JP2012166489A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which a support can be rapidly and easily peeled from a supported substrate with the support adhered thereto.SOLUTION: The laminate includes: the support having a plurality of through-holes formed in the thickness direction; the supported substrate supported by the support; and an adhesive layer provided between the support and the supported substrate and having at least three layers. In the adhesive layer, a resin (A) contained in a first adhesive layer contacting the supported substrate and a resin (B) contained in a second adhesive layer contacting the support each have a glass transition point of 80°C or lower, and a resin (C) contained in at least a third adhesive layer held between the first adhesive layer and the second adhesive layer has a glass transition point of 100°C or higher. The resin (C) has polar groups, and the resins (A) and (B) have no polar groups.

Description

  The present invention relates to a laminate in which a support and a supported body are bonded via a laminate.

  As mobile phones, digital AV devices, IC cards, etc. have become more sophisticated, the demand for higher integration of chips in packages has increased by reducing the size and thickness of semiconductor silicon chips (hereinafter referred to as chips). ing. In order to realize high integration of the chip 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 base of a chip is thinned 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 has to 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, the transport of the thinned semiconductor wafer can be automated.

  The wafer and the support plate are bonded together using an adhesive tape, a thermoplastic resin, an adhesive, or the like. After thinning the wafer to which the support plate is attached, the support plate is peeled from the substrate before dicing the wafer. For example, when the wafer and the support plate are bonded together using an adhesive, the adhesive is dissolved and the wafer is peeled off from the support plate.

  Conventionally, when the adhesive is dissolved and peeled off from the support plate, it took time to penetrate the solvent into the adhesive, dissolve the adhesive, etc., and as a result, it took a long time to peel the support plate from the wafer. Was. Also, when peeling the support plate from the thinned wafer, care must be taken not to damage the thinned wafer. A technique that takes such problems into consideration is described in Patent Document 1.

  In the technique described in Patent Document 1, in order to easily peel the support plate from the wafer, two adhesive layers having different dissolution rates are provided for bonding the wafer and the support plate.

  In recent years, in order to dissolve the adhesive easily and quickly, a perforated support plate having a plurality of through holes in the thickness direction is used to supply the solvent from the through holes and dissolve the adhesive. How to do is known.

JP 2010-109324 A (published on May 13, 2010)

  However, when the above-described support plate with holes is used, the resin forming the adhesive layer sinks into the holes of the support plate after the heat treatment process. In such a case, it is difficult to peel the support plate from the wafer. The technique described in Patent Document 1 does not sufficiently consider the resistance when the adhesive is exposed to a high temperature environment. Therefore, development of a laminate that can easily peel the support plate from the wafer in a short time is required.

  The present invention has been made in view of the above-described problems, and a purpose of the present invention is to provide a laminate capable of easily peeling the support from the supported substrate to which the support is attached in a short time. Is to provide.

  In order to solve the above-described problem, a laminate according to the present invention includes a support provided with a plurality of through holes in the thickness direction, a supported base supported by the support, and the support. And an adhesive layer having at least three layers provided between the supported substrate and included in the first adhesive layer in contact with the supported substrate among the adhesive layers. The resin (A) and the resin (B) contained in the second adhesive layer in contact with the support have a glass transition point of 80 ° C. or lower, and the first adhesive layer and the second adhesive layer The resin (C) contained in at least one third adhesive layer sandwiched between and has a glass transition point of 100 ° C. or higher, the resin (C) has a polar group, and the resin (A ) And the resin (B) are characterized by not having a polar group.

  Moreover, in the laminated body which concerns on this invention, it is more preferable that the glass transition point of the said resin (A) and the said resin (B) is 50 degreeC or more.

  Moreover, in the laminated body which concerns on this invention, it is more preferable that the glass transition point of the said resin (C) is 200 degrees C or less.

  Furthermore, in the laminated body which concerns on this invention, it is more preferable that the said resin (C) polymerizes the monomer composition containing an acryl-type monomer.

  In the laminate according to the present invention, the resin (A) and the resin (B) are more preferably formed by polymerizing a monomer composition containing a cycloolefin monomer.

  Furthermore, in the laminated body which concerns on this invention, it is more preferable that the said resin (A) and the said resin (B) consist of the same composition.

  According to this invention, the said support body can be easily peeled from the to-be-supported base material to which the support body was stuck in a short time.

