WO2014157306A1

WO2014157306A1 - Temporary adhesive for producing semiconductor device, adhesive support including same, and process for producing semiconductor device

Info

Publication number: WO2014157306A1
Application number: PCT/JP2014/058458
Authority: WO
Inventors: 悠岩井; 一郎小山; 藤牧　一広
Original assignee: 富士フイルム株式会社
Priority date: 2013-03-28
Filing date: 2014-03-26
Publication date: 2014-10-02
Also published as: TW201444938A; JP2014189731A

Abstract

A temporary adhesive for producing a semiconductor device is provided with which it is possible to diminish even at high temperatures the problem wherein, when a member to be treated (e.g., a semiconductor wafer) is mechanically or chemically treated while being temporarily supported by a temporary adhesive, the temporary adhesive evolves a gas and it is also possible to easily remove the temporary support of the treated member without damaging the treated member, even after high-temperature processing. The temporary adhesive for producing a semiconductor device comprises (A) a radical-polymerizable monomer having a functionality of 2 or less, (B) a radical-polymerizable monomer having a functionality of 3 or greater, (C) a polymer, and (D) a free-radical polymerization initiator.

Description

Temporary adhesive for manufacturing semiconductor device, adhesive support using the same, and method for manufacturing semiconductor device

The present invention relates to a temporary adhesive for producing a semiconductor device, and an adhesive support using the same. The present invention also relates to a method of manufacturing a semiconductor device using a temporary adhesive for manufacturing a semiconductor device.

Conventionally, in the process of manufacturing semiconductor devices such as ICs and LSIs, usually, a large number of IC chips are formed on a semiconductor silicon wafer and separated into pieces by dicing.
With the need for further miniaturization and higher performance of electronic devices, there is a demand for further miniaturization and higher integration of IC chips mounted on electronic devices. High integration is nearing its limit.

Although a wire bonding method has conventionally been widely known as an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a silicon substrate has recently been used to achieve miniaturization of the IC chip. There is known a method (so-called method of forming a silicon through electrode (TSV)) in which a through hole is provided and a metal plug as an external terminal is connected to an integrated circuit so as to penetrate the through hole. However, the method of forming the through silicon via alone can not sufficiently meet the above-mentioned recent need for higher integration of the IC chip.

In view of the above, there is known a technique for improving the degree of integration per unit area of a silicon substrate by forming integrated circuits in an IC chip in multiple layers. However, in order to increase the thickness of an IC chip, it is necessary to reduce the thickness of members constituting the IC chip. As thinning of such members, for example, thinning of the silicon substrate has been considered, which leads not only to miniaturization of the IC chip but also saves labor in the process of manufacturing the through hole of the silicon substrate in the manufacture of silicon through electrodes. It is considered promising because it can be done.

A semiconductor silicon wafer having a thickness of about 700 to 900 μm is widely known as a semiconductor silicon wafer used in a process of manufacturing a semiconductor device. It has been attempted to reduce the thickness to 200 .mu.m or less.
However, since semiconductor silicon wafers having a thickness of 200 μm or less are very thin and, consequently, members for manufacturing semiconductor devices based on them are also very thin, such members may be further processed or In the case of simply moving such a member, it is difficult to support the member stably and without damage.

In order to solve the above-mentioned problems, a semiconductor wafer before thinning on which a device is provided on the surface and a processing supporting substrate are temporarily bonded with a silicone adhesive, and the back surface of the semiconductor wafer is ground and thinned There is known a technique in which a semiconductor wafer is perforated to form a silicon through electrode, and thereafter, a processing support substrate is detached from the semiconductor wafer (see Patent Document 1). According to this technology, resistance to grinding during backside grinding of semiconductor wafers, heat resistance in anisotropic dry etching processes, etc., chemical resistance during plating and etching, and smooth peeling from the final support substrate for processing It is said that it is possible to simultaneously achieve low adherend contamination.

A method of supporting a wafer is a method of supporting a wafer by a support layer system, in which a plasma polymer layer obtained by a plasma deposition method is interposed as a separation layer between the wafer and the support layer system. The adhesive bond between the support layer system and the release layer is made greater than the bond bond between the wafer and the release layer, and the wafer is easily released from the release layer when the wafer is released from the support layer system. There is also known a technology configured to separate (see Patent Document 2).

Moreover, temporary adhesion is performed using a polyether sulfone and a tackifier, and the technique which cancels | releases temporary adhesion by heating is known (refer patent document 3).
Moreover, temporary adhesion is performed with the mixture which consists of carboxylic acids and amines, and the technique which cancels | releases temporary adhesion by heating is also known (refer patent document 4).
Also, with the bonding layer made of cellulose polymers etc. heated, the device wafer and the support substrate are adhered by pressure bonding to bond them, and the device wafer is detached from the support substrate by heating and sliding in the lateral direction. Technology is known (see Patent Document 5).

Further, a pressure-sensitive adhesive film is known which is composed of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and whose adhesive force is changed by irradiation of radiation (see Patent Document 6).
Further, the supporting substrate and the semiconductor wafer are temporarily bonded with an adhesive made of polycarbonates, and the semiconductor wafer is treated, then irradiated with irradiation radiation, and then heated to thereby process the treated semiconductor wafer. There is known a technique for detaching the support substrate from the support substrate (Patent Document 7).

Further, it is formed from a pressure-sensitive adhesive composition comprising an energy ray-curable copolymer having an energy ray-polymerizable unsaturated group in a side chain, an epoxy resin, and a heat-activated latent epoxy resin curing agent. There is known a pressure-sensitive adhesive tape which is made of a pressure-sensitive adhesive layer and whose adhesive force is changed by irradiation of radiation (see Patent Document 8).

JP, 2011-119427, A Japanese Patent Publication 2009-528688 JP, 2011-225814, A JP, 2011-052142, A Japanese Patent Publication No. 2010-506406 JP, 2007-045939, A U.S. Patent Publication No. 2011/0318938 Specification JP-A-8-53655

By the way, the surface of the semiconductor wafer on which the device is provided (that is, the device surface of the device wafer) and the supporting substrate (carrier substrate) are temporarily adhered via a layer made of an adhesive known in Patent Document 1 and the like. In some cases, the adhesive layer is required to have a certain degree of adhesion in order to stably support the semiconductor wafer.
Therefore, in the case where the entire surface of the device surface of the semiconductor wafer and the supporting substrate are temporarily bonded via the adhesive layer, the temporary bonding between the semiconductor wafer and the supporting substrate is made sufficient, and the semiconductor wafer is stabilized stably. On the other hand, the temporary adhesion between the semiconductor wafer and the support substrate is too strong to support the substrate without damaging it, so that the device may be damaged when the semiconductor wafer is detached from the support substrate, or from the semiconductor wafer It is easy for the problem that the device is detached.

In addition, as in Patent Document 2, in order to prevent the adhesion between the wafer and the support layer system from becoming too strong, the plasma polymer layer as the separation layer is interposed between the wafer and the support layer system by plasma deposition. The formation method is (1) usually, the equipment cost for carrying out plasma deposition is large; (2) layer formation by plasma deposition requires time for vacuuming in the plasma apparatus and deposition of monomers; (3) Even when a separation layer comprising a plasma polymer layer is provided, when supporting a wafer to be processed, the support of the wafer is released while securing sufficient adhesive bonding between the wafer and the separation layer. In such cases, it is not easy to control an adhesive bond such that the wafer is easily detached from the separation layer;

Further, as described in

Patent Documents

3, 4 and 5, in the method of releasing the temporary adhesion by heating, there is a tendency that the device is broken when the semiconductor wafer is detached.

Further, as described in Patent Documents 6, 7 and 8, in the method of releasing the temporary bonding by irradiating the radiation, it is necessary to use a supporting substrate which transmits the radiation.

The present invention has been made in view of the above background, and an object thereof is to temporarily support a processing member by high adhesion when the processing member (such as a semiconductor wafer) is subjected to mechanical or chemical processing. Semiconductor device manufacturing capable of easily releasing temporary support (with high removability) to a treated member without damaging the treated member even after passing through a process at vacuum and high temperature. It is an object of the present invention to provide a temporary adhesive, an adhesive support using the same, and a method of manufacturing a semiconductor device.

The present inventors have intensively studied to solve the above problems, and as a result, (A) a difunctional or lower radically polymerizable monomer, (B) a trifunctional or higher radically polymerizable monomer, (C) a polymer compound and (D) ) When an adhesive composition containing a radical polymerization initiator is used as a temporary adhesive in the temporary bonding step between the semiconductor wafer and the support substrate, it is possible to temporarily support the processing member with high adhesive strength, and It has been found that the support can be easily released, and the present invention has been completed.
Without being bound by any theory, in the temporary adhesive of the present invention, the polymerizable group of the radically polymerizable monomer achieves high adhesion. Here, in the present invention, by blending a bifunctional or less radically polymerizable monomer and a trifunctional or more radically polymerizable monomer, the bifunctional or less radically polymerizable monomer acts as a diluent and the trifunctional or more monomer is I have increased mobility. By adopting such a configuration, the polymerization of the polymerizable monomer present in the region irradiated with light proceeds, and the polymerizable group tends to disappear. Therefore, by partially irradiating the adhesive layer with light, it is possible to effectively form a high adhesive site and a low adhesive site in the adhesive layer. It has been found that an adhesive layer consisting of a part having high adhesiveness and a part having low adhesiveness has high shear adhesion and weak peel adhesion. Based on the above-mentioned view, it discovers that adhesion nature can form an adhesion layer which is easy to exfoliate, and came to complete the present invention.

