support plate 30 and the thin first adhesive layer 1.

  In the first bonding step, the protective film included in the adhesive film may be peeled off and the first adhesive layer 1 may be attached to the support plate 30. Thereafter, the adhesive laminate 10 may be thermocompression-bonded to the surface of the support plate 30 by moving a heating roller from above the film having releasability in the adhesive film. At this time, the protective film peeled off from the adhesive film can be stored and reused by winding it in a roll with a roller such as a winding roller.

[Second bonding process]
As shown in FIG. 1C, in the second bonding step, the substrate 20 is bonded to the second adhesive layer 3 of the adhesive laminate 10. Thereby, the substrate laminate 50 can be formed.

  In the second bonding step, the film having releasability included in the adhesive film according to the present embodiment may be peeled off and the second adhesive layer 3 may be attached to the substrate 20. Thereafter, for example, the substrate laminate 50 may be formed by applying a pressing force to the substrate laminate 50 while heating the substrate laminate 50 under vacuum conditions. Here, what is necessary is just to adjust a heating condition suitably according to the kind of thermoplastic resin used for the 1st and 2nd adhesive bond layers. Further, the pressing force applied to the substrate laminate 50 may be appropriately adjusted according to the size of the substrate laminate.

  As a result, the second adhesive layer 3 in the adhesive laminate 10 can embed the step due to the circuit of the substrate 20 with the second adhesive layer 3 even if the step due to the circuit is formed on the substrate 20. it can. For this reason, the support plate 30 and the board | substrate 20 can be adhere | attached suitably with the adhesive laminated body 10. FIG.

  Note that the bonding method according to the present invention is not limited to the method of bonding the substrate 20 and the support plate 30 using an adhesive film. That is, you may implement the adhesion | attachment method based on this invention by forming the adhesive laminated body 10 directly on a board | substrate or a support plate.

(Other processes)
After performing the second bonding step, the substrate 20 in the substrate stack 50 is thinned to a desired thickness by a grinder or the like, and then a desired circuit is formed on the surface of the substrate 20 by a photolithography step or the like. . Here, since the board | substrate 20 and the support plate 30 are adhere | attached by the adhesive laminated body 10 which concerns on this invention, it can prevent that the separation layer 2 is damaged by these processes.

<Separation method>
As shown in FIG. 1D, a separation method according to an embodiment of the present invention is a method of separating a substrate 20 and a support plate 30 that are bonded by the bonding method according to the present invention, and includes the above-described support. A separation step of separating the support plate 30 and the substrate 20 by irradiating light through the support plate 30 to the separation layer 2 of the adhesive laminate 10 in which the plate 30 and the substrate 20 are bonded. Is included.

  Accordingly, the substrate 20 and the support plate 30 can be suitably separated without applying a large force to the substrate laminate 50 ((e) in FIG. 1). Therefore, when the support plate 30 and the substrate 20 are separated, the substrate 20 can be prevented from being damaged.

[Separation process]
In the separation step according to the embodiment, the separation layer 2 of the adhesive laminate 10 is irradiated with light through the support plate 30.

In the separation step, the light applied to the separation layer 2 containing nanoparticles may be, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, depending on the wavelength that can be absorbed by the nanoparticles. Liquid laser such as solid laser, dye laser, etc., gas laser such as CO ₂ laser, excimer laser, Ar laser, He-Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light is used as appropriate That's fine.

  In the separation step, the wavelength of the light applied to the separation layer 2 through the support plate 30 is preferably in the range of 250 nm to 11000 nm, and in the range of 300 nm to 1100 nm. More preferably, it is most preferably in the range of 380 nm or more and 750 nm or less. If the wavelength of the light applied to the separation layer 2 via the support plate 30 is in the range of 250 nm or more and 11000 nm or less, the separation layer 2 containing nanoparticles can be suitably altered. Thereby, the board | substrate 20 and the support plate 30 can be isolate | separated suitably.

  In the separation method according to one embodiment, in the separation step, the wavelength of light applied to the separation layer 2 via the support plate 30 is more preferably in the range of visible light (380 nm or more, 750 nm or less). . Thereby, generation | occurrence | production of the particle | grains generate | occur | produced when isolate | separating the board | substrate 20 and the support plate 30 can be suppressed rather than the case where the separation layer 2 is decomposed | disassembled by irradiating radiant energy.

