JP2014189696A - Temporary adhesive for manufacturing semiconductor apparatus, adhesive support using the same, and method of manufacturing semiconductor apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a temporary adhesive for manufacturing a semiconductor apparatus which can reduce the problem that the temporary adhesive emits gas in the temporary support at high temperature when a member to be processed (such as a semiconductor wafer) is subjected to mechanical and chemical treatment and can easily release the temporal support to the member to be processed without damaging the member to be processed even after the high temperature process.SOLUTION: There is provided a temporary adhesive for manufacturing a semiconductor apparatus which comprises: (A) a radical polymerizable monomer; (B) a polymeric compound; (C) an aromatic ketone compound; and (D) an amine compound.

Description

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

Conventionally, in a manufacturing process of a semiconductor device such as an IC or an LSI, a large number of IC chips are usually formed on a semiconductor silicon wafer and separated into pieces by dicing.
With the need for further downsizing and higher performance of electronic devices, there is a need for further downsizing and higher integration of IC chips mounted on electronic devices. High integration is approaching its limit.

  As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known. However, in recent years, in order to reduce the size of the IC chip, a silicon substrate is used. A method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method). However, only the method of forming the through silicon vias cannot sufficiently meet the above-described needs for higher integration of the recent IC chip.

  In view of the above, a technique is known in which the degree of integration per unit area of a silicon substrate is improved by multilayering integrated circuits in an IC chip. However, since the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip. For example, the thinning of the silicon substrate is being considered as the thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves labor in the through hole manufacturing process of the silicon substrate in the manufacture of the silicon through electrode. Because it is possible, it is considered promising.

As a semiconductor silicon wafer used in a semiconductor device manufacturing process, a semiconductor silicon wafer having a thickness of about 700 to 900 μm is widely known. In recent years, the thickness of a semiconductor silicon wafer has been reduced for the purpose of miniaturizing an IC chip. Attempts have been made to reduce the thickness to 200 μm or less.
However, since the semiconductor silicon wafer having a thickness of 200 μm or less is very thin, and the semiconductor device manufacturing member based on this is also very thin, such a member can be further processed, or When such a member is simply moved, it is difficult to support the member stably and without causing damage.

  To solve the above problems, after pre-thinning the semiconductor wafer before thinning with the device provided on the surface and the processing support substrate with a silicone adhesive, grinding the back of the semiconductor wafer to make it thin A technique is known in which a semiconductor wafer is drilled to provide a silicon through electrode, and then a processing support substrate is detached from the semiconductor wafer (see Patent Document 1). According to this technology, resistance to grinding during back grinding of semiconductor wafers, heat resistance in anisotropic dry etching processes, chemical resistance during plating and etching, smooth separation from the final support substrate for processing, It is said that it is possible to simultaneously achieve low plastid contamination.

  Further, as a method for supporting the wafer, the wafer is supported by a support layer system, and 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 separation layer is made larger than the bond bond between the wafer and the separation layer, so that when the wafer is detached from the support layer system, the wafer is easily detached from the separation layer. A technique configured to be separated is also known (see Patent Document 2).

Moreover, the technique which performs temporary adhesion | attachment using a polyether sulfone and a viscosity imparting agent, and cancels | releases temporary adhesion by heating is known (refer patent document 3).
There is also known a technique in which temporary adhesion is performed with a mixture of carboxylic acids and amines and the temporary adhesion is released by heating (see Patent Document 4).
Also, with the bonding layer made of cellulose polymer, etc., heated, the device wafer and the support substrate are bonded together by pressure bonding, and the device wafer is detached from the support substrate by heating and sliding laterally. The technique which performs is known (refer patent document 5).

In addition, a pressure-sensitive adhesive film that is composed of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and whose adhesive force changes upon irradiation with radiation is known (see Patent Document 6).
Further, the support substrate and the semiconductor wafer are temporarily bonded with an adhesive made of polycarbonate, the semiconductor wafer is processed, irradiated with irradiation radiation, and then heated, thereby processing the processed semiconductor wafer. A technique for detaching the substrate from the support substrate is known (Patent Document 7).

  Moreover, it is formed from the adhesive composition which consists of an energy-beam curable copolymer which has an energy-beam polymerizable unsaturated group in a side chain, an epoxy resin, and a thermally activated latent epoxy resin hardening | curing agent. There is known an adhesive tape that is composed of an adhesive layer and whose adhesive force changes upon irradiation with radiation (see Patent Document 8).

  A photosensitive resin composition comprising a photopolymerization initiator composed of an acetophenone compound or a benzophenone compound and a photopolymerization assistant composed of an amine compound is also known. (See Patent Documents 9, 10, 11, and 12).

JP 2011-119427 A Special table 2009-528688 JP 2011-225814 A Japanese Unexamined Patent Publication No. 2011-052142 Special table 2010-506406 gazette JP 2007-045939 A US Patent Publication No. 2011/0318938 JP-A-8-53655 JP 2005-189574 A JP 2003-156842 A JP 62-32104 A JP 2010-250059 A

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 support substrate (carrier substrate) are temporarily bonded via a layer made of an adhesive known in Patent Document 1 or the like. In some cases, the adhesive layer is required to have a certain degree of adhesion to stably support the semiconductor wafer.
Therefore, in the case of temporarily adhering the entire device surface of the semiconductor wafer and the support substrate via the adhesive layer, the temporary adhesion between the semiconductor wafer and the support substrate is sufficient, and the semiconductor wafer is stably and However, the temporary adhesion between the semiconductor wafer and the support substrate is too strong, so that the device may be damaged or detached from the semiconductor wafer. There is a tendency for the device to be detached.

  Further, as in Patent Document 2, in order to suppress the adhesion between the wafer and the support layer system from becoming too strong, a plasma polymer layer as a separation layer is formed between the wafer and the support layer system by a plasma deposition method. The forming method is (1) the equipment cost for carrying out the plasma deposition method is usually high; (2) the layer formation by the plasma deposition method requires time for vacuuming and monomer deposition in the plasma apparatus; and (3) Even when a separation layer composed of a plasma polymer layer is provided, when supporting a wafer to be processed, the wafer is released from support while the adhesive bond between the wafer and the separation layer is sufficient. In such a case, it is not easy to control the adhesive bond so that the wafer is easily detached from the separation layer;

  In addition, as described in Patent Documents 3, 4 and 5, the method of releasing temporary adhesion by heating tends to cause a problem that the device is damaged when the semiconductor wafer is detached.

  In addition, as described in Patent Documents 6, 7, and 8, in the method of irradiating irradiation radiation to release temporary adhesion, it is necessary to use a support substrate that transmits the irradiation radiation.

  The present invention has been made in view of the above background, and its purpose is to temporarily support a member to be processed with a high adhesive force when a member to be processed (such as a semiconductor wafer) is subjected to mechanical or chemical treatment. In addition, even after a high temperature process, the temporary support for the processed member can be easily released (with high peelability) without damaging the processed member. An adhesive, an adhesive support using the adhesive, and a method for manufacturing a semiconductor device are provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound, and (D) an amine compound. When the agent was used as a temporary adhesive in the temporary bonding step between the semiconductor wafer and the support substrate, it was found that the member to be processed can be temporarily supported by a high adhesive force and the temporary support to the processing member can be easily released. Although not bound by any theory, in the temporary adhesive of the present invention, the polymerizable group of the (A) radical polymerizable monomer achieves high adhesiveness. On the other hand, when the (C) aromatic ketone compound absorbs light, the (C) aromatic ketone compound is excited, and this activates the (D) amine compound. (D) Due to the activated amine compound, (A) the radical polymerizable monomer starts to polymerize and the polymerizable group disappears. As a result, the adhesiveness of the portion irradiated with the light of the temporary adhesive can be reduced. Here, (C) aromatic ketone compound is not excited about the part which does not irradiate light, and the said reaction does not advance. That is, by partially irradiating light, a highly adhesive part and a low adhesive part can be formed in the adhesive layer. It has been found that such an adhesive layer composed of a part having a high adhesiveness and a part having a low adhesiveness has a high shear adhesive strength and a weak peel adhesive strength. As a result, the present inventors have found that an adhesive layer having high adhesiveness and easy peeling can be formed during processing of the member to be processed, and has completed the present invention.