Specifically, the above problems have been solved by the following means <1>, preferably by <2> to <17>.
<1> A temporary semiconductor device for manufacturing a semiconductor device, comprising: (A) a bifunctional or lower radically polymerizable monomer, (B) a trifunctional or higher radically polymerizable monomer, (C) a polymer compound, and (D) a radical polymerization initiator adhesive.
The temporary adhesive for semiconductor device manufacture as described in <1> whose <2> (A) bifunctional or less radically polymerizable monomer is a bifunctional radically polymerizable monomer.
<3> Of any two radically polymerizable groups in which at least one of (A) a bifunctional or lower radically polymerizable monomer and (B) a trifunctional or higher radically polymerizable monomer is contained in one molecule The temporary adhesive for manufacturing a semiconductor device according to <1> or <2>, wherein the number of atoms therebetween is 9 atoms or more.
<4> At least one of (A) bifunctional or lower radically polymerizable monomers and (B) trifunctional or higher radically polymerizable monomers has a polyoxyalkylene partial structure represented by the following general formula (1), < The temporary adhesive agent for semiconductor device manufacture as described in 1> or <2>.
General formula (1)

(In the general formula (1), R ²¹ represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
<5> (A) A bifunctional or lower radically polymerizable monomer according to any one of <1> to <3>, having a polyoxyalkylene partial structure represented by the following general formula (1) Temporary adhesive for semiconductor device manufacturing.
General formula (1)

(In the general formula (1), R ²¹ represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
The ratio (mass ratio) of the radically polymerizable monomer of <6> (A) bifunctional or less and the radically polymerizable monomer of (B) trifunctional or more is 80/20 to 20/80, <1> to <5 The temporary adhesive agent for semiconductor device manufacture in any one of>.
The <7> (A) bifunctional or less radically polymerizable monomer and / or the (B) trifunctional or higher radically polymerizable monomer is a (meth) acrylate monomer according to any one of <1> to <6> Temporary adhesive for semiconductor device manufacturing.
<8> An adhesive support comprising: a substrate; and an adhesive layer formed on the substrate by the temporary adhesive for producing a semiconductor device according to any one of <1> to <7>.
<9> bonding the first surface of the member to be treated and the substrate through the adhesive layer formed of the temporary adhesive for producing a semiconductor device according to any one of <1> to <7>,
Subjecting the second surface opposite to the first surface of the member to be treated mechanically or chemically to obtain a treated member;
A method of manufacturing a semiconductor device having the processed member, comprising the step of separating the adhesive layer and the processed member.
<10> The surface of the adhesive layer to be adhered to the first surface of the treated member before the step of adhering the first surface of the treated member to the substrate via the adhesive layer The method of manufacturing a semiconductor device according to <9>, further comprising the step of irradiating the actinic ray or radiation or heat.
<11> The method for producing a semiconductor device according to <10>, wherein the actinic ray or radiation is an actinic ray having a wavelength of 350 to 450 nm.
<12> After the step of bonding the first surface of the member to be treated and the substrate via the adhesive layer, and on the second surface of the member to be treated opposite to the first surface And the step of heating the adhesive layer at a temperature of 50 ° C. to 300 ° C. prior to the step of applying mechanical or chemical treatment to obtain a treated member <9> to <11> The manufacturing method of the semiconductor device in any one of these.
<13> The method of manufacturing a semiconductor device according to any one of <9> to <12>, wherein the step of separating the treated member from the adhesive layer includes the step of bringing a peeling liquid into contact with the adhesive layer. .
<14> The protective layer according to any one of <9> to <13>, further comprising a protective layer on the first surface of the member to be treated, between the member to be treated and the adhesive layer. Semiconductor device manufacturing method.
A <15> metal substrate, (A) a bifunctional or less radically polymerizable monomer, (B) a trifunctional or higher radically polymerizable monomer, (C) a polymer compound, and (D) a radical polymerization initiator Adhesive support having a solvent-free adhesive layer.
Adhesiveness containing <16> metal substrate, (A) bifunctional or less radically polymerizable monomer, (B) trifunctional or higher radically polymerizable monomer, (C) polymer compound and (D) radical polymerization initiator An adhesive support comprising a layer, wherein the adhesive layer has a region with a relatively high content of radical polymerizable monomers and a region with a relatively low content of radical polymerizable monomers.
Adhesiveness containing <17> metal substrate, (A) bifunctional or less radically polymerizable monomer, (B) trifunctional or higher radically polymerizable monomer, (C) polymer compound and (D) radical polymerization initiator It has a layer and the adhesive layer has a region in which the content of the radically polymerizable monomer is relatively large and a region in which the content of the radically polymerizable monomer is relatively small, and the content of the radically polymerizable monomer is contained An adhesive support comprising a region having a relatively large amount of the radical polymerizable monomer at least three times as large as a region having a relatively small content of the radical polymerizable monomer.

According to the present invention, when mechanical or chemical treatment is performed on a member to be treated, it is possible to temporarily support the member to be treated with high adhesive force, and to temporarily treat the treated member without damaging the treated member. It has become possible to provide a temporary adhesive for producing a semiconductor device, an adhesive support using the same, and a method for producing a semiconductor device, which can easily release the support.

FIGS. 1A, 1 B and 1 C are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer, a schematic plan view showing a device wafer temporarily bonded by an adhesive support, and bonding, respectively. It is a schematic sectional drawing which shows the state by which the device wafer temporarily bonded by the elastic support body was thinned. FIG. 2 is a schematic top view of an adhesive support in an embodiment of the present invention. FIG. 3 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 4 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 5 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 6 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 7 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 8 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 9 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 10 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 11 is a schematic top view of one aspect of an adhesive support in an embodiment of the present invention. FIG. 12 is a schematic top view of one aspect of the adhesive support in the embodiment of the present invention. FIG. 13 is a schematic cross-sectional view for explaining the release of the temporary adhesion state between the conventional adhesive support and the device wafer.

Hereinafter, embodiments of the present invention will be described in detail.
In the notations of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, "actinic radiation" or "radiation" is meant to include, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-rays and the like. Also, in the present invention, "light" means actinic rays or radiation.
In addition, unless otherwise specified, the "exposure" in the present specification means not only exposure by a mercury lamp, ultraviolet rays, far ultraviolet rays represented by an excimer laser, X-rays, EUV light, etc., but also electron beams and ion beams. It also means drawing by particle beam.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acrylic represents acrylic and methacrylic, and“ (meth) acryloyl ”represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous, and the monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the embodiment to be described below, the description of the members and the like described in the drawings already referred to will be simplified or omitted by attaching the same reference numerals or the corresponding reference numerals in the drawings.

The temporary adhesive for producing a semiconductor device of the present invention (hereinafter, also simply referred to as “temporary adhesive”) is (A) a difunctional or lower radically polymerizable monomer, (B) a trifunctional or higher radical polymerizable monomer, C) containing a polymer compound and (D) a radical polymerization initiator.
According to the temporary adhesive for manufacturing a semiconductor device of the present invention, when mechanical processing or chemical processing is performed on the processing member, the processing member can be temporarily supported with high adhesive force, and the processing member is damaged. As a result, a temporary adhesive for semiconductor device manufacture can be obtained which can release temporary support for the processed member.
It is preferable that the temporary adhesive for semiconductor device manufacture of this invention is for silicon penetration electrode formation. The formation of the through silicon via will be described in detail later.

Hereinafter, each component which the temporary adhesive for semiconductor device manufacture of this invention may contain is demonstrated in detail.

<Radical polymerizable monomer>
The temporary adhesive for producing a semiconductor device of the present invention has (A) a difunctional or lower difunctional radical polymerizable monomer and (B) a trifunctional or higher radical polymerizable monomer. Any radical polymerizable monomer may be used, and among the radical polymerizable monomers described below, (A) a difunctional or lower radical polymerizable monomer and (B) a trifunctional or higher radical polymerizable monomer Can be selected arbitrarily.
From the viewpoint of adhesiveness and releasability, the radically polymerizable monomer having (A) bifunctional or less is preferably a bifunctional radically polymerizable monomer. The (B) trifunctional or higher radically polymerizable monomer is preferably tetrafunctional or higher. The upper limit of the number of functional groups of the radically polymerizable monomer having three or more functions (B) is not particularly limited, but may be, for example, eight or less, or even six or less. In the present invention, a combination of (A) a difunctional radical polymerizable monomer and (B) a tetrafunctional or higher radical polymerizable monomer is particularly preferable.
The radically polymerizable monomers used in the present invention may be used singly or in combination of two or more of the radically polymerizable monomers having (A) bifunctional or less functionality and the (B) trifunctional or more radical polymerizable monomers. You may use together.

The radically polymerizable monomer has a radically polymerizable group. The functional group number of the radically polymerizable monomer in the present invention means the number of radically polymerizable groups in one molecule. A radically polymerizable group is a group which can be polymerized typically by irradiation with an actinic ray or radiation, or by the action of a radical.
The radical polymerizable monomer is a compound different from the binder. The polymerizable monomer is typically a low molecular weight compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1500 or less, and a low molecular weight compound having a molecular weight of 900 or less. It is further preferred that The molecular weight is usually 100 or more.

The polymerizable group is preferably, for example, a functional group capable of undergoing an addition polymerization reaction, and examples of the functional group capable of undergoing an addition polymerization reaction include an ethylenically unsaturated bonding group. As the ethylenically unsaturated bonding group, a styryl group, a (meth) acryloyl group and an allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radically polymerizable monomer used in the present invention is preferably a (meth) acrylate monomer, and more preferably an acrylate monomer.

The radically polymerizable monomer may be, for example, any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and multimers thereof.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, etc. And multimers thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group etc. with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or multifunctional Dehydration condensation products with functional carboxylic acids and the like are also suitably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogen groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced.

Specific examples of the ester monomer of polyhydric alcohol compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate and tetramethylene glycol diacrylate as acrylic acid ester. Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetramer Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanurate ethylene oxide (EO) modified tri There are acrylates, polyester acrylate oligomers and the like.

As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-) 2-hydroxy group Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetraitaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

As examples of other esters, for example, aliphatic alcohol-based esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are suitably used.

Further, specific examples of monomers of amides of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacryl Amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bis methacrylamide and the like.

Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

Further, urethane addition polymerization monomers produced by using an addition reaction of an isocyanate and a hydroxyl group are also suitable, and as such a specific example, for example, one molecule described in JP-B-48-41708 is used. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule in which a vinyl monomer containing a hydroxyl group represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups Etc.
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )
Also, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, JP-B-58-49860 and JP-B 56- Also suitable are urethane compounds having an ethylene oxide-based skeleton as described in JP-A-17654, JP-B-62-39417, and JP-B-62-39418.

Further, as the radically polymerizable monomer, compounds described in paragraph Nos. 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present invention.

Further, as the radical polymerizable monomer, a compound having at least one addition polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc .; (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as anurate, glycerin or trimethylol ethane and then forming (meth) acrylate, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-A-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
Polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
Moreover, as another preferable radically polymerizable monomer, it has a fluorene ring and is described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. It is also possible to use a compound having a functionality or more and a cardo resin.
Further, as other examples of the radical polymerizable monomer, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and JP-A-2-25493 can be mentioned. The vinyl phosphonic acid type compound etc. of a statement can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesive Association vol. 20, no. Also those introduced as photocurable monomers and oligomers on pages 7, 300-308 (1984) can be used.

Moreover, as a compound which has a boiling point of 100 degreeC or more under normal pressure, and has at least one addition polymerizable ethylenic unsaturated group, Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970. The compounds described are also suitable.

Besides the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the above general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T in one molecule may be identical to or different from each other.
In each of the radically polymerizable monomers represented by the above general formulas (MO-1) to (MO-5), at least one of the plural R's is —OC (= O) CHCHCH ₂ or This represents a group represented by —OC (OO) C (CH ₃ ) 表 CH ₂ .
As specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5), compounds described in paragraph Nos. 0248 to 0251 of JP-A-2007-269779 can be used. It can also be suitably used in the invention.