<Washing method>
As shown in FIG. 1F, a cleaning method according to an embodiment of the present invention is a method of cleaning a substrate 20 separated from a support plate 30 by a separation method according to an embodiment of the present invention. After the separation step, a cleaning step of cleaning the substrate 20 with the hydrocarbon solvent S is included.

  Thereby, the adhesive agent and the residue of a separated layer in the board | substrate 20 isolate | separated from the support plate 30 can be removed suitably. In addition, by using a hydrocarbon solvent in the washing step, even a residue of an adhesive layer having high heat resistance including an elastomer and a hydrocarbon resin can be suitably removed.

[Washing process]
In the cleaning step, the substrate 20 is cleaned with the hydrocarbon solvent S. In the cleaning step, the substrate 20 may be cleaned by supplying the hydrocarbon solvent S to the substrate 20 by spraying or a dispensing nozzle while spinning the substrate 20. Further, the substrate 20 may be cleaned by immersing the substrate 20 in the hydrocarbon solvent S.

(Hydrocarbon solvent)
Examples of the hydrocarbon solvent used in the washing step include linear or branched hydrocarbons, cyclic hydrocarbons, and terpene solvents described in the above section (Diluting solvent). These may be used alone or in combination of two or more.

  In the cleaning method according to the present embodiment, it is particularly preferable to use p-menthane, which is a terpene solvent, decahydronaphthalene, which is a cyclic hydrocarbon, among the hydrocarbon solvents. Here, p-menthane, decahydronaphthalene, and the like can adjust the dissolution rate of the adhesive by adjusting the ratio of the cis form and the trans form. For example, the dissolution rate of the adhesive by p-menthane can be increased by making the ratio of the trans form of p-menthan higher than the ratio of the cis form. Thereby, the washing | cleaning property with respect to the adhesive agent of p-menthane can be made higher.

  The hydrocarbon solvent preferably removes impurities having a boiling point higher than that of the hydrocarbon solvent by, for example, distillation. Thereby, when an adhesive agent is removed by washing | cleaning, it can prevent that a high boiling point impurity remains in the board | substrate 20 as a residue.

<Substrate laminate>
As shown in FIG. 1C, a substrate laminate 50 according to an embodiment of the present invention includes a support plate (support) 30 that transmits light and an adhesive laminate according to an embodiment of the present invention. 10 and the substrate 20 are stacked in this order.

  According to the above configuration, the substrate stack 50 can include nanoparticles in the separation layer 2. For this reason, the board | substrate laminated body 50 can be equipped with high adhesiveness and heat resistance. Further, it is possible to prevent the separation layer 2 from being damaged when a desired process is performed on the substrate 20 of the substrate laminate 50. Furthermore, it is possible to prevent the substrate 20 from being peeled off from the support plate 30. Further, the separation layer 2 of the substrate laminate 50 does not contain a thermoplastic resin. For this reason, when the substrate 20 and the support plate 30 are separated and then the substrate 20 is washed with the cleaning liquid, the residue of the separation layer and the adhesive layer attached to the substrate 20 can be suitably removed. In addition, since the separation layer 2 provided in the substrate laminate 50 can be suitably altered by visible light, the substrate 20 and the support plate 30 are separated from the case where the separation layer is decomposed by irradiating radiant energy. Generation of particles that occur when separating can be suppressed.

  The first and second thermoplastic resins are used for the adhesive layer of the adhesive laminate 10 provided in the substrate laminate 50. For this reason, the residue of the adhesive layer after separating the substrate 20 and the support plate 30 can be removed more favorably by washing than when the photocurable adhesive is used.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

(Preparation of adhesive composition)
First, the adhesive compositions A to C and G used in Examples 1 to 14 and Comparative Examples 1 to 3 were prepared. The resin, additive, main solvent and additive solvent used in each adhesive composition are shown in Table 1 below.

  The resins used for the adhesive compositions A to C and G were Septon V9827 (SEBS: styrene-ethylene-butylene-styrene block copolymer in which styrene block is a reactive crosslinking type), Septon 2002 (trade name) manufactured by Kuraray Co., Ltd. SEPS: styrene-isoprene-styrene block), TOPAS (trade name) TM (cycloolefin copolymer; ethylene-norbornene copolymer, Mw = 10,000, Mw / Mn = 2.08, manufactured by Polyplastics Co., Ltd., norbornene: ethylene = 50:50 (weight ratio)), Tuftec (trade name) H1051 (SEBS; hydrogenated styrene thermoplastic elastomer; styrene content 42%, Mw = 78,000) manufactured by Asahi Kasei Corporation.