（式（１）中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ、水素原子、ハロゲン原子、ＯＨ基または一価の有機基を表す。Ｒ¹は、水素原子または一価の有機基を表す。Ｒ¹で表される基は、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶のいずれかの基と連結し、環構造を形成してもよい。）
＜８＞（Ｄ）アミン化合物が、２級または３級アミン化合物であって、分子内に、水酸基、エステル（−Ｃ（＝Ｏ）Ｏ−）、およびカルボキシ基の少なくとも１つを有している化合物である、＜１＞〜＜７＞のいずれかに記載の半導体装置製造用仮接着剤。
＜９＞基板と、前記基板上に、＜１＞〜＜８＞のいずれかに記載の半導体装置製造用仮接着剤により形成された接着性層とを有する接着性支持体。
＜１０＞被処理部材の第１の面と基板とを、＜１＞〜＜８＞のいずれかに記載の半導体装置製造用仮接着剤により形成された接着性層を介して接着させる工程、
前記被処理部材の前記第１の面とは反対側の第２の面に対して、機械的または化学的な処理を施し、処理済部材を得る工程、および、
前記接着性層と前記処理済部材を分離する工程
を有する、前記処理済部材を有する半導体装置の製造方法。
＜１１＞前記被処理部材の第１の面と基板とを前記接着性層を介して接着させる工程の前に、前記接着性層の、前記被処理部材の第１の面に接着される面に対して、前記活性光線若しくは放射線または熱を照射する工程をさらに有する、＜１０＞に記載の半導体装置の製造方法。
＜１２＞前記活性光線もしくは放射線が３５０〜４５０ｎｍの波長の活性光線であることを特徴とする＜１１＞に記載の半導体装置の製造方法。
＜１３＞被処理部材の第１の面と基板とを前記接着性層を介して接着させる工程の後、かつ、前記被処理部材の前記第１の面とは反対側の第２の面に対して、機械的または化学的な処理を施し、処理済部材を得る工程の前に、前記接着性層を５０℃〜３００℃の温度で加熱する工程をさらに有する、＜１０＞〜＜１２＞のいずれかに記載の半導体装置の製造方法。
＜１４＞前記接着性層から前記処理済部材を分離する工程が、前記接着性層に剥離液を接触させる工程を含む、＜１０＞〜＜１３＞のいずれかに記載の半導体装置の製造方法。
＜１５＞前記被処理部材の第１の面上であって、前記被処理部材と前記接着性層の間に保護層を有している、＜１０＞〜＜１４＞のいずれかに記載の半導体装置の製造方法。
＜１６＞金属基板と、（Ａ）ラジカル重合性モノマー、（Ｂ）高分子化合物、（Ｃ）芳香族ケトン化合物および（Ｄ）アミン化合物を含有し、実質的に溶剤を含まない接着性層を有する接着性支持体。
＜１７＞金属基板と、（Ａ）ラジカル重合性モノマー、（Ｂ）高分子化合物、（Ｃ）芳香族ケトン化合物および（Ｄ）アミン化合物を含有する接着性層を有し、前記接着性層は、（Ａ）ラジカル重合性モノマーの含有量が相対的に多い領域と、（Ａ）ラジカル重合性モノマーの含有量が相対的に少ない領域を有する接着性支持体。
＜１８＞金属基板と、（Ａ）ラジカル重合性モノマー、（Ｂ）高分子化合物、（Ｃ）芳香族ケトン化合物および（Ｄ）アミン化合物を含有する接着性層を有し、前記接着性層は、（Ａ）ラジカル重合性モノマーの含有量が相対的に多い領域と、（Ａ）ラジカル重合性モノマーの含有量が相対的に少ない領域を有し、前記（Ａ）ラジカル重合性モノマーの含有量が相対的に多い領域は、（Ａ）ラジカル重合性モノマーの含有量が相対的に少ない領域の３倍以上の（Ａ）ラジカル重合性モノマーを含む接着性支持体。 Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <18>.
<1> A temporary adhesive for manufacturing a semiconductor device comprising (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound.
<2> Furthermore, (C) the aromatic ketone compound is at least one selected from acetophenone compounds, benzophenone compounds, thioxanthone compounds, anthraquinone compounds, xanthone compounds, and benzoin compounds, <1> The temporary adhesive for semiconductor device manufacture of description.
<3> (D) The temporary provision for manufacturing a semiconductor device according to <1> or <2>, wherein the amine compound is at least one selected from dialkylaminobenzoates, aminoacetic acids and aminoacetic esters. adhesive.
<4> The temporary adhesive for manufacturing a semiconductor device according to any one of <1> to <3>, further comprising (E) a thermal radical polymerization initiator.
<5> (E) The temporary adhesive for manufacturing a semiconductor device according to any one of <1> to <4>, wherein the thermal radical polymerization initiator is at least one selected from an organic oxide and an azo compound.
<6> Any one of <1> to <5>, wherein the ratio (mass ratio) of (C) the aromatic ketone compound and (D) the amine compound is 1: 0.1 to 1:10 Temporary adhesive for semiconductor device manufacture described in 2.
<7> (C) The temporary adhesive for manufacturing a semiconductor device according to any one of <1> to <6>, wherein the aromatic ketone compound is a compound represented by the following formula (1).

(In the formula (1), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, an OH group or a monovalent organic group. R ¹ represents a hydrogen atom or The group represented by R ¹ may be linked to any of R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ to form a ring structure.
<8> (D) The amine compound is a secondary or tertiary amine compound, and has at least one of a hydroxyl group, an ester (—C (═O) O—), and a carboxy group in the molecule. The temporary adhesive for semiconductor device manufacture in any one of <1>-<7> which is a compound which is.
An adhesive support comprising a <9> substrate and an adhesive layer formed on the substrate by the temporary adhesive for manufacturing a semiconductor device according to any one of <1> to <8>.
<10> a step of bonding the first surface of the member to be processed and the substrate via an adhesive layer formed of the temporary adhesive for manufacturing a semiconductor device according to any one of <1> to <8>;
Applying a mechanical or chemical treatment to a second surface opposite to the first surface of the member to be treated to obtain a treated member; and
The manufacturing method of the semiconductor device which has the said processed member which has the process of isolate | separating the said adhesive layer and the said processed member.
<11> The surface of the adhesive layer that is bonded to the first surface of the member to be processed before the step of bonding the first surface of the member to be processed and the substrate through the adhesive layer. The method of manufacturing a semiconductor device according to <10>, further comprising a step of irradiating the actinic ray, radiation, or heat.
<12> The method for producing a semiconductor device according to <11>, wherein the actinic ray or radiation is an actinic ray having a wavelength of 350 to 450 nm.
<13> After the step of bonding the first surface of the member to be processed and the substrate via the adhesive layer, and on the second surface opposite to the first surface of the member to be processed On the other hand, before the step of performing a mechanical or chemical treatment to obtain a treated member, the method further comprises a step of heating the adhesive layer at a temperature of 50 ° C. to 300 ° C. <10> to <12> A method for manufacturing a semiconductor device according to any one of the above.
<14> The method for manufacturing a semiconductor device according to any one of <10> to <13>, wherein the step of separating the treated member from the adhesive layer includes a step of bringing a release liquid into contact with the adhesive layer. .
<15> The surface according to any one of <10> to <14>, which is on the first surface of the member to be processed and has a protective layer between the member to be processed and the adhesive layer. A method for manufacturing a semiconductor device.
<16> a metal substrate, an adhesive layer containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound, and substantially free of a solvent. Having an adhesive support.
<17> A metal substrate, and an adhesive layer containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound, and the adhesive layer is (A) An adhesive support having a region having a relatively high content of radical polymerizable monomer and (A) a region having a relatively low content of radical polymerizable monomer.
<18> a metal substrate, and an adhesive layer containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound, and the adhesive layer is , (A) a region having a relatively high content of radical polymerizable monomer, and (A) a region having a relatively low content of radical polymerizable monomer, wherein the content of (A) the radical polymerizable monomer The region having a relatively large amount of (A) is an adhesive support comprising (A) a radically polymerizable monomer three times or more of a region having a relatively low content of the radically polymerizable monomer.

  According to the present invention, when performing mechanical or chemical treatment on a member to be treated, the member to be treated can be temporarily supported by a high adhesive force, and the treated member can be temporarily treated without damaging the treated member. It has become possible to provide a temporary adhesive for manufacturing a semiconductor device, an adhesive support using the same, and a method for manufacturing a semiconductor device that can be easily released from the support.