Further, compounds described by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 and its specific examples as General Formulas (1) and (2) are also converted into (meth) acrylates. And as radically polymerizable monomers.

Among them, as radical polymerizable monomers, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (made as KAYARAD D-310; Nippon Kayaku Co., Ltd. as a commercial product), dipentaerythritol hexa (meth) acrylate (made as a commercial product, KAYARAD DPHA; made by Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used.

The radically polymerizable monomer is a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is, but if necessary, the hydroxyl of the ethylenic compound described above A nonaromatic carboxylic acid anhydride may be reacted with the group to introduce an acid group. In this case, specific examples of non-aromatic carboxylic acid anhydrides used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydride Maleic acid is mentioned.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Polyfunctional monomers having an acid group are preferred, and particularly preferred in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

In the present invention, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g. When the acid value of the polyfunctional monomer is too low, the development dissolution characteristics are deteriorated, and when too high, the production and handling become difficult, the photopolymerization performance is deteriorated, and the curability such as the surface smoothness of the pixel tends to be inferior. Therefore, in the case of using two or more kinds of polyfunctional monomers having different acid groups in combination, or in the case of using a polyfunctional monomer having no acid group, the acid group as the entire polyfunctional monomer is adjusted to fall within the above range. Is preferred.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a radically polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane and penta Ε-caprolactone modified polyfunctional (ε) obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine Mention may be made of meta) acrylates. Among them, polyfunctional monomers having a caprolactone structure represented by the following general formula (B) are preferable.

General formula (B)

(Wherein all six R's are a group represented by the following general formula (C), or one to five of six R's are a group represented by the following general formula (C) And the remainder is a group represented by the following general formula (D).)

General formula (C)

(Wherein, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

General formula (D)

(Wherein, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such polyfunctional monomers having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (in the above general formulas (B) to (D), m = 1, a compound represented by the general formula (C) = 2, a compound wherein all R ¹ are hydrogen atoms, DPCA-30 (the same formula, m = 1, a group represented by the general formula (C)) Compounds in which the number is 3, all R ¹ are hydrogen atoms, DPCA-60 (in the formula, m = 1, the number of groups represented by general formula (C) = 6, and all R ¹ are hydrogen atoms And DPCA-120 (m = 2 in the same formula, the number of groups represented by general formula (C) = 6, compounds in which all R ¹ are hydrogen atoms), and the like.
In the present invention, polyfunctional monomers having a caprolactone structure can be used alone or in combination of two or more.

The polyfunctional monomer is also preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) yCH (} CH 3) O) - represents, y Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total of (meth) acryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the sum of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In general formula (i) or formula (ii) in the _{_{- ((CH 2) yCH 2}} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X Preferred is a form of binding to

In particular, in the general formula (ii), a form in which all six X's are an acryloyl group is preferable.

The compound represented by the above general formula (i) or (ii) has a ring-opening skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally known step. And the step of introducing a (meth) acryloyl group by, for example, reacting (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opened skeleton. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a) and (f) b), (e) and (f) are preferred.

Examples of commercially available radically polymerizable monomers represented by the general formulas (i) and (ii) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains.

Also, as radically polymerizable monomers, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765. Further, urethane compounds having an ethylene oxide-based skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, as polymerizable monomers, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 Monomers can also be used.
As commercially available products of radically polymerizable monomers, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA) And -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

Among the above radical polymerizable monomers, any two of (A) a bifunctional or less radical polymerizable monomer and (B) a trifunctional or more radical polymerizable monomer at least one of which is contained in one molecule It is preferable from the viewpoint of adhesiveness and easy removability that the number of atoms between the radically polymerizable groups is 9 atoms or more. That is, when it has three or more polymerizable groups in one molecule, it means that the number of atoms between any two polymerizable groups is 9 or more atoms apart.
As a linking group consisting of 9 or more atoms linking between any two radically polymerizable groups contained in one molecule, -CO-, -O-, -NH-, a divalent to tetravalent fat And a linking group having a valence of 2 or more selected from the group consisting of a divalent to hexavalent aromatic group and a combination thereof (usually having a valence corresponding to the number of functional groups). More preferred is a divalent linking group selected from the group consisting of -O-, and a divalent aliphatic group and a combination thereof. Here, the aliphatic group and the aromatic group may have a substituent.
The number of atoms between any two radically polymerizable groups contained in one molecule of (A) a difunctional or lower radically polymerizable monomer and / or (B) a trifunctional or higher radically polymerizable monomer is If the number of atoms of the linking group is too large, the releasability is reduced. Therefore, as the divalent linking group, 9 to 100 atoms are preferable, 10 to 80 atoms are more preferable, and 12 to 50 atoms are particularly preferable. The number of atoms between any two radically polymerizable groups contained in one molecule is the number of atoms between radically polymerizable ethylenically unsaturated groups, and more specifically, as in the following example It can be counted.

It is preferable that at least one of (A) a difunctional or lower radically polymerizable monomer and (B) a trifunctional or higher radically polymerizable monomer have a polyoxyalkylene partial structure represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ²¹ represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)

Examples of the alkyl group represented by R ²¹ include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, and a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, Examples thereof include isopentyl group, 2-ethylhexyl group, 2-methylhexyl group and cyclopentyl group.
As R ²¹ , a hydrogen atom is particularly preferred.
a is preferably 1 or 2, and 1 is particularly preferred.
l is preferably an integer of 2 to 50, more preferably an integer of 2 to 25, and particularly preferably an integer of 2 to 10.

The monomer which is connected by a divalent or higher linking group in which the number of atoms between any two radically polymerizable groups contained in one molecule is 9 atoms or more is not less than (A) bifunctional or less It is preferable that it is a radically polymerizable monomer of these, and it is further more preferable that it is a bifunctional radically polymerizable monomer. Furthermore, it is preferable that the difunctional or less radically polymerizable monomer has a polyoxyalkylene partial structure represented by the general formula (1), and the difunctional radical polymerizable monomer is represented by the general formula (1) More preferably, they have a polyoxyalkylene partial structure.

Furthermore, as a radically polymerizable monomer (A) bifunctional or less, it is especially preferable that it is a bifunctional monomer represented by following General formula (2).
General formula (2)

In the general formula (2), R ²¹ , R ²² and R ²³ each represent a hydrogen atom or an alkyl group, a represents an integer of 1 to 5, and l represents an integer of 2 to 150. X ¹ , X ² , Y ¹ and Y ² each consist of a single bond, or -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group and a combination thereof Represents a divalent linking group selected from the group)

Examples of the alkyl group represented by R ²¹ , R ²² and R ²³ include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, each of which is methyl group, ethyl group, propyl group or octyl group, And isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
As R ²¹ , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.
As R ²² and R ²³ , a hydrogen atom or a methyl group is particularly preferable.
a and l are respectively synonymous with a and l in the general formula (1), and preferred ranges are also the same.

Specific examples of X ¹ and X ² include the following L 1 to L 18 respectively. In the following example, the left side is bonded to Y ¹ or Y ² and the right side is bonded to an ethylenically unsaturated bond.

L1: -CO-NH2 divalent aliphatic group -O-CO-NH2 divalent aliphatic group -O-CO-
L2: -CO-NH2 divalent aliphatic group -O-CO-
L3: -CO-divalent aliphatic group -O-CO-
L4: -CO-O-divalent aliphatic group -O-CO-
L5: -divalent aliphatic group -O-CO-
L6: -CO-NH2 divalent aromatic group -O-CO-
L7: -CO-divalent aromatic group -O-CO-
L8: -divalent aromatic group -O-CO-
L9: -CO-O-divalent aliphatic group -CO-O-divalent aliphatic group -O-CO-
L10: -CO-O-divalent aliphatic group -O-CO-divalent aliphatic group -O-CO-
L11: -CO-O-divalent aromatic group -CO-O-divalent aliphatic group -O-CO-
L12: -CO-O-divalent aromatic group -O-CO-divalent aliphatic group -O-CO-
L13: -CO-O-divalent aliphatic group -CO-O-divalent aromatic group -O-CO-
L14: -CO-O-divalent aliphatic group -O-CO-divalent aromatic group -O-CO-
L15: -CO-O-divalent aromatic group -CO-O-divalent aromatic group -O-CO-
L16: -CO-O-divalent aromatic group -O-CO-divalent aromatic group -O-CO-
L17: -CO-O-divalent aromatic group -O-CO-NH-divalent aliphatic group -O-CO-
L18: -CO-O-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-

Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Among them, an alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable. It is preferable that these groups have no substituent.
As the divalent aliphatic group, a chain structure is more preferable than a cyclic structure, and a linear structure is more preferable than a chain structure having a branch. The number of carbon atoms of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 12, and still more preferably 1 to 10. The number is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group And alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.

Examples of divalent aromatic groups include phenylene, substituted phenylene, naphthalene and substituted naphthalene, with phenylene being preferred. As an example of the substituent of a bivalent aromatic group, in addition to the example of the substituent of the said bivalent aliphatic group, an alkyl group is mentioned.

Y ¹ and Y ² are each selected from the group consisting of a single bond or -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group and a combination thereof Represents a divalent linking group. It is preferable that either Y ¹ or Y ² have a divalent aromatic group or a polyoxyalkylene structure, and it is particularly preferable to have a divalent aromatic group and a polyoxyalkylene structure. The divalent aromatic group is preferably composed of one or more benzene rings, and more preferably a phenylene group.

Furthermore, in the present invention, (A) a bifunctional or less radically polymerizable monomer and / or (B) a trifunctional or more radically polymerizable monomer are selected only from atoms selected from carbon atom, oxygen atom, hydrogen atom and nitrogen atom. It is preferable to be comprised, and it is more preferable to be comprised only from a carbon atom, an oxygen atom, and a hydrogen atom.

As a radically polymerizable monomer in which the nearest radically polymerizable group in the molecule is linked by a divalent linking group consisting of at least 9 atoms, specifically, radically polymerizable monomers represented by the following structures can be mentioned Is not limited to these.

The ratio (mass ratio) of the (A) difunctional or less radically polymerizable monomer and the (B) trifunctional or higher radically polymerizable monomer is preferably 95/5 to 20/80, and 85/15 to 20 / It is more preferably 80, still more preferably 80/20 to 20/80, still more preferably 80/20 to 40/60, and particularly preferably 80/20 to 50/50.

The content of the polymerizable monomer is the total amount of (A) a bifunctional or less radically polymerizable monomer and (B) a trifunctional or more radically polymerizable monomer, and from the viewpoint of good adhesive strength and releasability, the adhesiveness 20 to 95% by mass is preferable, 30 to 80% by mass is more preferable, and 50 to 75% by mass is more preferable, with respect to the total solid content of the layer.
The radical polymerizable monomer (A) having a functionality of two or less and the radical polymerizable monomer having a functionality of three or more (B) may be used in combination of two or more, if necessary.