  Furthermore, in the adhesive compositions A and C, A1 (Mw = 10,000) was used as the acrylic resin.

  A1 is a random polymer having the following structure (wherein, 1 / m / n = 60/20/20).

  Further, “IRGANOX (trade name) 1010” manufactured by BASF was used as a thermal polymerization inhibitor (additive). Decahydronaphthalene was used as the main solvent. Moreover, butyl acetate was used as an additive solvent.

  First, an adhesive composition A was prepared using the resin, additive, main solvent, and additive solvent described above. Specifically, 70 parts by weight of Septon V9827 (manufactured by Kuraray Co., Ltd.) and 20 parts by weight of TOPAS ™ (manufactured by Polyplastics Co., Ltd.) are mixed with a solvent in which 15 parts by weight of butyl acetate is blended with 200 parts by weight of decahydronaphthalene. 10 parts by weight of A1 was dissolved, and 1 part by weight of IRGANOX as an additive and 15 parts by weight of butyl acetate as an additive solvent were added to prepare an adhesive composition A having a concentration of 30%. Thereafter, the adhesive composition A was diluted with decahydronaphthalene to a concentration of 15%.

  In addition, adhesive compositions B and C were respectively prepared using the above-described resin, additive, main solvent, and additive solvent. Moreover, the adhesive composition G was blended with nickel oxide nanoparticles as a pigment. The compositions of adhesive compositions A to C and G are shown in Table 1 below.

(Preparation of separation layer composition)
Next, separation layer compositions D to F, H and I used in Examples 1 to 14 and Comparative Examples 1 and 3 were prepared. The pigment, main solvent, and additives used in each separation layer composition are shown in Table 2 below. The transmittance (532 nm) was measured with a spectrophotometer (UV3100PK, manufactured by Shimadzu Corporation), and pyrolysis was performed at a temperature of 500 ° C. using a thermogravimetric measuring device (product name “TG-DTA6200” manufactured by Seiko Instruments Inc.). The weight loss rate at 500 ° C. was measured.

  First, a separation layer composition E having the composition shown in Table 2 was prepared. Specifically, a pure water dispersion of cobalt oxide nanoparticles (average particle diameter 37 nm) having a concentration of 43% was diluted with pure water so that the concentration of cobalt oxide was 17.2%. Next, 15 parts by weight of PGME is blended with 100 parts by weight of the pure water dispersion of the cobalt oxide nanoparticles having a concentration of 17.2% so that Softanol 120 (manufactured by Nippon Shokubai Co., Ltd.) becomes 1%. By mixing, a separation layer composition E having a pigment concentration of 15% was prepared. In the separation layer composition D, a pure water dispersion of nickel oxide nanoparticles having a concentration of 35% is diluted with pure water so that the concentration of nickel oxide is 17.2%, and F is an oxidation having a concentration of 26%. Separation layer compositions D and F were prepared in the same manner as separation layer composition E, except that the pure water dispersion of manganese nanoparticles was diluted so that the concentration of manganese oxide was 17.2%. The separation layer composition H is PGME for metal oxide TM black # 95550 (manufactured by Dainichi Seika Kogyo Co., Ltd.), and the separation layer composition I is PGME for carbon nanotubes (length: 1 μm, Tokyo Chemical Industry Co., Ltd.). And the pigment concentration was adjusted to 15%.

(Preparation of adhesive laminate)
The adhesive laminate of Example 1 was produced by the following procedure. The adhesive laminate was prepared by an applicator so as to have an area of 25 cm × 30 cm.

  First, a 30% concentration of the adhesive composition A was applied to a PET film with a release agent as a base film so that the final film thickness was 50 μm, and then at 90 ° C. for 10 minutes and at 145 ° C. for 10 minutes. And baking using an oven (second adhesive layer laminating step). Next, the separation layer composition D was applied so that the final film thickness was 10 μm, and baked using an oven at 90 ° C. for 10 minutes and 145 ° C. for 10 minutes (separation layer forming step). Next, the 15% strength adhesive composition A was applied so that the final film thickness was 5 μm, and baked in an oven at 90 ° C. for 10 minutes and 145 ° C. for 10 minutes (first adhesion) Agent layer lamination step).