[Laminated body according to the present invention]
The laminate according to the present invention includes a support provided with a plurality of through-holes in the thickness direction, a supported base supported by the support, and the support and the supported base. A resin (A) included in the first adhesive layer in contact with the substrate to be supported among the adhesive layers, and the support. The resin (B) contained in the second adhesive layer in contact with the glass has a glass transition point of 80 ° C. or lower, and at least one layer of the first adhesive layer sandwiched between the first adhesive layer and the second adhesive layer. The resin (C) contained in the adhesive layer 3 has a glass transition point of 100 ° C. or higher, the resin (C) has a polar group, and the resin (A) and the resin (B) are polar. It does not have to have a group. Thereby, even after passing through the heat treatment step, the support can be easily peeled off in a short time from the supported substrate to which the support is attached.

  If the laminated body which concerns on this invention is used as a laminated body which temporarily fixed the to-be-supported base material to the support body, a specific use will not be specifically limited. In the present embodiment, a laminated body in which a semiconductor wafer (supported substrate) is temporarily fixed to a support plate (support) used in a wafer handling system will be described as an example.

  The support plate is a substrate for bonding a semiconductor wafer (hereinafter referred to as a wafer) to the wafer and protecting the wafer thinned by grinding so that cracks and warpage do not occur. Further, the support plate used in the present embodiment is provided with a plurality of through holes in the thickness direction, and these through holes are holes for supplying a stripping solution when the support plate is peeled from the wafer.

(Adhesive layer)
The laminate according to the present invention includes a first adhesive layer containing a resin (A), a second adhesive layer containing a resin (B), and at least one third adhesive layer containing a resin (C). Are stacked. The first adhesive layer is provided on the wafer side, the second adhesive layer is provided on the support plate side, and the third adhesive layer is sandwiched between the first adhesive layer and the second adhesive layer. ing. Since the glass transition points of the resins (A) and (B) included in these adhesive layers and the glass transition point of the resin (C) are significantly different from each other, the resin (A), (B) and the resin (C ), The adhesive layer can have both heat resistance and chemical resistance.

  In the present embodiment, the structure in which the laminated body is composed of three layers will be described as an example. However, the present invention is not limited to this, and the resin (A) is formed on the adhesive layer in contact with the wafer. If the resin (B) is contained in the adhesive layer in contact with the support plate and the resin (C) is contained in at least one adhesive layer sandwiched between these adhesive layers, a multilayer of four or more layers It may be a structure. In this case, the glass transition point of the resin contained in the additional layer is not particularly limited, but is more preferably 50 ° C. or higher and 200 ° C. or lower.

  The thickness of each adhesive layer may be appropriately selected according to the thickness of the laminated body. For example, the thickness of the first adhesive layer is 10 to 120 μm, and the thickness of the second adhesive layer is 10 It is preferable that the thickness of the third adhesive layer is 10 to 30 μm. That is, the thickness of the entire adhesive layer is preferably in the range of 30 to 200 μm. When the thickness of the adhesive layer is within the above range, the wafer and the support plate can be suitably attached.

  In the present specification, “resin having a polar group” refers to a resin having at least one carboxyl group or hydroxyl group in the side chain.

(Resin (A))
The resin (A) contained in the first adhesive layer is a resin having a glass transition point of 80 ° C. or lower and does not have a polar group, and preferably has a glass transition point of 50 ° C. or higher and 80 ° C. or lower. Resin. When the glass transition point of the resin (A) is within such a range, the adhesive layer can be increased in film thickness, and the resistance to chemicals can be improved.

  The resin (A) may be a resin having a glass transition point within the above range, but is preferably a resin having no polar group. As such a resin, for example, a resin obtained by polymerizing a monomer composition containing a cycloolefin monomer can be used. 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 include bicyclics such as norbornene and norbornadiene, tricyclics such as cyclopentadiene and dihydroxypentadiene, tetracyclics such as tetracyclododecene, pentacyclics such as cyclopentadiene trimer, tetra Heterocycles such as cyclopentadiene, as well as alkyl (methyl, ethyl, propyl, butyl, etc.), alkenyl (vinyl, etc.), alkylidene (ethylidene, etc.), aryl (phenyl, tolyl, Naphthyl and the like) and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene represented by the following formula (1), or alkyl substituted products thereof are preferable.

(In Formula (1), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1)
In addition, a cycloolefin monomer may use only 1 type and may use it in combination of 2 or more type.