(C) Polymer Compound The temporary adhesive for producing a semiconductor device of the present invention is excellent in coatability by containing a polymer compound. In addition, coating property said here means the uniformity of the film thickness after application | coating, and the film formation property after application.
In the present invention, any high molecular compound can be used.
For example, it contains hydrocarbon resin, polystyrene resin (eg, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer (AS resin), methyl methacrylate / styrene copolymer (MS resin) ), Novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polyethylene resin, polypropylene v, polyvinyl chloride resin, polyvinyl acetate resin, Teflon (registration Trademarks, (meth) acrylic resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene teraphthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, poly Sulfone resins, polyether sulfone resins, polyarylate resins, polyether ether ketone resin, and synthetic resins such as polyamide-imide resins, and natural resins such as natural rubber. Among them, hydrocarbon resin, ABS resin, AS resin, MS resin, polyurethane resin, novolak resin, polyimide resin are preferable, hydrocarbon resin and MS resin are more preferable, and acrylic resin, ABS resin, AS resin and MS resin are further more preferable.
In the present invention, the binder may be used in combination of two or more as needed.

In the present invention, any hydrocarbon resin can be used.
The hydrocarbon resin in the present invention basically means a resin consisting only of carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, even when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin and polyvinyl pyrrolidone resin, to a hydrocarbon resin consisting only of carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention, and in this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more with respect to all the repeating units of the resin. Is preferred.

Examples of hydrocarbon resins meeting the above conditions include polystyrene resin, terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester , Polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum oil Resin, polystyrene-polyolefin copolymer, olefin polymer (eg, methylpentene copolymer), cycloolefin polymer (eg, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), etc. Can be mentioned.

The hydrocarbon resin is preferably, among others, polystyrene resin, terpene resin, rosin, petroleum resin, hydrogenated rosin, polymerized rosin, olefin polymer, or cycloolefin polymer, and polystyrene resin, terpene resin, rosin, olefin polymer, Alternatively, a cycloolefin polymer is more preferable, and a polystyrene resin, a terpene resin, a rosin, an olefin polymer, a polystyrene resin, or a cycloolefin polymer is more preferable, and a polystyrene resin, a terpene resin, a rosin, a cycloolefin polymer Or, it is particularly preferable that the polymer is an olefin polymer, more preferably a polystyrene resin or a cycloolefin monomer polymer.

Specific examples of the polystyrene resin include polystyrene, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, and methyl methacrylate-styrene resin. Preferably, it is methyl methacrylate styrene resin. The amount of outgas generation at the time of heating at 250 ° C. is preferably 3% by mass or less because heat resistance to a high temperature treatment process of a semiconductor substrate is required. More preferably, the resin is 2% by mass or less. Commercial products of methyl methacrylate / styrene resin include: Estyrene MS-200 NT, MS-300, MS-500, MS-600 (Nippon Steel Sumikin Chemical Co., Ltd.), Sebian MAS 10, MAS 30 (Daicel Polymer Co., Ltd.) It can be used.

Examples of cycloolefin polymers include norbornene polymers, polymers of monocyclic olefins, polymers of cyclic conjugated dienes, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin polymer include an addition (co) polymer containing at least one or more repeating units represented by the following general formula (II), and at least one of the repeating units represented by the general formula (I) Addition (co) polymers further comprising species may be mentioned. Moreover, as another preferable example of a cycloolefin polymer, the ring-opening (co) polymer which contains at least 1 sort (s) of cyclic repeating unit represented by General formula (III) is mentioned.

In the formula, m represents an integer of 0 to 4. R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ to X ³ and Y ¹ to Y ³ each independently represent a hydrogen atom or 1 to 10 carbon atoms A hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-(CH ₂ ) nCOOR ¹¹ ,-(CH ₂ ) n OCOR ¹² ,-(CH ₂ ) n NCO,-(CH ₂ ) NNO ₂ ,-(CH ₂ ) nCN,-(CH ₂ ) nCONR ¹³ R ¹⁴ ,-(CH ₂ ) nNR ¹⁵ R ¹⁶ ,-(CH ₂ ) nOZ,-(CH ₂ ) nW or X ¹ and (—CO) ₂ O, (—CO) ₂ NR ¹⁷ composed of Y ¹ , X ² and Y ² , or X ³ and Y ³ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having a carbon number of 1 to 20), and Z represents a carbon atom H represents a hydrogen group or a hydrocarbon group substituted with a halogen, W represents SiR ¹⁸ pD3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ Or -OR ¹⁸ is represented, and p is an integer of 0 to 3). n represents an integer of 0 to 10.

The norbornene polymers are disclosed in JP-A-10-7732, JP-A-2002-504184, US2004 / 229157A1 or WO2004 / 070463A1. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, norbornene-based polycyclic unsaturated compounds and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; and nonconjugated dienes such as ethylidene norbornene can also be addition-polymerized. This norbornene-based polymer is marketed by Mitsui Chemicals, Inc. under the trade name of Apel, and has a different glass transition temperature (Tg), such as APL 8008 T (Tg 70 ° C.), APL 6013 T (Tg 125 ° C.) or APL 6015 T (Tg 145 ° C.) There is a grade of Pellets such as TOPAS 8007, 5013, 6013 and 6015 are commercially available from Polyplastics Co., Ltd.
In addition, the Appear 3000 has been marketed by Ferrania.

The hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-1159767. Alternatively, as disclosed in JP-A-2004-309979, etc., it can be produced by addition polymerization or metathesis ring-opening polymerization of a polycyclic unsaturated compound, followed by hydrogenation.
In the general formula (III), R ⁵ and R ⁶ are preferably a hydrogen atom or a methyl group, X ³ and Y ³ are preferably a hydrogen atom, and the other groups are appropriately selected. This norbornene polymer is marketed by JSR Corporation under the trade name Arton G or Arton F, and Nippon Zeon Co., Ltd. sells Zeonor ZF14, ZF16, Zeonex 250, They are commercially available under the trade names 280 and 480R, and these can be used.

The weight average molecular weight of the polymer compound in terms of polystyrene equivalent by gel per emission chromatography (GPC) method is preferably 10,000 to 1,000,000, and preferably 50,000 to 500,000. More preferably, it is 100,000 to 300,000.

The content of the polymer compound is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more based on the total solid content of the temporary adhesive of the present invention. Is more preferred.
The content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, and 50% by mass or less, based on the total solid content of the temporary adhesive of the present invention. It is more preferable that the content be 40% by mass or less.
Only one type of polymer compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

The ratio (mass ratio) of the content of the radically polymerizable monomer and the polymer compound (radically polymerizable monomer / polymer compound) is preferably 90/10 to 10/90, and preferably 80/20 to 20 /. It is more preferably 80, and still more preferably 70/30 to 30/70.

<(D) Radical polymerization initiator>
The temporary adhesive for producing a semiconductor device of the present invention contains a radical polymerization initiator, that is, a compound which generates radicals by irradiation with actinic rays or radiation (light irradiation) or heat.
Since the temporary adhesive for producing a semiconductor device of the present invention has a radical polymerization initiator, the adhesive layer is irradiated or heated with light, so that a curing reaction by radicals occurs, and the adhesiveness in the light irradiation part or the heating part It can decrease.
As a compound which generates a radical upon irradiation with an actinic ray or radiation (hereinafter, also simply referred to as a photoradical polymerization initiator), for example, those known as polymerization initiators described below can be used.
The polymerization initiator is not particularly limited as long as it has an ability to initiate a polymerization reaction (crosslinking reaction) in a reactive compound having a polymerizable group as the polymerizable monomer, and any of known polymerization initiators is appropriately selected. It can be selected. For example, those having photosensitivity to light rays visible from the ultraviolet region are preferable. In addition, it may be an activator which produces an active radical by causing an action with a photoexcited sensitizer.
The polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

As the polymerization initiator, known compounds can be used without limitation, and for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), Acyl phosphine compounds such as acyl phosphine oxides, oxime compounds such as hexaaryl biimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether, aminoacetophenone compounds, hydroxyacetophenone, azo system Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like can be mentioned.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, an F. compound. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, specification of U.S. Pat. No. 4,129,976 Compounds described in the book, and the like.

Examples of the compounds described in the aforementioned US Pat. No. 4,129,976 include compounds having an oxadiazole skeleton (eg, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) ) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1 , 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4 -Oxadiazole etc.) and the like.

In addition, as polymerization initiators other than those described above, acridine derivatives (eg, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, etc.), N-phenylglycine, etc., polyhalogen compounds (eg, four) Carbon bromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone etc., coumarins (eg, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-) Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis ( 5,7-di-n-propoxycoumarin), 3,3'-car Nylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-Pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and JP-A-5-19475 and JP-A-7-2721028. 2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc., coumarin compounds, etc., acyl phosphine oxides (eg, bis (2, 4 , 6-Trimethylbenzoyl) -phenyl phosphite Oxides, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenyl phosphine oxide, LucirinTPO etc., metallocenes (eg bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 5-5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc. And JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and compounds described in US Pat. No. 3,615,455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-Ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (eg, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexyl Amino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophene , 4,4'-Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butyl anthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro anthraquinone -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin prop Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.
Among commercial products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxyacetophenone type initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF, Inc.) can be used. As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF AG) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source such as 365 nm or 405 nm can also be used. Moreover, as an acyl phosphine type | system | group initiator, IRGACURE-819 and DAROCUR-TPO (brand name: all are BASF Corporation make) which are commercial items can be used.

As a photoinitiator, More preferably, an oxime type compound is mentioned. As specific examples of the oxime initiator, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.

Examples of oxime compounds such as oxime derivatives which are preferably used as a polymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxyiminobutane -2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- (4- (4-hydroxy-4-amino) phenyl) Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

As oxime ester compounds, J.I. C. S. Perkin II (1979) p. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A-2000-66385, and compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used.

Further, as oxime ester compounds other than those described above, compounds described in JP-T-2009-519904, in which an oxime is linked to the carbazole N-position, and compounds described in US Pat. No. 7,626,957, in which a hetero substituent is introduced in the benzophenone moiety, Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site, ketooxime compounds described in WO2009-131189, triazine skeleton and oxime skeleton identical The compound described in US Pat. No. 7,556,910 contained in the molecule, the compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used. .

Preferably, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used. Among cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in, for example, JP-A-2010-32985 and JP-A-2010-185072 have high light absorption and high sensitivity. preferable.
In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the oxime compound, can also be used preferably because high sensitivity can be achieved by regenerating the active radical from the polymerization inactive radical. it can.

Most preferably, an oxime compound having a specific substituent described in JP-A-2007-269779 or an oxime compound having a thioaryl group shown in JP-A-2009-191061 can be mentioned.