  In addition, adhesive laminates of Examples 2 to 14 and Comparative Examples 1 to 3 were produced under the conditions shown in Table 3 below. In Examples 2 to 14, in each step of the second adhesive layer laminating step, the separation layer forming step, and the first adhesive layer laminating step, baking with an oven was performed at 90 ° C. for 10 minutes and 145 This was carried out at 10 ° C. for 10 minutes. In addition, the adhesive laminated body of the comparative example 1 is a structure which is not provided with a 2nd adhesive bond layer, and the adhesive laminated body of the comparative example 2 is a structure which mix | blended the adhesive composition with the separated layer. Moreover, the adhesive laminated body of the comparative example 3 is the structure which used the particle | grains with an average particle diameter of 500 micrometers for a separated layer composition.

[Production of substrate laminate]
The adhesive laminate of Example 1 was produced by the following procedure.

  The adhesive laminate of Example 1 was laminated on glass having a diameter of 200 mm using a laminator at a speed of 0.5 m / min under the conditions of 100 ° C. and 0.2 MPa, and then the base film was peeled off. This formed the adhesive laminated body of Example 1 on the glass support plate. Thereafter, the glass support plate on which the adhesive laminate of Example 1 was formed was baked under vacuum conditions at 200 ° C. for 5 minutes. Next, the glass support plate on which the adhesive laminate of Example 1 was formed and the 8-inch semiconductor wafer substrate were overlapped, and the pressing force was applied for 5 minutes under the condition of 215 ° C. and 4000 kg while maintaining the vacuum condition. added. This produced the board | substrate laminated body of Example 1. FIG. Moreover, the board | substrate laminated body of Examples 2-14 and Comparative Examples 1-3 was produced on the same conditions.

[Evaluation of substrate laminate]
The following evaluation was performed about the board | substrate laminated body of Examples 1-14 produced by the above, and Comparative Examples 1-3.

(Pasteability)
At the time of producing the substrate laminate, visual evaluation was performed with “◯” indicating that there was no defective bonding between the semiconductor wafer substrate and the glass support plate, and “X” indicating that there was defective bonding.

(Grindability)
Thinning processing was performed on the back surface of the semiconductor wafer substrate in the substrate laminate until the thickness became 50 μm with a back grinder manufactured by DISCO. Thereafter, whether or not the edge portion of the wafer substrate was peeled off or chipped was evaluated by a microscope. A case where there was no peeling or chipping was indicated as “◯”, and a case where there was peeling or chipping was indicated as “X”.

(Heat-resistant)
The semiconductor wafer substrate of the substrate laminate subjected to the grindability evaluation was subjected to plasma CVD treatment at 200 ° C. for 10 minutes under vacuum conditions. After that, the adhesive sticks out at the edge of the substrate laminate, or the presence or absence of an unadhered part between the wafer substrate and the adhesive laminate, is evaluated as `` ○ '' The thing with an unbonded part was made into "x".

Further, the substrate laminate subjected to the plasma CVD treatment was baked in an oven for 10 minutes under a N ₂ atmosphere at 260 ° C. After that, the adhesive sticks out at the edge of the substrate laminate, or the presence or absence of an unadhered part between the wafer substrate and the adhesive laminate, is evaluated as `` ○ '' The thing with an unbonded part was made into "x".

(Laser separation)
The substrate laminate subjected to the heat resistance evaluation was irradiated with a laser beam having a wavelength of 532 nm to evaluate the separation between the support plate and the semiconductor wafer substrate. If the support plate and the substrate could be separated by laser irradiation, “◯” was given, and if the separation was not possible, “x” was given.

(Cleanability)
The wafer substrate of the substrate laminate subjected to laser separation evaluation was subjected to spin cleaning using p-menthane as a cleaning liquid. Then, the presence or absence of the residue of an adhesive agent or a separated layer was evaluated, the thing without a residue was set as "(circle)", and the thing with a residue was set as "x".

(result)
Table 4 below shows the evaluation results of stickability, grindability, heat resistance, laser separability, and cleanability in the substrate laminates of Examples 1 to 14 and Comparative Examples 1 to 3.