1A and 1B are a schematic cross-sectional view illustrating temporary bonding between an adhesive support and a device wafer, and a schematic cross-section illustrating a state in which the device wafer temporarily bonded by the adhesive support is thinned. FIG. It is a schematic sectional drawing explaining cancellation | release of the temporary adhesion state of the conventional adhesive support body and a device wafer. 3A, 3B, 3C, and 3D are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer with a protective layer, respectively, and a device wafer with a protective layer temporarily bonded by the adhesive support FIG. 2 is a schematic cross-sectional view showing a state in which a thin film is thinned, a schematic cross-sectional view showing a thin device wafer with a protective layer peeled from an adhesive support, and a schematic cross-sectional view showing a thin device wafer. 4A and 4B are a schematic cross-sectional view illustrating a state in which a device wafer temporarily bonded by an adhesive support is thinned, and a device wafer with a protective layer temporarily bonded by an adhesive support, respectively. It is a schematic sectional drawing explaining the state reduced in thickness. FIG. 5A shows a schematic cross-sectional view illustrating exposure of the adhesive support, and FIG. 5B shows a schematic top view of the mask. 6A shows a schematic cross-sectional view of a pattern-exposed adhesive support, and FIG. 6B shows a schematic top view of the pattern-exposed adhesive support. The schematic sectional drawing explaining irradiation of actinic light or a radiation, or a heat | fever with respect to an adhesive support body is shown.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of a group (atomic group) in this specification, the description which does not indicate substitution and non-substitution includes 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).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. In the present invention, “light” means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure by far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc. It also means drawing with particle beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a mass average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. say.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.

The temporary adhesive for manufacturing a semiconductor device of the present invention (hereinafter also simply referred to as “temporary adhesive”) includes (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound, and (D ) Contains an amine compound.
According to the temporary adhesive for manufacturing a semiconductor device of the present invention, when a member to be processed is subjected to mechanical or chemical treatment, the member to be processed can be temporarily supported by a high adhesive force, and the processed member is damaged. The temporary adhesive for semiconductor device manufacture which can cancel | release temporary support with respect to a processed member without obtaining is obtained.
The temporary adhesive for manufacturing a semiconductor device of the present invention is preferably for forming a silicon through electrode. 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.

(A) Radical polymerizable monomer In the present invention, any (A) temporary polymerizable adhesive radical polymerizable monomer (hereinafter sometimes simply referred to as “polymerizable monomer”) can be used. Here, the radical polymerizable monomer has a radical polymerizable group. The radical polymerizable group is typically a group that can be polymerized by irradiation with actinic rays or radiation, or by the action of radicals.
The radical polymerizable monomer is a compound different from the binder. The polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is. The molecular weight is usually 100 or more.

  The polymerizable group is preferably, for example, a functional group that can undergo an addition polymerization reaction, and examples of the functional group that can undergo an addition polymerization reaction include an ethylenically unsaturated bond group. The polymerizable group may be a functional group capable of generating a radical upon irradiation with light. Examples of such a polymerizable group include a thiol group and a halogen group. Of these, the polymerizable group is preferably an ethylenically unsaturated bond group. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.

Specifically, the radically polymerizable compound is selected from compounds having at least one radically polymerizable group, preferably 2 or more, and more preferably a compound having 2 to 6 radically polymerizable groups. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The radically polymerizable compound in the present invention may be used alone or in combination of two or more.
The radical polymerizable group is preferably an ethylenically unsaturated group. The ethylenically unsaturated group is preferably a styryl group, a (meth) acryloyl group, or an allyl group, more preferably a (meth) acryloyl group, and even more preferably a (meth) acryloyloxy group.

  More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether, or the like is used instead of the unsaturated carboxylic acid.

  Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Intererythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide (EO) modified tri Examples include acrylates and polyester acrylate oligomers.

  Methacrylic acid esters include 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-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  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 acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, 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 also preferably used.
As commercial products, A-DCP, DCP and A-DPH (all manufactured by Shin-Nakamura Chemical Co., Ltd.) can be used.

  Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

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

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) 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 such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.

  Moreover, as a radically polymerizable compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP2009-288705A can be preferably used in the present invention.

The radical polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (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 Polyfunctional alcohols such as anurate, glycerin and trimethylolethane, which are added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51- Urethane (meth) acrylates as described in JP-B-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.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable radical polymerizable compounds, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. It is also possible to use a compound having a functionality or higher, a cardo resin.
Further, other examples of the radical polymerizable compound include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  In addition to the above, radically polymerizable compounds 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 said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an -OC (= O) C (CH 3) = groups represented by CH _2.
Specific examples of the radical polymerizable compound represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  In addition, compounds described in JP-A-10-62986 as general formulas (1) and (2), together with specific examples thereof, are compounds that have been (meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol. Can be used as a radically polymerizable compound.

  Among them, as the radical polymerizable compound, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by Co., Ltd.) (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Corporation) 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 compound is a polyfunctional monomer and may have an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxy group as in the case of a mixture as described above, this can be used as it is, but in the need, the hydroxyl group of the above-mentioned ethylenic compound can be used. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous 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 non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and 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.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a radically polymerizable compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

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

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

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

In the general formulas (i) and (ii), E represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —, respectively, Each represents an integer of 0 to 10, and X represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxy group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10, respectively, and the sum of each m is an integer of 0-40. However, when the sum of each m is 0, any one of X is a carboxy group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10, respectively, and the sum of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxy group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, 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 The form which couple | bonds with is preferable.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the radically polymerizable compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the 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 include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available radical polymerizable compounds represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds. Compounds can also be used.
Commercially available products of radically polymerizable compounds include 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 -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  As the radical polymerizable compound, a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable. Particularly preferred are those represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n represents 2 to 4).

  If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in a temporary adhesive, it adds in 0.3-8.9 mass% with respect to the total solid content except a solvent, More preferably, it adds in 0.8-6.4 mass%. It is desirable to do. By adding the polyfunctional thiol, the stability, odor, sensitivity, adhesion, etc. of the temporary adhesive can be improved.

  About the radically polymerizable compound, details of the usage method such as its structure, single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the temporary adhesive. For example, from the viewpoint of sensitivity (efficiency in reducing adhesiveness with respect to irradiation with actinic rays or radiation), a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the adhesive layer, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. Furthermore, it is also preferable to use a radically polymerizable compound having a trifunctional or higher functional group and different ethylene oxide chain length. In addition, selection and use of radically polymerizable compounds is an important factor for compatibility and dispersibility with other components (such as polymer compound (B)) contained in the temporary adhesive. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving the adhesion with the carrier substrate.

  The content of the polymerizable monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 40% by mass or more with respect to the total solid content of the temporary adhesive from the viewpoint of good adhesive strength and peelability. Is more preferable. Moreover, 90 mass% or less is preferable, 80 mass% or less is more preferable, 75 mass% or less is further more preferable, and 70 mass% or less is especially preferable.

(B) High molecular compound The temporary adhesive for semiconductor device manufacture of this invention is excellent in applicability | paintability by containing a high molecular compound. Here, the coating property means the uniformity of the film thickness after coating and the film forming property after coating.
In the present invention, any polymer compound can be used.
For example, hydrocarbon resin, polystyrene resin (for example, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer (AS resin), methyl methacrylate / styrene copolymer (MS resin) are included. ), Novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polyethylene resin, polypropylene, polyvinyl chloride resin, polyvinyl acetate resin, Teflon (registered trademark) ), (Meth) acrylic resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, police Sulfone resin, polyether sulfone resin, polyarylate resin, polyether ether ketone resin, and synthetic resins such as polyamide-imide resins, and natural resins such as natural rubber. Among these, hydrocarbon resin, ABS resin, AS resin, MS resin, polyurethane resin, novolac resin, and polyimide resin are preferable, hydrocarbon resin and MS resin are more preferable, and acrylic resin, ABS resin, AS resin, and MS resin are more preferable. ABS resin, AS resin, and MS resin are particularly preferable.
In this invention, you may use a binder in combination of 2 or more type as needed.

In the present invention, any hydrocarbon resin can be used.
The hydrocarbon resin in the present invention basically means a resin composed of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, to a hydrocarbon resin consisting of only 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 based on the total repeating unit of the resin. Is preferred.

  Examples of hydrocarbon resins that meet 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, and 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, inden petroleum Resin, polystyrene-polyolefin copolymer, olefin polymer (for example, methylpentene copolymer), and cycloolefin polymer (for example, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), etc. Is mentioned.

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

  Specific examples of the polystyrene resin include polystyrene, styrene / acrylonitrile resin, acrylonitrile / butadiene / styrene resin, and methyl methacrylate / styrene resin. A methyl methacrylate / styrene resin is preferable. Since the heat resistance with respect to the high temperature process of a semiconductor substrate is calculated | required, the generation amount of the outgas at the time of 250 degreeC heating is 3 mass% or less. More preferably, the resin is 2% by mass or less. As commercial products of methyl methacrylate / styrene resin, styrene MS-200NT, MS-300, MS-500, MS-600 (Nippon Steel & Sumikin Chemical Co., Ltd.), Sebian MAS10, MAS30 (Daicel Polymer Co., Ltd.) are most preferable. Can be used.

  Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following general formula (II), and at least one repeating unit represented by the general formula (I). An addition (co) polymer further comprising a species or more is mentioned. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).

In formula, m represents the integer of 0-4. R ^{1 to} R ⁶ each 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 are each a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. A hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, — (CH ₂ ) nCOOR ¹¹ , — (CH ₂ ) nOCOR ¹² , — (CH ₂ ) nNCO, — (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 Y ¹ , X ² and Y ² , or (—CO) ₂ O and (—CO) ₂ NR ¹⁷ composed of X ³ and Y ³ are represented. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z is a carbon atom 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, and —OCOR ¹⁸ or represents -OR ^18, p represents an an integer of 0 to 3). n represents an integer of 0 to 10.

The norbornene-based polymer is disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1, WO2004 / 070463A1, and the like. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization. This norbornene polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C), APL6015T (Tg145 ° C), etc. There are grades. Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics.
Furthermore, Appear 3000 is sold 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, and JP-A-2003-1159767. Alternatively, as disclosed in JP-A-2004-309979, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.
In the general formula (III), R ⁵ and R ⁶ are preferably hydrogen atoms or methyl groups, X ³ and Y ³ are preferably hydrogen atoms, and other groups are appropriately selected. This norbornene-based polymer is sold under the trade name Arton G or Arton F by JSR Co., Ltd., and Zeonor ZF14, ZF16, Zeonex 250, Nippon Zeon Co., Ltd., These are commercially available under the trade names 280 and 480R, and these can be used.

  The polystyrene equivalent weight average molecular weight of the polymer compound by gel per emission chromatography (GPC) method is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, It is more preferable that it is 100,000-300,000.

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 with respect to the total solid content of the temporary adhesive of the present invention. Is more preferable.
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. More preferably, it is particularly preferably 40% by mass or less.

  Further, the content ratio (mass ratio) of the radical polymerizable monomer and the polymer compound (radical polymerizable monomer / polymer compound) is preferably 90/10 to 10/90, and preferably 80/20 to 20 /. 80 is more preferable, and 70/30 to 30/70 is even more preferable.

(C) Aromatic ketone compound The aromatic ketone compound used in the present invention is not particularly defined as long as it has an aromatic group and has a ketone group, and widely known compounds can be used. In the present invention, the ketone group is preferably bonded to an aromatic group. With such a structure, it becomes easy to absorb light, and the effect of the present invention is more effectively exhibited. In the present invention, unlike the thermal radical polymerization initiator and the like, the aromatic ketone compound excited by the absorption of light activates the amine compound, thereby achieving the effects of the present invention.
Hereinafter, specific compounds of the aromatic ketone compound used in the present invention will be described.

（式（１）中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ、水素原子、ハロゲン原子、ＯＨ基または一価の有機基を表す。Ｒ¹は、水素原子または一価の有機基を表す。Ｒ¹で表される基は、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶のいずれかの基と連結し、環構造を形成してもよい。） Examples of the aromatic ketone compound include compounds represented by the following formula (1).
Formula (1)

(In the formula (1), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, an OH group or a monovalent organic group. R ¹ represents a hydrogen atom or The group represented by R ¹ may be linked to any of R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ to form a ring structure.

上記２つのＲは、それぞれ、水素原子または置換基を表し、互いに、結合して環を形成してもよい。２つのベンゼン環は、置換基を有していても良い。 The aromatic ketone compound used in the present invention preferably has a structure having two or more aromatic rings in the molecule, and more preferably a compound having the following skeleton.

The two R's each represent a hydrogen atom or a substituent, and may be bonded to each other to form a ring. The two benzene rings may have a substituent.

  Examples of monovalent organic groups include organic groups composed of 3 to 10 non-metallic atoms, such as 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 atoms. Organic groups composed of at least one element selected from up to oxygen atoms, up to 1 to 100 hydrogen atoms, and up to 0 to 20 sulfur atoms.

The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. Examples of alkenyl groups include vinyl, allyl, prenyl, geranyl, oleyl and the like. Examples of alkynyl groups include ethynyl group, propargyl group, trimethylsilylethynyl group and the like. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Furthermore, examples of the heterocyclic group include a furanyl group, a thiophenyl group, and a pyridinyl group.
The monovalent organic group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group. , Alkyl group, alkenyl group, alkynyl group, aryl group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonate Group, silyl group, heterocyclic group and the like. The organic group may contain an ether bond, an ester bond, or a ureido bond.
The monovalent organic group represented by R ¹ is preferably an aryl group, more preferably a phenyl group. The monovalent organic group may be linked to any of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ to form a ring structure.

  More specifically, examples of the compound represented by the formula (1) include acetophenone compounds, benzophenone compounds, thioxanthone compounds, anthraquinone compounds, xanthone compounds, and benzoin compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-2-morpholino-1- (4-methylthiophenyl). ) Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane -1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, preferably 2-methyl -2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4′-dimethoxybenzophenone, etc.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chloro-thioxanthone, and the like. .

  Examples of the anthraquinone compound include anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone and the like.

Xanthone is mentioned as a xanthone type compound.

Examples of the benzoin compounds include benzoin and benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzyl dimethyl ketal).

（式（２）中、Ｒ¹¹〜Ｒ¹⁸は、それぞれ、水素原子、ハロゲン原子、ＯＨ基または一価の有機基を表す。） Among the aromatic ketone compounds, specifically, a compound represented by the following formula (2) is preferable.
Formula (2)

(In formula (2), R ^{11 to} R ¹⁸ each represent a hydrogen atom, a halogen atom, an OH group, or a monovalent organic group.)

Specific examples of the monovalent organic group include the groups described above. Of these, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group are preferable. Specific examples of the alkyl group, alkenyl group, alkynyl group, and aryl group include those described in the above formula (1), and preferred ranges are also synonymous. R ^{11 to} R ¹⁸ are each preferably a hydrogen atom, a halogen atom, or an alkyl group.

As the thioxanthones represented by the above formula (2), specifically, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxy Thioxanthone and 2-chloro-thioxanthone, with 2-isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diethylthioxanthone being most preferred.
An aromatic ketone compound may be used alone or in combination of two or more.

  The molecular weight of the (C) aromatic ketone compound used in the present invention is preferably 200 to 2,000.

The compounding amount of the aromatic ketone compound (C) in the temporary adhesive of the present invention is preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass of the temporary adhesive including the solvent, and 0.2 -3.5 mass% is more preferable.
Moreover, 0.1-15 mass% is preferable and, as for the compounding quantity of (C) aromatic ketone compound with respect to the total solid of a temporary adhesive, 0.8-9 mass% is more preferable.

（式（３）中、Ｒ²¹およびＲ²²は、それぞれ、水素原子、アルキル基、またはアリール基を表す。Ｒ²³〜Ｒ²⁷としては、それぞれ、水素原子、ハロゲン原子、ＯＨ基または一価の有機基を表す。） (D) Amine compound As the amine compound, a known amine compound can be arbitrarily used, but a secondary or tertiary amine compound (more preferably a tertiary amine) is preferable, and a secondary or tertiary amine compound is used. A compound having at least one of a hydroxyl group, an ester (—C (═O) O—), and a carboxy group in the molecule is preferable.
The secondary amine or the tertiary amine can easily extract hydrogen radicals from the excited aromatic ketone compound, and can further promote the polymerization of the polymerizable monomer.
Anilines represented by the following formula (3) or glycines represented by the following formula (4) can be used more preferably, and anilines represented by the following formula (3) are more preferable.
Formula (3)

(In Formula (3), R ²¹ and R ²² each represent a hydrogen atom, an alkyl group, or an aryl group. R ^{23 to} R ²⁷ are each a hydrogen atom, a halogen atom, an OH group, or a monovalent group. Represents an organic group.)

As the alkyl group represented by R ²¹ and R ²² , an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, Examples include 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
The alkyl group or aryl group may be substituted with a substituent, and is preferably substituted with a carboxy group or an alkyloxycarbonyl group.

The monovalent organic group represented by R ^{23 to} R ²⁷ is preferably a monovalent organic group in the above formula (1), a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, or an amino group. , Alkyl group, alkenyl group, alkynyl group, aryl group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonate Group, silyl group, heterocyclic group and the like.
As R ^{23 to} R ²⁷ , at least one group is a carboxy group, a sulfonate group, a cyano group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a substituted sulfonyl group, a substituted carbonyl group, or a substituted sulfinyl group. Group, a sulfo group, a phosphono group, and a phosphonato group, and at least one is more preferably an alkyloxycarbonyl group.