The molar absorption coefficient of the compound may be a known method, and specifically, for example, 0.01 g of an ethyl acetate solvent is used in a UV-visible spectrophotometer (Varry Carry-5 spctrophotometer). It is preferable to measure at a concentration of / L.

As a radical photopolymerization initiator, trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, from the viewpoint of exposure sensitivity Selected from the group consisting of triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyl oxadiazole compound, 3-aryl substituted coumarin compound Compounds are preferred.

More preferably, a trihalomethyl triazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triaryl imidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, a trihalomethyl triazine compound, an α-amino ketone Most preferably, at least one compound selected from the group consisting of a compound, an oxime compound, a triarylimidazole dimer and a benzophenone compound is used, and most preferably an oxime compound is used.

As a compound which radically generates by heat (hereinafter, also simply referred to as a thermal radical polymerization initiator), known thermal radical generators can be used.
The thermal radical polymerization initiator is a compound which generates a radical by the energy of heat to initiate or accelerate the polymerization reaction of the polymerizable monomer. When heat is applied to the adhesive layer formed using a temporary adhesive by adding a thermal radical generating agent, the heat is applied to the adhesive support and the member to be treated is then heated. As a result of the crosslinking reaction in the reactive compound having a crosslinkable group proceeding, the adhesion (i.e., tackiness and tackiness) of the adhesive layer can be reduced in advance, as described in detail later.
On the other hand, in the case where the adhesive layer in the adhesive support is irradiated with heat after temporary bonding between the member to be treated and the adhesive support, in the case of a reactive compound having a crosslinkable group by heat The progress of the crosslinking reaction makes the adhesive layer more tough, and can suppress cohesive failure of the adhesive layer which is likely to occur when the mechanical or chemical treatment of the member to be treated is performed. That is, the adhesiveness in an adhesive layer can be improved.
Preferred thermal radical polymerization initiators include compounds that generate radicals upon irradiation with actinic rays or radiation described above, but compounds having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C. It can be used preferably.
As a thermal radical polymerization initiator, aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon The compound which has a halogen bond, an azo compound, etc. are mentioned. Among them, organic peroxides or azo compounds are more preferable, and organic peroxides are particularly preferable.
Specifically, the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be mentioned.

When the temporary adhesive of the present invention contains a thermal radical polymerization initiator as the radical polymerization initiator (C) (more preferably, it contains a photo radical polymerization initiator and a thermal radical polymerization initiator), The adhesion at high temperatures (eg, 100 ° C.) can be further improved.

The temporary adhesive of the present invention preferably contains a photo radical polymerization initiator.
In addition, the temporary adhesive of the present invention may contain one or two or more radical polymerization initiators.

The content (total content in the case of two or more types) of the radical polymerization initiator of the present invention is preferably 0.1% by mass to 50% by mass with respect to the total solid content of the temporary adhesive, and more preferably Is 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less.

<Chain transfer agent>
It is preferable that the temporary adhesive for semiconductor device manufacture of this invention contains a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary Third Edition (edited by the Polymer Society of Japan, 2005), pp. 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to a low active radical species to form a radical or be oxidized and then deprotonated to form a radical. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) are preferably used as the temporary adhesive. be able to.

The preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the temporary adhesive. is there.
One type of chain transfer agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Polymerization inhibitor>
The temporary adhesive of the present invention contains a small amount of a polymerization inhibitor to prevent unnecessary thermal polymerization of the polymer compound (A) and the radically polymerizable monomer (B) during the production or storage of the temporary adhesive. Preferably it is added.
As a polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol And 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and N-nitroso-N-phenylhydroxylamine aluminum salt are preferably mentioned.
The addition amount of the polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the temporary adhesive.
One type of polymerization inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Higher fatty acid derivatives etc>
In the temporary adhesive of the present invention, in order to prevent polymerization inhibition by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to the surface of the adhesive layer in the process of drying after application. It may be unevenly distributed. The addition amount of the higher fatty acid derivative is preferably about 0.1 to about 10% by mass with respect to the total solid content of the temporary adhesive.

<Solvent>
When making the temporary adhesive of this invention into a layer by application | coating, it is preferable to mix | blend a solvent.
A solvent can be used without limitation as long as it can form an adhesive layer.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-hydroxypropionate Esters (eg methyl 3-oxypropionate, ethyl 3-oxypropionate etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.) ), 2) Alkyl oxypropionates (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methylpropionate) Methyl methyl propionate, ethyl 2-ethoxy-2-methyl propionate, etc., methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc , And with ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc., and aromatic hydrocarbons such as torue And xylene are preferably mentioned.

It is also preferable to mix two or more of these solvents from the viewpoint of improving the coated surface condition. In this case, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl are particularly preferable in this case. It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

From the viewpoint of coatability, the content of the solvent in the coating solution of the temporary adhesive is preferably such that the total solid concentration of the temporary adhesive is 5 to 80% by mass, and more preferably 5 to 70% by mass. Preferably, 10 to 60% by mass is particularly preferable.
When two or more solvents are used, the total amount is preferably in the above range.

<Surfactant>
Various surfactants may be added to the temporary adhesive of the present invention from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.

In particular, the temporary adhesive of the present invention further improves the liquid properties (in particular, the flowability) when it is prepared as a coating liquid by containing a fluorine-based surfactant, so that the uniformity of the coating thickness and the reduction of the coating thickness can be obtained. Liquidity can be further improved.
That is, in the case of film formation using a coating liquid to which a temporary adhesive containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced to wet the surface to be coated. The properties are improved, and the coatability on the surface to be coated is improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with a uniform thickness with small thickness unevenness can be more suitably performed.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the temporary adhesive is also good.

Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. Same F482, same F554, same F780, same F781 (above, DIC Corporation), Florard FC430, same FC431, same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, same SC-101, The SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerine ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid Co) polymer poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and the like.

As silicone type surfactant, for example, Toray Dow Corning Co., Ltd. product "Tore silicone DC3PA", "Tore silicone SH7PA", "Tore silicone DC11PA", "Tore silicone SH21PA", "Tore silicone SH28PA", "Tore silicone SH21PA" Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials' TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF “4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BIC Chemie, and the like.
Only one surfactant may be used, or two or more surfactants may be combined.
The amount of surfactant added is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass, with respect to the total solid content of the temporary adhesive.

<Other additives>
In addition, the temporary adhesive of the present invention may contain various additives, for example, a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, oxidation, as needed, as long as the effects of the present invention are not impaired. An inhibitor, an ultraviolet absorber, an aggregation inhibitor, etc. can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the temporary adhesive.

Next, an adhesive support and a method for producing a semiconductor device using the temporary adhesive for producing a semiconductor device of the present invention described above will be described.
A method of manufacturing a semiconductor manufacturing apparatus according to the present invention comprises: bonding a first surface of a member to be treated and a substrate through an adhesive layer formed of the temporary adhesive for manufacturing a semiconductor device according to the present invention; Performing mechanical or chemical treatment on a second surface opposite to the first surface of the member to be treated to obtain a treated member; and the adhesive layer and the treated member And the step of separating the
Furthermore, prior to the step of bonding the first surface of the member to be treated and the substrate via the adhesive layer, the adhesive layer is provided on the surface of the adhesive layer to be adhered to the first surface of the member to be treated. On the other hand, it is preferable to further include the step of irradiating the actinic ray or radiation or heat. The actinic radiation or radiation is preferably an actinic radiation having a wavelength of 350 to 450 nm.
Further, in the method of manufacturing a semiconductor device according to the present invention, after the step of adhering the first surface of the member to be treated and the substrate through the adhesive layer, the first surface of the member to be treated and Heating the adhesive layer at a temperature of 50.degree. C. to 300.degree. C. prior to the step of mechanically or chemically treating the second surface on the opposite side to obtain a treated member. It is preferable to have.
Further, it is preferable that the step of separating the treated member from the adhesive layer includes a step of contacting the adhesive layer with a peeling liquid. Furthermore, it is preferable to have a protective layer on the first surface of the member to be treated between the member to be treated and the adhesive layer. That is, the treated member can be separated from the adhesive layer by dissolving the protective layer with a peeling solution.
The details of these will be described below.

FIGS. 1A and 1B are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer, and a schematic cross-sectional view showing a thinned state of a device wafer temporarily bonded by an adhesive support. FIG.

In the embodiment of the present invention, as shown in FIG. 1A, first, an adhesive support 100 in which an adhesive layer 11 is provided on a carrier substrate 12 is prepared.
Although the material of the carrier substrate 12 is not particularly limited, for example, a silicon substrate, a glass substrate, a metal substrate and the like can be mentioned. However, the point that the silicon substrate typically used as a substrate of a semiconductor device is not easily contaminated In view of the fact that an electrostatic chuck generally used in the process can be used, a silicon substrate is preferable.
The thickness of the carrier substrate 12 is, for example, in the range of 300 μm to 5 mm, but is not particularly limited.

An embodiment of the adhesive support 100 includes a metal substrate as a carrier substrate and the temporary adhesive of the present invention, that is, (A) radically polymerizable monomer, (B) polymer compound, (C) aromatic ketone compound And (D) is preferable an embodiment having an adhesive layer that contains an amine compound and is substantially free of solvent.
The adhesive support 100 has an adhesive layer containing a metal substrate, (A) radically polymerizable monomer, (B) polymer compound, (C) aromatic ketone compound and (D) amine compound. Preferably, the adhesive layer has a region in which the content of the (A) radically polymerizable monomer is relatively large and a region in which the content of the (A) radically polymerizable monomer is relatively small. . The adhesive support 100 has an adhesive layer containing a metal substrate, (A) radically polymerizable monomer, (B) polymer compound, (C) aromatic ketone compound and (D) amine compound. The adhesive layer has a region in which the content of the (A) radically polymerizable monomer is relatively high, and a region in which the content of the (A) radically polymerizable monomer is relatively small, The region in which the content of the radically polymerizable monomer is relatively large is an aspect including (A) the radically polymerizable monomer at least three times the region in which the content of the radically polymerizable monomer is relatively small More preferable.

The adhesive layer 11 is a carrier substrate 12 using the temporary adhesive for producing a semiconductor device of the present invention, using a conventionally known spin coat method, spray method, roller coat method, flow coat method, doctor coat method, immersion method or the like When a protective layer to be described later is provided thereon, it can be formed by applying (preferably applying) to the surface of the protective layer and then drying (baking). Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
The thickness of the adhesive layer 11 is, for example, in the range of 1 to 500 μm, preferably 1 to 100 μm, and more preferably 1 to 10 μm, but is not particularly limited.