  As shown in Table 4, in the substrate laminate using the adhesive laminates of Examples 1 to 14, the wafer substrate can be obtained even if the substrate is subjected to a desired process such as a thinning process, a CVD process, or a heating process. There was no peeling. Moreover, the substrate and the support plate could be suitably separated by irradiating the laser in the separation step. Furthermore, by using p-menthane, which is a hydrocarbon solvent, in the cleaning step, the substrate could be cleaned without leaving an adhesive and separation layer residue.

  On the other hand, in the board | substrate laminated body using the adhesive laminated body of the comparative example 1 which is not provided with the 1st adhesive bond layer, the wafer board | substrate could not fully be affixed on a support plate. Moreover, in the board | substrate laminated body using the adhesive laminated body of the comparative example 2 which mix | blended the adhesive composition in the separated layer, the residue of an adhesive agent and a separated layer remains in evaluation of cleaning property, and it becomes an inadequate result. It was. Moreover, in the board | substrate laminated body using the adhesive laminated body of the comparative example 3 which does not use a nanoparticle for a separated layer, peeling generate | occur | produced in the perimeter of the edge part of a board | substrate laminated body in grindability evaluation.

  From the above results, if a substrate laminate is produced using the adhesive laminate according to the present invention, it is possible to suitably prevent the substrate from being peeled off from the support plate when a desired treatment is performed on the substrate. confirmed. It was also confirmed that the wafer substrate separated by laser irradiation can be suitably cleaned without leaving a residue such as an adhesive.

  The present invention can be widely used, for example, in a manufacturing process of a miniaturized semiconductor device.

DESCRIPTION OF SYMBOLS 1 First adhesive layer 2 Separation layer 3 Second adhesive layer 10 Adhesive laminate 20 Substrate 30 Support plate 50 Substrate laminate

Claims (15)

A first adhesive layer comprising a first thermoplastic resin;
A separation layer containing nanoparticles and altered by light irradiation;
An adhesive laminate, wherein a second adhesive layer containing a second thermoplastic resin is laminated in this order.   The adhesive laminate according to claim 1, wherein the nanoparticles are a metal, a metal oxide, carbon, or an organic pigment.   The adhesive laminate according to claim 1 or 2, wherein the nanoparticles have an average particle diameter in the range of 5 nm or more and 100 nm or less.   The adhesive laminate according to any one of claims 1 to 3, wherein a thickness of the separation layer is in a range of 0.3 µm to 20 µm.   The adhesive laminate according to any one of claims 1 to 4, wherein the first adhesive layer and the second adhesive layer have the same composition.   The adhesive laminate according to any one of claims 1 to 5, wherein the first thermoplastic resin and the second thermoplastic resin are elastomers.   The adhesive laminate according to claim 6, wherein the elastomer is a triblock resin or a water-added styrene elastomer.   The film thickness of the first adhesive layer is in the range of 0.5 μm or more and 50 μm or less, and the film thickness of the second adhesive layer is in the range of 10 μm or more and 200 μm or less. The adhesive laminate according to any one of claims 1 to 7.   An adhesive film comprising the adhesive laminate according to any one of claims 1 to 8 on a film. A method for producing the adhesive film according to claim 9,
A first adhesive layer laminating step of laminating the first adhesive layer containing the first thermoplastic resin;
A separation layer laminating step of laminating the separation layer containing the nanoparticles;
A second adhesive layer laminating step of laminating the second adhesive layer containing the second thermoplastic resin;
Including
A method for producing an adhesive film, comprising: laminating the first adhesive layer, the separation layer, and the second adhesive layer in this order on the film. An adhesion method for adhering a substrate and a support that transmits light,
A first adhesion step of adhering the support to the first adhesive layer of the adhesive laminate according to any one of claims 1 to 8,
A second bonding step of bonding the substrate to the second adhesive layer of the adhesive laminate;
A bonding method characterized by comprising: A method for separating a substrate and a support bonded by the bonding method according to claim 11,
A separation step of separating the support and the substrate by irradiating light to the separation layer of the adhesive laminate bonded with the support and the substrate through the support;
The separation method characterized by including.   The separation method according to claim 12, wherein in the separation step, the wavelength of the light applied to the separation layer through the support is in the range of visible light. A method for cleaning a substrate separated from a support by the separation method according to claim 12 or 13,
A cleaning method comprising a cleaning step of cleaning the substrate with a hydrocarbon solvent after the separation step. A support that transmits light;
The adhesive laminate according to any one of claims 1 to 8,
A substrate laminate, wherein the substrate is laminated in this order.

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