In the present invention, one or both of R ²¹ and R ²² is a chain consisting of at least one —CH ₂ — and / or ester (—C (═O) O—), and the terminal thereof is a hydrogen atom, a hydroxyl group, Or a chain that is a carboxy group, or a chain consisting of at least one of R ^{23 to} R ²⁷ with at least one —CH ₂ — and / or ester (—C (═O) O—), the end of which is a hydrogen atom An atom, a hydroxyl group, or a carboxy group is preferred.

（式（４）中、Ｒ³¹およびＲ³²は、それぞれ、水素原子、アルキル基、またはアリール基を表す。Ｒ³³、Ｒ³⁴は、それぞれ、水素原子、ハロゲン原子、ＯＨ基または一価の有機基を表す。） Formula (4)

(In Formula (4), R ³¹ and R ³² each represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ represent a hydrogen atom, a halogen atom, an OH group, or a monovalent organic group, respectively. Represents a group.)

Specific examples of the monovalent organic group represented by R ³³ or R ³⁴ include those specifically mentioned for the monovalent organic group in formula (3). Among these, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group are preferable, and specific examples of these groups include the groups described above. R ^{33 to} R ³⁴ are preferably a hydrogen atom or an alkyl group.

R ³⁵ represents a hydrogen atom, an alkyl group, or an aryl group. Examples of the alkyl group are preferably alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, and 2-methylhexyl. Group, cyclopentyl group and the like. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰⁴ ) —, and R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R ¹⁰⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity. Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxy groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

  Specific examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, dialkylaminobenzoates (methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamino). Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-dimethylhexyl 4-dimethylaminobenzoate), N, N-dimethylparatoluidine, Michler's ketones (4,4′-bis (dimethylamino) benzophenone, 4,4 ′ -Bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone), aminoacetic acids (glycine, iminodiacetic acid, N-phenylglycine, N-phenyliminodiacetic acid), aminoacetic acid esters (glycine ethyl) Ester, glycine methyl ester, N- phenylglycine ethyl ester) and the like.

The molecular weight of the (D) amine compound used in the present invention is preferably 150 to 1,000.
One amine compound may be used alone, or two or more amine compounds may be mixed and used.

The compounding amount of the (D) amine compound in the temporary adhesive of the present invention is preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% of the temporary adhesive including the solvent. More preferable is 5% by mass.
Moreover, 0.1-15 mass% is preferable and, as for the compounding quantity of the (D) amine compound with respect to the total solid of a temporary adhesive, 0.8-9 mass% is more preferable.

(C) A combination of an aromatic ketone compound and (D) an amine compound includes thioxanthones and dialkylaminobenzoates (methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate). Acid isoamyl, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate), aminoacetic acids (glycine, iminodiacetic acid, N-phenylglycine, N-phenyliminodiacetic acid), or aminoacetic acid esters ( A combination of glycine ethyl ester, glycine methyl ester, and N-phenylglycine ethyl ester) is preferable, and a combination of thioxanthones and aminoacetic acids (glycine, iminodiacetic acid, N-phenylglycine, N-phenyliminodiacetic acid) is more preferable. Like .

  (C) Aromatic ketone compound and (D) amine compound are preferably in a mass ratio of 1: 0.1 to 1:10, more preferably 1: 0.5 to 1: 2.0, and 1: 0. 8 to 1: 1.5 is more preferable.

  The total mass of the (C) aromatic ketone compound and the (D) amine compound in the temporary adhesive of the present invention is 1.0 to 25.0% by mass relative to the total solid content of the temporary adhesive. Preferably, 2.0-20.0 mass% is more preferable, and 3.0-15.0 mass% is more preferable.

<Other ingredients>
<< Radical polymerization initiator >>
The temporary adhesive may contain (C) an aromatic ketone compound and (D) an amine compound, as well as any radical polymerization initiator, that is, a compound that generates radicals upon irradiation with actinic rays or radiation, or heat. .
By having a radical polymerization initiator, the adhesive layer is irradiated or heated with light, whereby the temporary adhesive is cured by radicals, and the adhesiveness in the light irradiation part or heating part can be reduced. If this irradiation or heating is performed on, for example, the central portion of the adhesive layer and the adhesiveness is left only at the peripheral edge, the area of the release layer that should be dissolved by solvent immersion during peeling is reduced, so the time required for peeling is shortened. There is an advantage that.

<<< Photoinitiator >>>
As the compound that generates radicals upon irradiation with actinic rays or radiation, for example, those known as photopolymerization initiators described below can be used.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) in the reactive compound having a polymerizable group as the polymerizable monomer. It can be selected appropriately. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.

  The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

  As the photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group) , Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, Azide compounds, metallocene compounds, organoboron compounds, iron arene complexes and the like can be mentioned.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in 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, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 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-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Further, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 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′-cal Nilbis (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, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine Oxides, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

As the photopolymerization initiator, an acylphosphine compound can also be suitably used. More specifically, for example, an acylphosphine oxide initiator described in Japanese Patent No. 4225898 can also be used.
As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  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 N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton Even if a compound described in US Pat. No. 7,556,910 contained in the same molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, etc. Good.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

  Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.

  For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer) using an ethyl acetate solvent is used. It is preferable to measure at a concentration of / L.

  You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

  As compounds that generate radicals upon irradiation with actinic rays or radiation, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers , An onium compound, a benzothiazole compound, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound are preferable.

  More preferably, it is a trihalomethyltriazine compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, or an onium compound, and at least selected from the group consisting of a trihalomethyltriazine compound, an oxime compound, and a triallylimidazole dimer. One type of compound is most preferred, and an oxime compound is most preferred.

<< Thermal radical polymerization initiator >>
As the compound that generates radicals by heat (hereinafter, also simply referred to as a thermal radical polymerization initiator), a known thermal radical polymerization initiator can be used.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable monomer. In the case of performing temporary adhesion between the member to be treated and the adhesive support after irradiating heat to the adhesive layer formed using the temporary adhesive by adding a thermal radical polymerization initiator, As the crosslinking reaction proceeds in the reactive compound having a crosslinkable group by heat, the adhesiveness (that is, tackiness and tackiness) of the adhesive layer can be lowered in advance, as will be described in detail later.
On the other hand, in the case of the reactive compound having a crosslinkable group by heat in the case where heat is applied to the adhesive layer in the adhesive support after temporary bonding between the member to be processed and the adhesive support. By proceeding with the crosslinking reaction, the adhesive layer becomes tougher, and cohesive failure of the adhesive layer that is likely to occur when the member to be treated is subjected to mechanical or chemical treatment can be suppressed. That is, the adhesiveness in the adhesive layer can be improved.
Preferred thermal radical polymerization initiators include compounds that generate radicals upon irradiation with actinic rays or radiation as described above, and compounds having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It can be preferably used.
Thermal radical polymerization initiators include onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond And azo compounds. Among these, organic peroxides or azo compounds are more preferable, and organic peroxides are particularly preferable.
Specific examples of the organic peroxide include lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxyacetate, Examples thereof include t-butyl peroxypivalate.
In addition to the above, specific examples of the thermal radical polymerization initiator used in the present invention include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554, the contents of which are incorporated herein. It is.
Only one type of thermal radical polymerization initiator may be used, or two or more types may be blended.

When the polymerization initiator is contained, the content of the polymerization initiator in the present invention is 0.1% by mass or more and 50% by mass or less based on the total solid content of the temporary adhesive. More preferably, it is 0.1 mass% or more and 30 mass% or less, More preferably, it is 0.1 mass% or more and 20 mass% or less.
In the present invention, it is also exemplified as a preferable embodiment that a photopolymerization initiator is not substantially blended. For example, it can be 0.1 mass% or less of the total solid content of the temporary adhesive.
In the present invention, it is also exemplified as a preferable embodiment that a thermal polymerization initiator is not substantially blended. For example, it can be 0.1 mass% or less of the total solid content of the temporary adhesive.

<Chain transfer agent>
The temporary adhesive for manufacturing a semiconductor device of the present invention preferably contains a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by Polymer Society, 2005) pages 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 low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) are preferably used for the temporary adhesive. be able to.

The content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the temporary adhesive. is there.
Only one type of chain transfer agent may be used, or two or more types may be blended.

<Polymerization inhibitor>
In order to prevent unnecessary thermal polymerization of the polymer compound (A) and the radical polymerizable monomer (B) during the production or storage of the temporary adhesive, the temporary adhesive of the present invention contains a small amount of a polymerization inhibitor. It is preferable to add.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol). ), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxylamine aluminum salt.
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.
Only one type of polymerization inhibitor may be used, or two or more types may be blended.