Next, an adhesive support having a substrate and an adhesive layer (more preferably a substrate, an adhesive layer and an adhesive support having a protective layer) obtained as described above, and a device wafer The temporary adhesion to the workpiece, thinning of the device wafer, and separation of the adhesive support and the device wafer will be described in detail.

As shown in FIG. 1A, the device wafer 60 (member to be processed) has a plurality of device chips 62 provided on the surface 61 a of the silicon substrate 61.
Here, the thickness of the silicon substrate 61 is, for example, in the range of 200 to 1200 μm.
Then, the surface 61 a of the silicon substrate 61 is pressed against the adhesive layer 11 of the adhesive support 100. Thereby, the surface 61a of the silicon substrate 61 and the adhesive layer 11 adhere to each other, and the adhesive support 100 and the device wafer 60 temporarily adhere to each other.
After this, if necessary, the bonded body of the adhesive support 100 and the device wafer 60 may be heated (irradiated with heat) to make the adhesiveness of the adhesive layer more robust. Thereby, the anchor effect at the interface between the adhesive support and the member to be treated is promoted, and cohesive failure of the adhesive layer which is likely to occur when the device wafer 60 is subjected to mechanical or chemical treatment described later, etc. As a result, the adhesion of the adhesive support 100 is enhanced.
The heating temperature in this case is preferably 50 ° C. to 300 ° C., more preferably 80 ° C. to 250 ° C., and still more preferably 80 ° C. to 220 ° C.
The heating time in this case is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, and still more preferably 40 seconds to 3 minutes.

Next, as shown in FIG. 1B, the back surface 61 b of the silicon substrate 61 is subjected to mechanical or chemical treatment, specifically, thinning treatment such as grinding or chemical mechanical polishing (CMP). The thickness of the silicon substrate 61 is reduced (eg, to a thickness of 1 to 200 μm) to obtain a thin device wafer 60 ′.
Also, as a mechanical or chemical treatment, after the thinning process, a through hole (not shown) is formed through the silicon substrate from the back surface 61b ′ of the thin device wafer 60 ′, and the silicon is penetrated in the through hole. A process of forming an electrode (not shown) may be performed as needed.

Then, the surface 61 a of the thin device wafer 60 ′ is detached from the adhesive layer 11 of the adhesive support 100.
The method of detachment is not particularly limited, but is it possible to contact the adhesive layer 110 with a peeling solution and then, if necessary, slide the thin device wafer 60 'against the adhesive support 100? Alternatively, it is preferable to perform by peeling the thin device wafer 60 'from the adhesive support 100. Since the temporary adhesive of the present invention has high affinity to the peeling liquid, temporary bonding between the adhesive layer 110 and the surface 61 a of the thin device wafer 60 ′ can be easily released by the above method.

After detaching the thin device wafer 60 'from the adhesive support 100, the thin device wafer 60' is subjected to various known processes as needed to manufacture a semiconductor device having the thin device wafer 60 '. Do.

<Peeling solution>
Hereinafter, the peeling solution will be described in detail.

Water and a solvent (organic solvent) can be used as the stripping solution. As the peeling solution, organic solvents such as acetone and p-menthane are preferable.
Furthermore, from the viewpoint of peelability, the peeling solution may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
Furthermore, from the viewpoint of peelability, a mode in which two or more organic solvents and water, two or more alkalis, an acid and a surfactant are mixed is also preferable.

As the alkali, for example, sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic, sodium phosphate dibasic, potassium phosphate dibasic, ammonium phosphate dibasic, sodium carbonate, potassium carbonate, ammonium carbonate Inorganic alkaline agents such as sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, and monomethylamine Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.

As the acid, inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, etc., methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass, and more preferably 1 to 10% by mass, with respect to the total amount of the alkaline aqueous solution.
By setting the content of the surfactant within the above range, the releasability between the adhesive support 100 and the thin device wafer 60 'tends to be further improved.

The anionic surfactant is not particularly limited, and fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, Alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkyl phenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodiums, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, sulfate salts of fatty acid alkyl esters, alkyl sulfate salts, polio Siethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkyl phenyl ether sulfuric acid ester salts, polyoxyethylene styryl phenyl ether sulfuric acid ester salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxy acid Ethylene alkyl phenyl ether phosphate ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensates, etc. may be mentioned. Among these, alkyl benzene sulfonates, alkyl naphthalene sulfonates and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

The cationic surfactant is not particularly limited, but conventionally known ones can be used. For example, alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives can be mentioned.

The nonionic surfactant is not particularly limited, but may be polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid Ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Among them, those having an aromatic ring and an ethylene oxide chain are preferable, and alkyl-substituted or unsubstituted phenol ethylene oxide adducts or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts are more preferable.

The zwitterionic surfactant includes, but is not particularly limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkyl betaine, and amino acids such as sodium alkylamino fatty acid. In particular, alkyldimethylamine oxide which may have a substituent, alkyl carboxy betaine which may have a substituent, and alkyl sulfo betaine which may have a substituent are preferably used. Specifically, a compound represented by the formula (2) in paragraph [0256] of JP-A 2008-203359, a compound represented by the formula (I) in paragraph [0028] of JP-A 2008-276166, or the formula (II) And compounds represented by formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927.

Furthermore, if necessary, additives such as an antifoamer and a water softener may be contained.

Next, a conventional embodiment will be described.
FIG. 2 is a schematic cross-sectional view for explaining the release of the temporary adhesion state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 2, an adhesive support comprising an adhesive layer 11 'formed of a conventional temporary adhesive on a carrier substrate 12 as an adhesive support. The adhesion support 100 'and the device wafer are temporarily adhered to each other similarly to the procedure described with reference to FIGS. 1A and 1B using 100', and the thinning process of the silicon substrate in the device wafer is performed. And then strip the thin device wafer 60 'from the adhesive support 100' in the same manner as described above.

However, according to the conventional temporary adhesive, it is difficult to temporarily support the target member with high adhesive strength and easily release the temporary support on the treated member without damaging the treated member. For example, in order to make the temporary adhesion between the device wafer and the carrier substrate sufficiently high, if a conventional temporary adhesive having high adhesiveness is adopted, the temporary adhesion between the device wafer and the carrier substrate tends to be too strong. Become. Therefore, in order to release the excessively strong temporary adhesion, for example, as shown in FIG. 3, a tape (for example, dicing tape) 70 is attached to the back surface 61b ′ of the thin device wafer 60 ′. In the case of peeling off the device wafer 60 ′, the device chip 62 is apt to be broken due to, for example, detachment of the bumps 63 from the device chip 62 provided with the bumps 63.
On the other hand, among conventional temporary adhesives, those with low adhesiveness can easily release temporary support for the treated member, but the temporary bonding between the device wafer and the carrier substrate is too weak, and the device The problem that the wafer can not be reliably supported by the carrier substrate tends to occur.

However, the adhesive layer formed by the temporary adhesive of the present invention exhibits sufficient adhesiveness, and the temporary adhesion between the device wafer 60 and the adhesive support 100 is particularly a peeling liquid on the adhesive layer 11. It can be easily released by bringing That is, according to the temporary adhesive of the present invention, the device wafer 60 can be temporarily supported with high adhesive force, and temporary support for the thin device wafer 60 'can be easily released without damaging the thin device wafer 60'. .

FIGS. 3A, 3B, 3C, and 3D are schematic cross-sectional views for explaining temporary adhesion between an adhesive support and a device wafer with a protective layer, respectively, a device wafer with a protective layer temporarily adhered by an adhesive support. 1 is a schematic sectional view showing a thinned state, a schematic sectional view showing a thin device wafer with a protective layer peeled from an adhesive support, and a schematic sectional view showing a thin device wafer.

FIGS. 4A and 4B are schematic cross-sectional views for explaining the thinned state of the device wafer temporarily bonded by the adhesive support, and the device wafer with protective layer temporarily bonded by the adhesive support. It is a schematic sectional drawing explaining the state by which it was thinned.

In the above-described first embodiment of the present invention, as shown in FIG. 3A, instead of the device wafer 60, a device wafer with protective layer 160 (member to be processed) may be used.
Here, the device wafer with protective layer 160 is provided on the silicon substrate 61 (substrate to be treated) on which the plurality of device chips 62 are provided on the surface 61 a and the surface 61 a of the silicon substrate 61 to protect the device chips 62. And a protective layer 80.
The thickness of the protective layer 80 is, for example, in the range of 1 to 1000 μm, preferably 1 to 100 μm, and more preferably 5 to 40 μm.
As the protective layer 80, although a known one can be used without limitation, one that can reliably protect the device chip 62 is preferable.
As a material which comprises the protective layer 80, if it is the purpose of protecting a to-be-processed base material, a well-known compound can be used without a restriction | limiting. Specifically, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, polyimide, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, Teflon (registered trademark), ABS Resin, AS resin, acrylic resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene teraphthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyether sulfone, polyarylate, polyether ether ketone, polyamide imide, etc. Synthetic resins and natural resins such as rosin and natural rubber can be preferably used. As a commercial item, ZEONEX 480R (made by Nippon Zeon Co., Ltd.) etc. can be used preferably.
Moreover, the protective layer 80 can contain the compound which may be contained in the said temporary adhesive agent as needed in the range which does not impair the effect of this invention.
The protective layer is applied (preferably coated) on the carrier substrate 12 using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, immersion method or the like, and then dried. It can be formed by Drying can be performed, for example, at 80 to 200 ° C. for 1 to 10 minutes.

Then, the surface 160 a (the surface of the protective layer 80 opposite to the silicon substrate 61) of the device wafer 160 with a protective layer is pressed against the adhesive layer 11 of the adhesive support 100. Thereby, the surface 160a of the device wafer 160 with a protective layer adheres to the adhesive layer 21, and the adhesive support 100 and the device wafer 160 with a protective layer temporarily adhere.

Next, as described above, as shown in FIG. 3B, the thickness of the silicon substrate 61 is reduced (for example, a silicon substrate 61 'having a thickness of 1 to 200 μm is formed) to obtain a thin device wafer 160' with a protective layer.

Next, as described above, the surface 160a of the thin device wafer with protective layer 160 'is detached from the adhesive layer 11 of the adhesive support 100 to obtain a thin device wafer with protective layer 160' as shown in FIG. 3C. .

Then, by removing the protective layer 80 in the thin device wafer 160 'with protective layer from the silicon substrate 61' and the device chip 62, as shown in FIG. 3D, the device chip 62 is provided on the silicon substrate 61 '. A thin device wafer is obtained.
Any known method can be employed to remove the protective layer 80. For example, (1) a method of dissolving and removing the protective layer 80 with a solvent; (2) affixing a peeling tape or the like to the protective layer 80 A method of mechanically peeling the layer 80 from the silicon substrate 61 ′ and the device chip 62; (3) exposing the protective layer 80 with light such as ultraviolet light and infrared light or irradiating the laser with the protective layer 80; A method of decomposing or improving the releasability of the protective layer 80 may, for example, be mentioned.
The above (1) and (3) have an advantage that the removal of the protective layer 80 is easy because the actions in these methods are performed on the entire surface of the protective film.
The above (2) has the advantage that it can be carried out at room temperature without requiring a special device.