  The monomer composition constituting the resin (A) may contain other monomers copolymerizable with the cycloolefin monomer in addition to the cycloolefin monomer. Examples of other monomers include alkene monomers represented by the following formula (2).

(In Formula (2), R < ₃ > -R < ₆ > is a hydrogen atom or a C1-C4 alkyl group each independently)
The alkene monomer may be linear or branched. Examples of the alkene monomer include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. Only one alkene monomer may be used, or two or more alkene monomers may be used in combination.

  When the monomer composition constituting the resin (A) contains a monomer other than the cycloolefin monomer, the content of the cycloolefin monomer is preferably 15% by weight or more of the entire monomer composition, More preferably, it is 20% by weight or more. When the content of the cycloolefin monomer is 10% by weight or more of the entire monomer composition, softening of the adhesive layer in a high temperature environment can be suitably prevented.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be appropriately selected according to a conventionally known method. The resin (A) may be a commercially available resin. For example, “TOPAS” (trade name) manufactured by Polyplastics, “APEL” manufactured by Mitsui Chemicals, and “ZEONOR” manufactured by Nippon Zeon Co., Ltd. Or “ZEONEX”, “ARTON” manufactured by JSR Corporation, and the like.

  The weight average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene) of the resin (A) is 30,000 to 300,000, more preferably 50,000 to 200,000. If the weight average molecular weight of the resin (A) is within the above range, the degassing amount can be reduced.

(Resin (B))
The resin (B) contained in the second adhesive layer is a resin having a glass transition point of 80 ° C. or lower and does not have a polar group, and preferably has a glass transition point of 50 ° C. or higher and 80 ° C. or lower. Resin. When the glass transition point of the resin (B) is within such a range, it is possible to increase the thickness of the adhesive layer and improve resistance to chemicals.

  The resin (B) may be a resin having a glass transition point within the above range, but is preferably a resin having no polar group. As such a resin, for example, a resin obtained by polymerizing a monomer composition containing a cycloolefin monomer can be used. As the cycloolefin monomer, those exemplified in the description of the resin (A) can be used.

  The monomer composition constituting the resin (B) may contain other monomers copolymerizable with the cycloolefin monomer in addition to the cycloolefin monomer. As another monomer, the monomer illustrated in description of the said resin (A) can be used.

  When the monomer composition constituting the resin (B) contains a monomer other than the cycloolefin monomer, the content of the cycloolefin monomer is preferably 15% by weight or more of the entire monomer composition, More preferably, it is 20% by weight or more. When the content of the cycloolefin monomer is 10% by weight or more of the entire monomer composition, softening of the adhesive layer in a high temperature environment can be suitably prevented.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be appropriately selected according to a conventionally known method. The resin (B) may be the above-described commercially available resin.

  The weight average molecular weight (Mw) of the resin (B) is 30,000 to 300,000, more preferably 50,000 to 200,000. When the weight average molecular weight of the resin (B) is within the above range, the degassing amount can be reduced.

  In addition, it is more preferable that resin (B) consists of the same composition as resin (A) from the point that handling is easy.

(Resin (C))
The resin (C) contained in the third adhesive layer may be a resin having a glass transition point of 100 ° C. or higher, more preferably a resin having a glass transition point of 100 ° C. or higher and 200 ° C. or lower and having a polar group. It is. If the glass transition point of the resin (C) is within such a range, it is possible to prevent softening of the adhesive layer even if the laminate is exposed to a high temperature environment, and to prevent sinking into the holes formed in the support plate. Can do.

  Further, the ratio of the polar group contained in the resin (C) is more preferably 1 mol% to 10 mol%. If it has a polar group in the ratio within the above range, the amount of degassing can be suppressed.

  Examples of the monomer constituting such a resin include a polar group-containing acrylic monomer or a polar group-containing styrene monomer, and examples of the polar group-containing acrylic monomer include (meth) acrylic acid, carboxymethyl (meth) acrylate, carboxyethyl (meth) ) Acrylate, hydroxyethyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, and the like. Examples of the polar group-containing styrene monomer include hydroxystyrene, dihydroxystyrene, and vinyl benzoic acid. These monomers may be used alone or in combination of two or more.

  The monomer composition constituting the resin (C) may contain other monomers such as styrene or maleimide monomers in addition to the acrylic monomer.