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the temporary adhesive of the present invention, and it is applied to the surface of the adhesive layer during the drying process after coating. 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.
Only one type of higher fatty acid derivative may be used, or two or more types may be blended.

<Solvent>
When the temporary adhesive of the present invention is layered by coating, it is preferable to mix a solvent.
Any known solvent can be used without limitation as long as an adhesive layer can be formed.

  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, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (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- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And 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 and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as toluene And xylene are preferred.

  These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl 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 applicability, the content of the solvent in the temporary adhesive coating solution is preferably such that the total solid concentration of the temporary adhesive is 5 to 80% by mass, more preferably 5 to 70% by mass. 10 to 60% by mass is preferable.
Only one type of solvent may be used, or two or more types of solvents may be blended.

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

In particular, the temporary adhesive of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. Liquidity can be further improved.
That is, when a film is formed using a coating liquid to which a temporary adhesive containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant 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. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid-saving properties, and has good solubility in the temporary adhesive.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant 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 polyflow 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.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and 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 can be added to various additives such as a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an oxidation as long as the effects of the present invention are not impaired. An inhibitor, an ultraviolet absorber, an aggregation inhibitor and the like can be blended. When blending these additives, 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 manufacturing a semiconductor device using the temporary adhesive for manufacturing a semiconductor device of the present invention described above will be described.
The manufacturing method of the semiconductor manufacturing apparatus of the present invention includes the step of bonding the first surface of the member to be processed and the substrate via the adhesive layer formed from the temporary adhesive for manufacturing a semiconductor device of the present invention, A step of applying a mechanical or chemical treatment to 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 It has the process of isolate | separating.
Further, before the step of bonding the first surface of the member to be processed and the substrate through the adhesive layer, the surface of the adhesive layer to be bonded to the first surface of the member to be processed. On the other hand, it is preferable to further include a step of irradiating the actinic ray, radiation or heat. The actinic ray or radiation is preferably actinic rays having a wavelength of 350 to 450 nm.
In addition, the method for manufacturing a semiconductor device of the present invention includes the step of bonding the first surface of the member to be processed and the substrate through the adhesive layer, and the first surface of the member to be processed. Is a step of heating the adhesive layer at a temperature of 50 ° C. to 300 ° C. prior to the step of subjecting the second surface on the opposite side to mechanical or chemical treatment to obtain a treated member. It is preferable to have.
Moreover, it is preferable that the process of isolate | separating the said processed member from the said adhesive layer includes the process which makes a peeling liquid contact the said adhesive layer. Furthermore, it is preferable that a protective layer is provided on the first surface of the member to be processed and between the member to be processed and the adhesive layer. That is, the treated member can be separated from the adhesive layer by dissolving the protective layer with the release liquid.
Details of these will be described below.

  1A and 1B are a schematic cross-sectional view illustrating temporary bonding between an adhesive support and a device wafer, and a schematic cross-section illustrating a state in which the device wafer temporarily bonded by the adhesive support is thinned. 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.
The material of the carrier substrate 12 is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, and a metal substrate. However, a silicon substrate that is typically used as a substrate of a semiconductor device is hardly contaminated, and a semiconductor device is manufactured. In view of the fact that an electrostatic chuck widely 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.

The 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) a radical polymerizable monomer, (B) a polymer compound, and (C) an aromatic ketone compound. And (D) It is preferable to have an adhesive layer containing an amine compound and substantially free of a solvent.
Further, the adhesive support 100 has a metal substrate and an adhesive layer containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound. In addition, the adhesive layer is preferably an aspect having a region where the content of the radically polymerizable monomer (A) is relatively high and a region where the content of the radically polymerizable monomer is relatively low (A). . Further, the adhesive support 100 has a metal substrate and an adhesive layer containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound. The adhesive layer has (A) a region having a relatively high content of radical polymerizable monomer and (A) a region having a relatively low content of radical polymerizable monomer. The region having a relatively high content of radically polymerizable monomer may be an embodiment containing (A) a radically polymerizable monomer that is three times or more of the region having a relatively low content of the (A) radically polymerizable monomer. More preferred.

The adhesive layer 11 is formed by applying the temporary adhesive for manufacturing a semiconductor device of the present invention to a carrier substrate 12 using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. In addition, when a protective layer to be described later is provided, it can be formed by applying (preferably coating) 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, more preferably 1 to 10 μm, but is not particularly limited.

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

As shown in FIG. 1A, a device wafer 60 (member to be processed) is formed by providing a plurality of device chips 62 on a surface 61 a of a silicon substrate 61.
Here, the thickness of the silicon substrate 61 is in the range of 200 to 1200 μm, for example.
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 are bonded, and the adhesive support 100 and the device wafer 60 are temporarily bonded.
After that, if necessary, the adhesive body between the adhesive support 100 and the device wafer 60 may be heated (heated) to make the adhesive layer more adhesive. As a result, the anchor effect at the interface between the adhesive support and the member to be processed is promoted, and cohesive failure of the adhesive layer is likely to occur when the device wafer 60 is subjected to mechanical or chemical treatment described later. Therefore, the adhesiveness 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 further preferably 80 ° C to 220 ° C.
In this case, the heating time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, and further preferably 40 seconds to 3 minutes.

Next, as shown in FIG. 1B, the back surface 61b 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 (for example, a thickness of 1 to 200 μm) to obtain a thin device wafer 60 ′.
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b ′ of the thin device wafer 60 ′ after the thinning process, and the silicon is penetrated into the through hole. You may perform the process which forms an electrode (not shown) as needed.

Next, 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 the adhesive layer 110 is brought into contact with the stripping solution, and then the thin device wafer 60 ′ is slid with respect to the adhesive support 100 as necessary. Alternatively, it is preferable that the thin device wafer 60 ′ is peeled off from the adhesive support 100. Since the temporary adhesive of the present invention has a high affinity for the stripping solution, the temporary adhesion between the adhesive layer 110 and the surface 61a of the thin device wafer 60 ′ can be easily released by the above method.

  After the thin device wafer 60 ′ is detached from the adhesive support 100, various known processes are performed on the thin device wafer 60 ′ as necessary to manufacture a semiconductor device having the thin device wafer 60 ′. To do.

<Release solution>
Hereinafter, the stripping solution will be described in detail.

As the stripping solution, water and a solvent (organic solvent) can be used. Moreover, as a peeling liquid, organic solvents, such as acetone and p-menthane, are preferable.
Furthermore, from the viewpoint of peelability, the stripping solution may contain an alkali, an acid, and a surfactant. When mix | blending these components, it is preferable that a compounding quantity is 0.1-5.0 mass% of stripping solution, respectively.
Further, from the viewpoint of peelability, a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.

  Examples of the alkali include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate. , Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine Emissions, 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.

  Acids include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, boric acid, 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, an anionic, cationic, nonionic or zwitterionic surfactant 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 making the content of the surfactant within the above-described range, the peelability between the adhesive support 100 and the thin device wafer 60 ′ tends to be further improved.

  Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxy Ethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene Examples thereof include alkyl phenyl ether phosphate esters, saponification products of styrene-maleic anhydride copolymers, partial saponification products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

  Although it does not specifically limit as a cationic surfactant, A conventionally well-known thing can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

  The nonionic surfactant is not particularly limited, but is a 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 adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, 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 these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.

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

  Further, if necessary, additives such as an antifoaming agent and a hard water softening agent can be contained.

Next, a conventional embodiment will be described.
FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 2, an adhesive support in which an adhesive layer 11 ′ formed of a conventional temporary adhesive is provided on a carrier substrate 12 as an adhesive support. Otherwise, the adhesive support 100 ′ and the device wafer are temporarily bonded in the same manner as described with reference to FIGS. 1A and 1B, and the silicon substrate is thinned on the device wafer. Then, similarly to the above-described procedure, the thin device wafer 60 ′ is peeled from the adhesive support 100 ′.

However, according to the conventional temporary adhesive, it is difficult to easily release the temporary support for the processed member without temporarily damaging the processed member with high adhesive force and damaging the processed member. For example, in order to make sufficient temporary adhesion between the device wafer and the carrier substrate, if a highly temporary adhesive is used among the conventional temporary adhesives, the temporary adhesion between the device wafer and the carrier substrate tends to be too strong. Become. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. When the device wafer 60 ′ is peeled off, there is a tendency that the device chip 62 is damaged due to the bump 63 being detached from the device chip 62 provided with the bump 63.
On the other hand, when a conventional temporary adhesive having low adhesiveness is adopted, temporary support to the processed member can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. A problem that the wafer cannot be reliably supported by the carrier substrate is likely 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 applied to the adhesive layer 11 as a peeling solution. Can be easily released by bringing them into contact. That is, according to the temporary adhesive of the present invention, the device wafer 60 can be temporarily supported by a high adhesive force, and the temporary support for the thin device wafer 60 ′ can be easily released without damaging the thin device wafer 60 ′. .