The configuration using the device wafer 160 with a protective layer instead of the device wafer 60 as a member to be processed is TTV (Total Thickness) of a thin device wafer obtained by thinning the device wafer 60 temporarily bonded by the adhesive support 100. This is effective when it is desired to further reduce the variation) (ie, to improve the flatness of the thin device wafer).
That is, when thinning the device wafer 60 temporarily bonded by the adhesive support 100, as shown in FIG. 4A, the uneven shape of the device wafer 60 formed by the plurality of device chips 62 is thin device wafer 60 '. TTV tends to be transferred to the back surface 61b 'of the H.sup.
On the other hand, in the case of thinning the device wafer with protective layer 160 temporarily attached by the adhesive support 100, first, as shown in FIG. 4B, a plurality of device chips 62 are protected by the protective layer, In the contact surface of the protective layer-attached device wafer 160 with the adhesive support 110, it is possible to almost eliminate the uneven shape. Therefore, even if the device wafer 160 with a protective layer is supported by the adhesive support 110 and thinned, the shape derived from the plurality of device chips 62 is the back surface 61 b of the thin device wafer with protective layer 160 ′ ′ The risk of being transferred to the device can be reduced, and as a result, the TTV of the thin device wafer finally obtained can be further reduced.

Moreover, when the temporary adhesive agent of this invention contains the thermal radical polymerization initiator, the adhesive layer 11 can be made into an adhesive layer in which adhesiveness reduces by irradiation of a heat | fever. In this case, specifically, the adhesive layer 11 is a layer having adhesiveness before being subjected to heat irradiation, but a layer in which the adhesiveness declines or disappears in a region subjected to the heat irradiation. It can be done.
When the temporary adhesive of the present invention further contains a radical photopolymerization initiator, the adhesive layer 11 can be made an adhesive layer whose adhesiveness is reduced by irradiation with an actinic ray or radiation. In this case, specifically, the adhesive layer is a layer having adhesiveness before being irradiated with an actinic ray or radiation, but in the area irradiated with the actinic ray or radiation, the adhesive property is It can be a layer that decreases or disappears.

Therefore, in the present invention, before the device wafer 60 and the adhesive support 100 are bonded to each other, the surface of the adhesive layer 100 of the adhesive support 100 to be bonded to the device wafer 60 is Radiation or heat may be applied.
For example, the adhesive layer is converted into an adhesive layer having a low adhesive area and a high adhesive area formed by irradiation with actinic rays or radiation or heat, and then temporary adhesion is performed with the adhesive support of the treated member. You may Hereinafter, this embodiment will be described.

FIG. 5A shows a schematic cross-sectional view illustrating exposure to an adhesive support, and FIG. 5B shows a schematic top view of the mask.

First, the adhesive layer 11 of the adhesive support 100 is irradiated (that is, exposed) with an actinic ray or radiation 50 through the mask 40.

As shown in FIGS. 5A and 5B, the mask 40 is composed of a light transmission area 41 provided in the central area and a light shielding area 42 provided in the peripheral area.
Thus, the exposure is a pattern exposure in which the central area of the adhesive layer 11 is exposed but not the peripheral area surrounding the central area.

FIG. 6A shows a schematic cross-sectional view of the pattern-exposed adhesive support, and FIG. 6B shows a schematic top view of the pattern-exposed adhesive support.

As described above, in the case where the adhesive layer 11 is an adhesive layer whose adhesiveness is reduced by irradiation with an actinic ray or radiation, the adhesive support 100 is obtained by performing the above-described pattern exposure as shown in FIG. As shown in 6B, the adhesive support 110 is converted to the adhesive support 110 having the adhesive layer 21 in which the low adhesive area 21A and the high adhesive area 21B are formed in the central area and the peripheral area, respectively.
Here, the "low adhesion area" in the present specification means an area having low adhesion as compared to the "high adhesion area", and an area without adhesion (ie, "non-adhesion" Encompass the sexual area "). Similarly, "high adhesion area" means an area having high adhesion as compared to "low adhesion area".

The adhesive support 110 is provided with the low adhesive area 21A and the high adhesive area 21B by pattern exposure using the mask 40, but the areas of the light transmitting area and the light shielding area in the mask 40 and The shape can be controlled in micron or nano order. Therefore, since the area, shape, etc. of each of the high adhesion region 21B and the low adhesion region 21A formed in the adhesive layer 21 of the adhesive support 110 by pattern exposure can be finely controlled, the entire adhesive layer can be obtained. The adhesive property can temporarily support the silicon substrate 61 of the device wafer 60 more reliably and easily, and release the temporary support of the thin device wafer 60 'to the silicon substrate more easily without damaging the thin device wafer 60'. The degree of adhesion can be controlled with high precision and easily.

Further, although the high-adhesiveness region 21B and the low-adhesiveness region 21A in the adhesive support 110 are considered to have different surface physical properties by pattern exposure, they are integrated as a structure. Therefore, there is no big difference in mechanical physical properties between the high adhesive area 21B and the low adhesive area 21A, and the surface 61a of the silicon substrate 61 of the device wafer 60 is adhered to the adhesive layer 21 of the adhesive support 110, Then, even if the back surface 61b of the silicon substrate 61 is subjected to a thinning process or a process for forming a silicon through electrode, the area of the back surface 61b corresponding to the high adhesion area 21B of the adhesive layer 21 and the low adhesion area 21A. It is hard to produce a difference in the pressure (for example, grinding pressure, polishing pressure, etc.) related to the above process from the corresponding area of the back surface 61b, and the high adhesion area 21B and the low adhesion area 21A There is little impact on processing accuracy. This is particularly effective in the case of obtaining a thin device wafer 60 'having a thickness of, for example, 1 to 200 μm, which is likely to cause the above problems.

Therefore, in the embodiment using the adhesive support 110, when performing the above processing on the silicon substrate 61 of the device wafer 60, temporary support of the silicon substrate 61 can be performed more reliably and easily while suppressing the influence on the processing accuracy. While being possible, it is preferable as a form which can release temporary support with respect to thin device wafer 60 'more easily, without damaging thin device wafer 60'.

Further, the adhesive layer 11 is converted to an adhesive layer having reduced adhesiveness from the inner surface to the outer surface of the adhesive layer by irradiation with an actinic ray or radiation or heat. Temporary bonding may be performed by the adhesive support of the member to be treated. Hereinafter, this embodiment will be described.

FIG. 7 is a schematic cross-sectional view illustrating irradiation of an adhesive support with actinic rays or radiation or heat.

First, the adhesive support 100 is irradiated with an actinic ray or radiation or heat 50 'toward the outer surface of the adhesive layer 11, as shown in FIG. 7, from the inner surface 31b to the outer surface 31a of the substrate side. To the adhesive support 120 having the adhesive layer 31 with reduced adhesion.
That is, the adhesive layer 31 has the low adhesive region 31A on the outer surface 31a side and the high adhesive region 31B on the inner surface 31b side.
Such an adhesive layer 31 has an irradiation dose of actinic rays or radiation or heat 50, while the outer surface 31a is sufficiently irradiated with actinic rays or radiation or heat 50, but is active up to the inner surface 31b. It can be easily formed by setting the irradiation dose so that the light beam or radiation or heat 50 does not reach.
Here, since such change of the irradiation amount can be easily performed by changing the setting of the exposure device and the heating device, equipment cost can be suppressed, and many of the adhesive layers 21 and 31 can be formed. It's not about spending time.
Further, in the embodiment of the present invention described above, although the structure is integrated by combining the above adhesive layer 11 and the above irradiation method, the adhesion on the outer surface 31a is the adhesion on the inner surface 31b. Since the adhesive layer 31 which is positively lowered than the sex is formed, it is not necessary to provide another layer such as a separation layer.
As described above, the adhesive layer 31 is easy to form.

Furthermore, each of the adhesiveness on the outer surface 31a and the adhesiveness on the inner surface 31b can be accurately controlled by the selection of the material constituting the adhesive layer 11 and the adjustment of the dose of actinic rays or radiation or heat. It is a thing.
As a result, the adhesiveness of the adhesive layer 31 to each of the substrate 12 and the silicon substrate 61 can be temporarily and securely supported on the silicon substrate 61 of the device wafer 60 without damaging the thin device wafer 60 '. The adhesiveness of the thin device wafer 60 'to the extent that the temporary support of the thin device wafer 60' can be easily released can be controlled with high precision and easily.

Therefore, also in the embodiment using the adhesive support 120, when the silicon substrate 61 of the device wafer 60 is subjected to the above processing, the silicon substrate 61 can be temporarily supported more reliably and easily, and the thin device wafer 60 'is damaged. It is preferable as a form which can release temporary support to thin device wafer 60 'more easily, without giving.

The method of manufacturing a semiconductor device of the present invention is not limited to the above-described embodiment, and appropriate modifications, improvements, and the like can be made.

In the embodiment described above, the adhesive layer formed of the temporary adhesive for producing a semiconductor device of the present invention constitutes an adhesive support by being provided on a carrier substrate before temporary bonding of a device wafer. However, the substrate to be treated may first be provided on a member to be treated such as a device wafer, and then the substrate to be treated may be temporarily adhered.

Also, for example, the mask used for pattern exposure may be a binary mask or a halftone mask.

Further, although the exposure is a mask exposure via a mask, it may be a selective exposure by drawing using an electron beam or the like.

Moreover, in the embodiment described above, the adhesive layer has a single layer structure, but the adhesive layer may have a multilayer structure. As a method of forming the adhesive layer having a multilayer structure, a method of applying a temporary adhesive stepwise by the above-mentioned conventionally known method before irradiation with actinic rays or radiation, or after irradiation with actinic rays or radiation The method of applying a temporary adhesive by the conventionally well-known method mentioned above etc. are mentioned. In a form in which the adhesive layer has a multilayer structure, for example, in the case where the adhesive layer 11 is an adhesive layer whose adhesion is reduced by irradiation with actinic rays or radiation or heat, irradiation with actinic rays or radiation or heat Thus, the adhesion of the entire adhesive layer can also be reduced by reducing the adhesion between the layers. In the present invention, actinic radiation or radiation is preferably actinic radiation at a wavelength of 350 to 450 nm.

Further, in the above-described embodiment, although the silicon substrate is mentioned as an object to be treated supported by the adhesive support, the present invention is not limited to this, and in the method of manufacturing a semiconductor device, mechanical or chemical It may be any treated member that can be subjected to various treatments.
For example, the member to be treated may also include a compound semiconductor substrate, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate It can be mentioned.