  Examples of other monomers include methyl acrylate, methacrylic acid, methyl methacrylate, N, N-dimethylacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-dimethylaminopropylacrylamide, N-methylacrylamide, Diacetone acrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-isobutylmaleimide, N-sec-butyl Maleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stere Aliphatic hydrocarbon groups such as maleimide having an alkyl group such as rilmaleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide And an aromatic maleimide having an aryl group such as N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np-methylphenylmaleimide.

  When the monomer composition constituting the resin (C) contains a monomer other than the acrylic monomer, the content of the acrylic monomer is preferably 30% by weight or more of the entire monomer composition, More preferably, it is 40% by weight or more. When the content of the acrylic monomer is 20% by weight or more of the entire monomer composition, a laminate can be formed without cracks.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be appropriately selected according to a conventionally known method.

  The weight average molecular weight (Mw) of the resin (C) is 50,000 to 400,000, more preferably 80,000 to 200,000. When the weight average molecular weight of the resin (C) is within the above range, both heat resistance and crack resistance can be achieved.

(Other ingredients)
The first adhesive layer, the second adhesive layer, and the third adhesive layer may further contain other miscible materials as long as the essential characteristics of the present invention are not impaired. For example, various commonly used additives such as an additional resin for improving the performance of the adhesive, a plasticizer, an adhesion aid, a stabilizer, a colorant, and a surfactant may be further used.

[Method for producing laminate]
The laminate according to the present invention can be produced, for example, by the following method.

  First, a first adhesive layer containing a resin (A) is formed on a wafer, and then a third adhesive layer containing a resin (C) is formed on the first adhesive layer. The laminated body of the present invention is obtained by forming a second adhesive layer containing the resin (B) on the adhesive layer and adhering the support plate. Moreover, after forming the 2nd contact bonding layer containing resin (B) on a support plate and then forming the 3rd contact bonding layer containing resin (C) on the 2nd contact bonding layer, resin (A The first adhesive layer may be bonded to the wafer, or the first adhesive layer may be previously formed on the wafer, and the second adhesive layer may be formed on the support plate. An adhesive layer may be formed, a third adhesive layer may be formed on either the first adhesive layer or the second adhesive layer, and these may be bonded together.

(Preparation of adhesive)
First, the following seven types of adhesives were prepared.

(Adhesive 1)
A cycloolefin copolymer obtained by copolymerization of norbornene and ethylene with a metallocene catalyst (“TOPAS (trade name) 8007” manufactured by Polyplastics, norbornene: ethylene = 35: 65 (weight ratio), glass transition point: 70 ° C., Mw : 98,200, thermal decomposition temperature: 459 ° C.) and dissolved in p-menthane to obtain an adhesive 1 having a solid content concentration of 25% by weight.

(Adhesive 2)
Cycloolefin copolymer obtained by copolymerization of cyclododecene and ethylene (“APL (trade name) 8008T” manufactured by Mitsui Chemicals, Ltd., cyclododecene: ethylene = 80: 20 (weight ratio)), glass transition point: 65 ° C., Mw: 100200, thermal decomposition Temperature: 446 ° C.) and dissolved in p-menthane to obtain an adhesive 2 having a solid concentration of 25% by weight.

(Adhesive 3)
Using cyclohexylmaleimide, styrene, methyl methacrylate, acrylic acid, dimethylol-tricyclodecane diacrylate in 18: 32: 40: 10: 0.7 (molar ratio), dissolved in PGMEA, solid content concentration 30 wt. % Adhesive 3 was obtained. The obtained adhesive 3 had a glass transition point: 124 ° C., Mw: 153000, and a thermal decomposition temperature: 319 ° C.

(Adhesive 4)
Using cyclohexylmaleimide, styrene, methyl methacrylate, acrylic acid, dimethylol-tricyclodecane diacrylate at 18: 32: 40: 1: 0.7 (molar ratio), dissolved in PGMEA, solid content concentration 30 wt. % Adhesive 4 was obtained. The obtained adhesive 4 had a glass transition point: 125 ° C., Mw: 163,000, and a thermal decomposition temperature: 322 ° C.

(Adhesive 5)
Using cyclohexylmaleimide, phenylmaleimide, styrene, methyl methacrylate, acrylic acid, dimethylol-tricyclodecane diacrylate in 20: 20: 10: 40: 10: 0.7 (molar ratio), dissolved in PGMEA, An adhesive 5 having a solid content concentration of 30% by weight was obtained. The obtained adhesive 5 had a glass transition point: 159 ° C., Mw: 179,000, and thermal decomposition temperature: 335 ° C.