  3A, 3B, 3C, and 3D are schematic cross-sectional views illustrating temporary bonding between an adhesive support and a device wafer with a protective layer, respectively, and a device wafer with a protective layer temporarily bonded by the adhesive support FIG. 2 is a schematic cross-sectional view showing a state in which a thin film is thinned, a schematic cross-sectional view showing a thin device wafer with a protective layer peeled from an adhesive support, and a schematic cross-sectional view showing a thin device wafer.

  4A and 4B are a schematic cross-sectional view illustrating a state in which a device wafer temporarily bonded by an adhesive support is thinned, and a device wafer with a protective layer temporarily bonded by an adhesive support, respectively. It is a schematic sectional drawing explaining the state reduced in thickness.

In the above-described first embodiment of the present invention, as shown in FIG. 3A, a device wafer 160 with a protective layer (member to be processed) may be used instead of the device wafer 60.
Here, the protective layer-equipped device wafer 160 is provided on the surface 61a of the silicon substrate 61 (substrate to be processed) provided with a plurality of device chips 62 on the surface 61a and the surface 61a 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, a known layer can be used without limitation, but a layer that can reliably protect the device chip 62 is preferable.
As a material constituting the protective layer 80, any known compound can be used without limitation as long as it is intended to protect the substrate to be treated. 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 terephthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyethersulfone, polyarylate, polyetheretherketone, polyamideimide, etc. Synthetic resins and natural resins such as rosin and natural rubber can be preferably used. As a commercial item, ZEONEX480R (made by Nippon Zeon Co., Ltd.) etc. can be used preferably.
Moreover, the protective layer 80 can contain the compound which can 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 applied) on the carrier substrate 12 using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, and the like, and then dried. Can be formed. For example, the drying can be performed at 80 to 200 ° C. for 1 to 10 minutes.

  Then, the surface 160a of the protective layer-equipped device wafer 160 (the surface of the protective layer 80 opposite to the silicon substrate 61) 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 and the adhesive layer 21 are bonded, and the adhesive support 100 and the device wafer 160 with a protective layer are temporarily bonded.

  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 160 ′ with a protective layer is detached from the adhesive layer 11 of the adhesive support 100 to obtain a thin device wafer 160 ′ with a protective layer as shown in FIG. 3C. .

Then, by removing the protective layer 80 in the thin device wafer 160 ′ with the protective layer from the silicon substrate 61 ′ and the device chip 62, the device chip 62 is provided on the silicon substrate 61 ′ as shown in FIG. 3D. A thin device wafer is obtained.
As the removal of the protective layer 80, any known one can be employed. For example, (1) a method of dissolving and removing the protective layer 80 with a solvent; (2) attaching a peeling tape or the like to the protective layer 80 for protection A method of mechanically peeling the layer 80 from the silicon substrate 61 ′ and the device chip 62; (3) the protective layer 80 is exposed to light such as ultraviolet rays and infrared rays or laser irradiation to thereby form the protective layer 80. Examples of the method include decomposing and improving the peelability of the protective layer 80.
The above (1) and (3) have an advantage that the protective layer 80 can be easily removed because the action in these methods is performed on the entire surface of the protective film.
The above (2) has an advantage that it can be implemented without requiring a special apparatus at room temperature.

The form using the device wafer 160 with a protective layer instead of the device wafer 60 as the member to be processed is a thin device wafer TTV (Total Thickness) 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 (that is, when it is desired to further improve the flatness of the thin device wafer).
That is, when the device wafer 60 temporarily bonded by the adhesive support 100 is thinned, as shown in FIG. 4A, the concavo-convex shape of the device wafer 60 formed by the plurality of device chips 62 is a thin device wafer 60 ′. The back surface 61b ′ of the film tends to be transferred, and can be an element that increases TTV.
On the other hand, in the case of thinning the protective layer-equipped device wafer 160 temporarily bonded by the adhesive support 100, first, as shown in FIG. 4B, a plurality of device chips 62 are protected by the protective layer. It is possible to almost eliminate the uneven shape on the contact surface of the device wafer 160 with the protective layer with the adhesive support 110. Therefore, even when such a device wafer 160 with a protective layer is thinned while being supported by the adhesive support 110, the shape derived from the plurality of device chips 62 is the back surface 61b "of the thin device wafer 160 'with a protective layer. As a result, the TTV of the thin device wafer finally obtained can be further reduced.

Moreover, when the temporary adhesive of this invention contains the thermal radical polymerization initiator, the adhesive layer 11 can be made into the adhesive layer from which adhesiveness reduces by heat irradiation. In this case, specifically, the adhesive layer 11 is a layer having adhesiveness before being irradiated with heat, but the layer in which the adhesiveness is reduced or disappeared in the region irradiated with heat. It can be.
When the temporary adhesive of the present invention further contains a radical photopolymerization initiator, the adhesive layer 11 can be an adhesive layer whose adhesiveness is reduced by irradiation with actinic rays or radiation. In this case, specifically, the adhesive layer is a layer having adhesiveness before being irradiated with actinic rays or radiation. 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, the active ray or the active ray or the surface of the adhesive layer 11 of the adhesive support 100 is bonded to the device wafer 60. Radiation or heat may be irradiated.
For example, the adhesive layer is converted into an adhesive layer in which a low-adhesive region and a high-adhesive region are formed by irradiation with actinic light, radiation, or heat, and then temporarily bonded by an adhesive support of a member to be processed May be performed. Hereinafter, this embodiment will be described.

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

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

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

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

As described above, when the adhesive layer 11 is an adhesive layer whose adhesiveness is reduced by irradiation with actinic rays or radiation, the adhesive support 100 is formed as shown in FIG. As shown to 6B, it converts into the adhesive support body 110 which has the adhesive layer 21 in which the low adhesiveness area | region 21A and the high adhesiveness area | region 21B were formed in the center area | region and the peripheral area, respectively.
Here, the “low adhesion region” in the present specification means a region having lower adhesion compared to the “high adhesion region” and is a region having no adhesion (that is, “non-adhesion region”). Sex region "). Similarly, the “high adhesion region” means a region having higher adhesion than the “low adhesion region”.

  The adhesive support 110 is provided with the low adhesive region 21A and the high adhesive region 21B by pattern exposure using the mask 40, and the areas of the light transmitting region and the light shielding region in the mask 40 and The shape can be controlled on the order of microns or nanometers. Therefore, the area and shape of each of the high adhesive region 21B and the low adhesive region 21A formed on the adhesive layer 21 of the adhesive support 110 by pattern exposure can be finely controlled, so that the adhesive layer as a whole can be controlled. Adhesiveness can more reliably and easily temporarily support the silicon substrate 61 of the device wafer 60, and more easily release the temporary support of the thin device wafer 60 ′ to the silicon substrate without damaging the thin device wafer 60 ′. Highly accurate and easily controllable to the possible adhesiveness.

  Moreover, although the surface physical properties of the high adhesive region 21B and the low adhesive region 21A in the adhesive support 110 are different due to pattern exposure, they are integrated as a structure. Therefore, there is no significant difference in mechanical properties between the high adhesive region 21B and the low adhesive region 21A, and the surface 61a of the silicon substrate 61 of the device wafer 60 is bonded to the adhesive layer 21 of the adhesive support 110, Next, even if the back surface 61b of the silicon substrate 61 is subjected to a thinning process or a process of forming a silicon through electrode, the region of the back surface 61b corresponding to the high adhesive region 21B of the adhesive layer 21 and the low adhesive region 21A A difference in pressure (for example, grinding pressure or polishing pressure) related to the above processing hardly occurs between the corresponding back surface 61b regions, and the high adhesive region 21B and the low adhesive region 21A are used in the above processing. There is little impact on processing accuracy. This is particularly effective in obtaining a thin device wafer 60 ′ having a thickness of 1 to 200 μm, which is likely to cause the above problem.

  Therefore, in the form using the adhesive support 110, the silicon substrate 61 is temporarily supported more reliably and easily while suppressing the influence on the processing accuracy when the silicon substrate 61 of the device wafer 60 is subjected to the above processing. In addition, the temporary support to the thin device wafer 60 ′ can be easily released without damaging the thin device wafer 60 ′.