Furthermore, in the above-described embodiment, as the mechanical or chemical treatment for the silicon substrate supported by the adhesive support, the thinning treatment of the silicon substrate and the treatment for forming the through silicon electrode are mentioned. And any process required in the method of manufacturing a semiconductor device.

In addition, the light transmitting area and the light shielding area in the mask, the high adhesive area and the low adhesive area in the adhesive layer, and the shape, size, number, arrangement place of the device chip in the device wafer, etc. Is optional and not limited as long as the invention can be achieved.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, unless there is particular notice, "part" and "%" are mass references.

<Formation of adhesive support>
The following temporary adhesives were coated on a 4-inch Si wafer using a spin coater (Opticoat MS-A100 manufactured by Mikasa, 1200 rpm, 30 seconds), baked at 100 ° C. for 30 seconds, and provided with a 3 μm thick adhesive layer Wafer 1 (ie adhesive support) was formed.

<Temporary adhesive>
・ Difunctional or less radically polymerizable monomers listed in the table (A)
Trifunctional or higher functional radically polymerizable monomer (B) described in part by mass / table described in column X1 of the above table
The polymer compound (C) described in parts by mass and table described in column X2 of the above table
The light radical polymerization initiator (Da) of the mass part and the table statement given in the X3 column of the above-mentioned table
The thermal radical polymerization initiator (Db) of the mass part and the table description given in column X 4 of the above table
Parts by mass as described in column X5 of the above table, polymerization inhibitors (p-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.008 parts by mass of surfactant (PF6320, manufactured by OMNOVA)
0.032 parts by weight of solvent (propylene glycol monopropyl ether acetate)
69.96 parts by mass

<Bifunctional or Less Radically Polymerizable Monomer (A)>
(A-1) Brenmer PME 400 (manufactured by NOF Corporation)
(A-2) NK Ester HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-3) Light acrylate 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.)
(A-4) FA-P240A (manufactured by Hitachi Chemical Co., Ltd.)
(A-5) NK ESTER ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-6) NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-7) NK Ester A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-8) NK Ester A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-9) NK Ester BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(A-10) Divinylbenzene (manufactured by Wako Pure Chemical Industries, Ltd.)

<Trifunctional or Higher Radically Polymerizable Monomer (B)>
(B-1) Light acrylate TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.)
(B-2) NK Ester A-TMP-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-3) NK Ester AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-4) NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-5) Triaryl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Polymer Compound (C)>
Polymer compound (C1): methyl methacrylate / styrene copolymer resin, ethylene styrene MS 600 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Polymer compound (C2): polymethyl methacrylate (manufactured by Aldrich, Mw: 120,000)

<Radical polymerization initiator (D)>
Photo radical polymerization initiator (Da1): IRGACURE OXE 02 (manufactured by BASF)
Photo radical polymerization initiator (Da2): Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.)
Thermal radical polymerization initiator (Db1): Perbutyl Z (manufactured by NOF Corporation, tert-butylperoxybenzoate, decomposition temperature (10 hours half-life temperature = 104 ° C.))

<Creating a member to be treated>
A 4-inch Si wafer was used as it was as a processed member having no protective layer.
As a member to be treated having a protective layer, a 20% by mass p-menthane solution of the following compound for a protective layer is applied to a 4-inch Si wafer by a spin coater (Opticoat MS-A100 manufactured by Mikasa, 1200 rpm, 30 seconds), The wafer was baked at 100 ° C. for 300 seconds to form a wafer provided with a protective layer having a thickness of 20 μm.
With or without the protective layer, the above-described wafer as the member to be processed is collectively referred to as a wafer 2.

<Compound for protective layer>
Compound for protective layer (1): ultrason E6020P (manufactured by BASF)

<Creation of adhesion test pieces>
As described in the following table, adhesion test pieces were prepared through the respective steps of exposure and pressure bonding using each temporary adhesive.

<< exposure >>
From the side of the adhesive layer of the wafer 1, using a UV exposure device (LC8 manufactured by Hamamatsu Photonics, 200 W high stability mercury xenon lamp L10852), the light transmitting area and the light shielding area form a dot pattern and The adhesive layer was exposed at 2000 mJ / cm ² for a halftone image through a photomask in which the halftone region was a light shielding region. The photomask used was a photomask in which a square light-shielding area with a side of 3 mm occupies 5% of the whole. The pattern formed by the halftone dot area (high adhesion area) on the surface of the adhesive layer is a pattern according to FIG.

<< Crimping >>
The wafer 1 and the wafer 2 were divided into sample pieces of 20 mm × 30 mm. The adhesive layer of the sample piece of wafer 1 was overlaid on the sample piece of wafer 2 in a 20 mm × 20 mm square and pressure bonded at 25 ° C. and 20 N / cm ² for 5 minutes.

<Measurement of adhesion of adhesive test piece>
The shear adhesive strength of the test piece prepared under the conditions described in the following table was measured using a tensile tester (digital force gauge manufactured by Imada Co., Ltd., model: ZP-50N), using an adhesive layer under the conditions of 250 mm / min. It measured by pulling in the direction along the face of. The results are shown in the following table.

<Peelable>
The test pieces prepared under the conditions described in the following table were pulled in the vertical direction of the adhesive layer under the conditions of 250 mm / min to confirm peelability. Moreover, after heating the produced test piece at 250 degreeC for 30 minutes, it pulled similarly to the perpendicular direction of an adhesive layer on 250 mm / min conditions, and confirmed the peelability after a heat process. "A" if the maximum peel strength is less than 5N, "B" if the maximum peel strength is at least 5N but less than 10N, "C" if the maximum peel strength is at least 10N to less than 15N, "C", the maximum peel strength Is 15N or more, or "D" when the wafer is broken. The presence or absence of breakage of the Si wafer was visually confirmed.

As described above, a semiconductor containing (A) a bifunctional or less radically polymerizable monomer, (B) a trifunctional or higher radically polymerizable monomer, (C) a polymer compound, and (D) a radical polymerization initiator according to the present invention It was found that the temporary adhesive for device manufacture not only gives good results in terms of adhesion and releasability, but also shows good results in terms of releasability after passing through a high temperature process.
Thus, the temporary adhesive of the present invention does not damage the treated member even after the high temperature process when mechanically or chemically treating the treatment member (such as a semiconductor wafer). It is possible to easily release the temporary support to the processed member.
Furthermore, in the adhesive layer formed through the exposure step, the area irradiated with light did not have any adhesiveness. With this technology, an adhesive support can be formed only on the peripheral portion of the adhesive layer with respect to the processing member, and in particular, when the processing member is a device wafer, adhesion from the device wafer can be obtained. When removing the support, it is possible to further reduce the internal damage of the device.

11, 21 to 30, 11 '

Adhesive Layer

11A, 21A to 30A High

Adhesive Region

11B, 21B to 30B Low Adhesive Region 12 Carrier Substrate 60 Device Wafer 60' Thin Device Wafer 61, Silicon Substrate 61a Silicon Substrate Surface 61b Silicon substrate backside 61b 'Backside of thin device wafer 62 Device chip 63 Bump 70 Tape 71 Protective layer 80 Temporary bonding layer 100, 100' Adhesive support

Claims

A temporary adhesive for producing a semiconductor device, comprising (A) a radically polymerizable monomer having 2 or less functionality, (B) a radically polymerizable monomer having 3 or more functionality, (C) a polymer compound, and (D) a radical polymerization initiator.
The temporary adhesive for semiconductor device manufacture according to claim 1, wherein the radically polymerizable monomer (A) having a functionality of two or less is a radically polymerizable monomer having two functionality.
An atom between any two radically polymerizable groups in which at least one of (A) a bifunctional or lower radically polymerizable monomer and (B) a trifunctional or higher radically polymerizable monomer is contained in one molecule. The temporary adhesive for semiconductor device manufacture according to claim 1 or 2 whose number is 9 atoms or more.
4. The polyoxyalkylene partial structure represented by the following general formula (1), wherein at least one of (A) a bifunctional or lower radically polymerizable monomer and (B) a trifunctional or higher radically polymerizable monomer is used. The temporary adhesive agent for semiconductor device manufacture of any one of 3.
General formula (1)

(In the general formula (1), R 21 represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
The semiconductor device according to any one of claims 1 to 3, wherein at least one of the radical polymerizable monomers (A) having a functionality of 2 or less has a polyoxyalkylene partial structure represented by the following general formula (1). Temporary adhesive.
General formula (1)

(In the general formula (1), R 21 represents a hydrogen atom or an alkyl group. A represents an integer of 1 to 5. l represents an integer of 2 to 150.)
The ratio (mass ratio) of (A) a difunctional or lower radically polymerizable monomer and (B) a trifunctional or higher radically polymerizable monomer is 80/20 to 20/80. The temporary adhesive agent for semiconductor device manufacture as described in a term.
The semiconductor device according to any one of claims 1 to 6, wherein (A) the bifunctional or lower radically polymerizable monomer and / or (B) the trifunctional or higher radically polymerizable monomer is a (meth) acrylate monomer. Temporary adhesive.
An adhesive support comprising a substrate and an adhesive layer formed of the temporary adhesive for producing a semiconductor device according to any one of claims 1 to 7 on the substrate.
Bonding the first surface of the member to be treated and the substrate through the adhesive layer formed of the temporary adhesive for producing a semiconductor device according to any one of claims 1 to 7;
Subjecting the second surface opposite to the first surface of the member to be treated mechanically or chemically to obtain a treated member;
A method of manufacturing a semiconductor device having the processed member, comprising the step of separating the adhesive layer and the processed member.
Before the step of bonding the first surface of the member to be treated and the substrate through the adhesive layer, the surface of the adhesive layer to be adhered to the first surface of the member to be treated The method of manufacturing a semiconductor device according to claim 9, further comprising the step of irradiating an actinic ray or radiation or heat.
The method of manufacturing a semiconductor device according to claim 10, wherein the actinic ray or radiation is an actinic ray having a wavelength of 350 to 450 nm.
After the step of adhering the first surface of the member to be treated and the substrate via the adhesive layer, and with respect to the second surface opposite to the first surface of the member to be treated, The method according to any one of claims 9 to 11, further comprising the step of heating the adhesive layer at a temperature of 50 ° C to 300 ° C prior to the step of applying mechanical or chemical treatment to obtain a treated member. The manufacturing method of the semiconductor device as described in these.
The method of manufacturing a semiconductor device according to any one of claims 9 to 12, wherein the step of separating the treated member from the adhesive layer includes the step of bringing a peeling solution into contact with the adhesive layer.
The semiconductor device according to any one of claims 9 to 13, further comprising a protective layer on the first surface of the member to be treated, between the member to be treated and the adhesive layer. Production method.