(Adhesive 6)
A random copolymer resin containing styrene, methyl methacrylate, isobornyl methacrylate, n-butyl acrylate, and acrylic acid in a molar ratio of 52: 15: 10: 13: 10 was dissolved in PGMEA and solid. An adhesive 6 having a partial concentration of 40% by weight was obtained. The obtained adhesive 6 had a glass transition point: 65 ° C., Mw: 82,000, and a thermal decomposition temperature: 258 ° C.

(Adhesive 7)
A cycloolefin copolymer obtained by copolymerizing norbornene and ethylene with a metallocene catalyst (“TOPAS (trade name) 5013” manufactured by Polyplastics Co., Ltd., norbornene: ethylene = 40: 60 (weight ratio), glass transition point: 126 ° C., Mw : 85,100, thermal decomposition temperature: 463 ° C.) and dissolved in p-menthane to obtain an adhesive 7 having a solid content concentration of 25% by weight.

<Examples 1-7>
In Examples 1-7, the laminated body was produced by the combination shown in the following Table 1. Specifically, an adhesive containing a resin having a glass transition point of 80 ° C. or lower is used for the first layer (first adhesive layer) and the third layer (second adhesive layer). 3), an adhesive containing a resin having a glass transition point of 100 ° C. or higher was used.

(Production of laminate)
In Examples 1-7, the laminated body was produced as follows.

First, an adhesive serving as a first layer was applied to a silicon substrate (wafer), and baked at 110 ° C., 170 ° C., and 220 ° C. for 5 minutes each to form a first layer having a thickness of 50 μm. Next, an adhesive to be the second layer was applied on the formed first layer, and baked at 110 ° C., 170 ° C., and 220 ° C. for 3 minutes each to form a second layer having a thickness of 15 μm. Finally, an adhesive to be a third layer was applied on the formed second layer, and baked at 110 ° C., 170 ° C., and 220 ° C. for 5 minutes each to form a third layer having a thickness of 35 μm. Thereafter, a perforated support plate was affixed on the third layer at 170 ° C. and a pressure of 0.21 kg / cm ² to obtain laminates of Examples 1 to 7.

[Evaluation of adhesive layer]
The laminates of Examples 1 to 7 were evaluated by the following test items.

(Evaluation of heat resistance)
The heat resistance was evaluated by the amount of sinking of the adhesive layer after heating at 220 ° C. for 1 hour. As a method for evaluating the sinking, a method of measuring the thickness of the adhesive layer before and after heating was used. As a result, in all the laminated bodies of Examples 1 to 7, the difference between the thickness before heating and the thickness after heating was 10 μm or less, and the amount of subsidence was extremely small, and the evaluation of subsidence was good. .

(Evaluation of chemical resistance)
For chemical resistance, the laminates of Examples 1 to 7 were prepared using H ₂ O, IPA (Isopropyl alcohol), PGMEA (Propylene Glycol Monomethyl Ether Acetate), TMAH (Tetra methylammonium hydroxide) (2.38 mass% aqueous solution), NaOH ( It was evaluated by immersing in 1 mass% aqueous solution) and HF (hydrogen fluoride) (1 mass% aqueous solution) and observing the dissolved state after 10 minutes. As a result, all the laminates of Examples 1 to 7 did not dissolve in the above-mentioned solvent and had resistance.

(Evaluation of crack resistance)
After forming the adhesive layer on the wafer, the presence or absence of cracks in the adhesive layer was visually observed. As a result, no crack was observed in all the laminates of Examples 1 to 7, and the crack resistance was good.

(Evaluation of peelability)
After heating the laminate at 220 ° C., it was immersed in p-menthane and sonicated to evaluate the peelability. In all laminates of Examples 1 to 7, the support plate was peeled from the wafer. Well done.

  In order to clean the silicon substrate, the second layer was dissolved by immersing in NMP (N-methylpyrrolidone), and finally the first layer was dissolved by immersing in p-menthane. When the cleaned silicon substrate was observed with a microscope, it was confirmed that there was no residue.

(Evaluation of degassing amount)
The degassing amount was evaluated by measuring the degassing amount from the adhesive layer after forming the adhesive layer on the wafer. A TDS (Thermal Desorption Spectroscopy) apparatus was used for measuring the degassing amount.

  As a result, all the laminates of Examples 1 to 7 had a good value of less than 100,000 in strength (Indensity) required by the TDS measuring apparatus at 220 ° C.

(Evaluation of adhesive strength)
Regarding the adhesive strength, after an adhesive layer was formed on the wafer, a glass substrate was adhered on the adhesive layer at 200 ° C. under a load of 1 kg. The glass substrate was pulled, and the adhesive strength when the glass substrate was peeled from the wafer was calculated using a vertical electric measurement stand MX-500N (manufactured by Imada Co., Ltd.). The glass substrate was adhered to the adhesive layer at 200 ° C. and a load of 1 kg.

As a result, in all the laminates of Examples 1 to 7, it was confirmed that the adhesive strength required by the measuring device was sufficient strength of 1 kgf / cm ² or more.

<Comparative Examples 1-3>
In Comparative Examples 1 to 3, laminates were produced with combinations shown in Table 2 below.

In Comparative Example 1, an adhesive was applied to a silicon substrate and baked at 110 ° C., 170 ° C., and 220 ° C. for 5 minutes each to form a single-layer 100 μm thick adhesive layer. Thereafter, a perforated support plate was affixed on the adhesive layer at 170 ° C. and a pressure of 0.21 kg / cm ² to obtain a laminate of Comparative Example 1.

  In Comparative Examples 2 and 3, laminates composed of three layers were produced in the same manner as the laminates of Examples 1 to 7.

[Evaluation of adhesive layer]
The laminates of Comparative Examples 1 to 3 were evaluated according to the following test items. In addition, evaluation of each test item was performed according to the procedure similar to an Example.

(Evaluation of heat resistance)
The amount of subsidence in the laminate of each comparative example was 48 μm in Comparative Example 1, 10 μm or less in Comparative Example 2, and 45 μm in Comparative Example 3. Thus, in Comparative Examples 1 and 3 using only a resin having a low glass transition point, the heat resistance was low.

(Evaluation of chemical resistance)
No change was observed in the laminates of Comparative Examples 1 and 3 using only a resin having a low glass transition point, but the laminate of Comparative Example 2 using only a resin having a high glass transition point was immersed in IPA and PGMEA. As a result, cracks occurred.

(Evaluation of peelability)
In the laminates of Comparative Examples 1 and 2, it took three times or more time of Examples 1 to 7 when peeling the support plate from the wafer. Further, in the laminate of Comparative Example 3, mixing occurred in the adhesive layer, and the support plate could not be peeled from the wafer.

(Evaluation of degassing amount)
As a result of measuring the degassing amount, the laminates of Comparative Examples 1 to 3 had an intensity (Indensity) of less than 100,000 determined by the TDS measuring apparatus at 220 ° C.

(Evaluation of adhesive strength)
The adhesive strength of the laminates of Comparative Examples 1 to 3 was 1 kgf / cm ² or more.

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

  Since the laminate according to the present invention can be easily peeled off in a short time, it can be suitably used for processing a semiconductor wafer or the like.

Claims (6)

A support provided with a plurality of through holes in the thickness direction;
A supported substrate supported by the support;
An adhesive layer having at least three layers provided between the support and the substrate to be supported;
Among the adhesive layers, the resin (A) contained in the first adhesive layer in contact with the supported substrate, and the resin (B) contained in the second adhesive layer in contact with the support, The glass transition point is 80 ° C. or lower, and the resin (C) contained in at least one third adhesive layer sandwiched between the first adhesive layer and the second adhesive layer has a glass transition point of 100. ℃ or more,
The resin (C) has a polar group, and the resin (A) and the resin (B) do not have a polar group.   The laminated body according to claim 1, wherein the glass transition point of the resin (A) and the resin (B) is 50 ° C or higher.   The laminated body according to claim 1 or 2, wherein the resin (C) has a glass transition point of 200 ° C or lower.   The said resin (C) superposes | polymerizes the monomer composition containing an acryl-type monomer, The laminated body of any one of Claims 1-3 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 4, wherein the resin (A) and the resin (B) are obtained by polymerizing a monomer composition containing a cycloolefin monomer.   The laminate according to any one of claims 1 to 5, wherein the resin (A) and the resin (B) have the same composition.