  Moreover, after converting the adhesive layer 11 to an adhesive layer whose adhesiveness is reduced from the inner surface on the substrate side of the adhesive layer toward the outer surface by irradiating with actinic rays or radiation or heat, You may perform temporary adhesion | attachment by the adhesive support body of a to-be-processed member. Hereinafter, this embodiment will be described.

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

First, by irradiating the outer surface of the adhesive layer 11 with actinic rays, radiation, or heat 50 ′, the adhesive support 100 is changed from the inner surface 31b on the substrate side to the outer surface 31a as shown in FIG. It is converted into an adhesive support 120 having an adhesive layer 31 whose adhesiveness has been lowered.
That is, the adhesive layer 31 has a low adhesive region 31A on the outer surface 31a side and a high adhesive region 31B on the inner surface 31b side.
Such an adhesive layer 31 is irradiated with actinic rays, radiation or heat 50, and the outer surface 31a is sufficiently irradiated with actinic rays, radiation or heat 50, but is active by the inner surface 31b. It can be easily formed by setting the irradiation amount such that the light beam, radiation, or heat 50 does not reach.
Here, such a change in the irradiation amount can be easily performed by changing the setting of the exposure device and the heating device, so that the equipment cost can be suppressed and the adhesive layers 21 and 31 can be formed in a large amount. It is not time consuming.
In the embodiment of the present invention described above, the structure is integrated by combining the adhesive layer 11 and the irradiation method, but the adhesion on the outer surface 31a is the adhesion on the inner surface 31b. Since the adhesive layer 31 is formed so as to be lower than the property, it is not necessary to provide a separate layer such as a separation layer.
As described above, the adhesive layer 31 can be easily formed.

Furthermore, each of the adhesiveness on the outer surface 31a and the adhesiveness on the inner surface 31b can be accurately controlled by selecting a material constituting the adhesive layer 11 and adjusting an irradiation amount of active light, radiation, or heat. Is.
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 easily supported by the silicon substrate 61 of the device wafer 60, and without damaging the thin device wafer 60 ′. The adhesiveness to such an extent that temporary support of the thin device wafer 60 ′ with respect to the silicon substrate can be easily released can be controlled with high accuracy and easily.

  Therefore, the form using the adhesive support 120 can also temporarily support the silicon substrate 61 more reliably and easily when the above-described processing is performed on the silicon substrate 61 of the device wafer 60, and damage the thin device wafer 60 ′. It is preferable that the temporary support to the thin device wafer 60 ′ can be released more easily without giving

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

  In the embodiment described above, the adhesive layer formed from the temporary adhesive for manufacturing a semiconductor device according to the present invention is provided on the carrier substrate before the device wafer is temporarily bonded, thereby constituting an adhesive support. However, the substrate to be processed may first be provided on a member to be processed such as a device wafer, and then the substrate to be processed provided with an adhesive layer may be temporarily bonded.

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

  The exposure is mask exposure through a mask, but may be selective exposure by drawing using an electron beam or the like.

  In the above-described embodiment, the adhesive layer has a single layer structure, but the adhesive layer may have a multilayer structure. As a method of forming an adhesive layer having a multilayer structure, before irradiating with actinic rays or radiation, a method of applying a temporary adhesive stepwise by the above-mentioned conventionally known method, or after irradiating with actinic rays or radiation And a method of applying a temporary adhesive by a conventionally known method. In the form in which the adhesive layer has a multilayer structure, for example, when the adhesive layer 11 is an adhesive layer whose adhesiveness is reduced by irradiation with active light, radiation, or heat, irradiation with active light, radiation, or heat Therefore, the adhesiveness of the adhesive layer as a whole can be reduced by reducing the adhesiveness between the respective layers. In the present invention, actinic rays or radiation is preferably actinic rays having a wavelength of 350 to 450 nm.

In the above-described embodiment, the silicon substrate is exemplified as the member to be processed supported by the adhesive support. However, the present invention is not limited to this, and in the semiconductor device manufacturing method, mechanical or chemical Any member to be processed that can be subjected to various processing may be used.
For example, the member to be processed can include a compound semiconductor substrate. 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. Can be mentioned.

  Further, in the above-described embodiment, the silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the adhesive support. However, the present invention is not limited to these, and any processing necessary in the method for manufacturing a semiconductor device can be used.

  In addition, the light transmissive region and the light shielding region in the mask, the high adhesive region and the low adhesive region in the adhesive layer, and the shape, size, number, arrangement location, etc. of the device chip in the device wafer, etc. Is arbitrary as long as the present invention can be achieved, and is not limited.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Formation of adhesive support>
Each of the following temporary adhesives was applied to a 4-inch Si wafer by a spin coater (Opticat MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa) and then baked at 100 ° C. for 30 seconds to provide an adhesive layer having a thickness of 3 μm. Wafer 1 (that is, an adhesive support) was formed.

<Temporary adhesive>
-The radically polymerizable monomer (A) described in the table-The mass part described in the X1 column of the above table-The polymer compound (B) described in the table-The mass part described in the X2 column of the above table-The aromatic ketone compound described in the table ( C) Mass parts described in X3 column of the above table / amine compounds described in the table (D) Mass radicals described in the X4 column of the above table / thermal radical polymerization initiator described in the table Mass parts described in the X5 column of the above table・ Polymerization inhibitor (p-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.008 parts by mass. Surfactant (PF6320, manufactured by OMNOVA) 0.032 parts by mass. Solvent (propylene glycol monopropyl ether acetate) 69.96 parts by mass.

<Radically polymerizable monomer (A)>
Polymerizable monomer (1): A-DCP (manufactured by Shin-Nakamura Chemical, bifunctional acrylate)
Polymerizable monomer (2): DCP (manufactured by Shin-Nakamura Chemical, bifunctional methacrylate)
Polymerizable monomer (3): A-DPH (manufactured by Shin-Nakamura Chemical, 6-functional acrylate)

<Polymer compound (B)>
Polymer compound (1): Methyl methacrylate-styrene random copolymer, Estylene MS200NT (manufactured by Nippon Steel Chemical Co., Ltd.)
Polymer compound (2): polymethyl methacrylate (manufactured by Aldrich, Mw: 12 million)
Polymer compound (3): acrylonitrile-styrene copolymer (manufactured by Aldrich, Mw: 185,000)

芳香族ケトン化合物（２）：２−イソプロピルチオキサントン

芳香族ケトン化合物（３）：２, ４−ジエチルチオキサントン

芳香族ケトン化合物（４）：２−ｔｅｒｔ−ブチルアントラキノン

芳香族ケトン化合物（５）：キサントン

芳香族ケトン化合物（６）：ベンゾイン

<Aromatic ketone compound (C)>
Aromatic ketone compound (1): Benzophenone

Aromatic ketone compound (2): 2-isopropylthioxanthone

Aromatic ketone compound (3): 2,4-diethylthioxanthone

Aromatic ketone compound (4): 2-tert-butylanthraquinone

Aromatic ketone compound (5): Xanthone

Aromatic ketone compound (6): Benzoin

アミン化合物（２）：４−ジメチルアミノ安息香酸エチル

アミン化合物（３）：Ｎ−フェニルグリシン

アミン化合物（４）：Ｎ−フェニルイミノジ酢酸

<Amine compound (D)>
Amine compound (1): Triethanolamine

Amine compound (2): ethyl 4-dimethylaminobenzoate

Amine compound (3): N-phenylglycine

Amine compound (4): N-phenyliminodiacetic acid

<Thermal radical polymerization initiator>
Thermal radical polymerization initiator (1): Park mill D (manufactured by NOF Corporation, dicumyl peroxide, decomposition temperature (10-hour half-life temperature = 116.4 ° C))

<Creation of processed material>
As a member to be processed without a protective layer, a 4-inch Si wafer was used as it was.
As a member to be processed having a protective layer, a 20 wt% p-menthane solution of the following protective layer compound was applied to a 4-inch Si wafer by a spin coater (Micosa Opticoat MS-A100, 1200 rpm, 30 seconds), By baking at 100 ° C. for 300 seconds, a wafer provided with a protective layer having a thickness of 20 μm was formed.
The wafer as a member to be processed is collectively referred to as a wafer 2 with or without a protective layer.

<Compound for protective layer>
Compound for protective layer (1): ZEONEX 480R (manufactured by Nippon Zeon Co., Ltd.)

<Creation of adhesive test piece>
As described in the following table, an adhesive test piece was prepared through each step in the order of exposure and pressure bonding using a temporary adhesive.

<< Exposure >>
A UV exposure apparatus (Hamamatsu Photonics) is applied to the central portion of the adhesive layer excluding the 3 mm circumference from the adhesive layer side of the wafer 1 through a PET mask that protects (shields) the 3 mm circumference of the adhesive layer. LC8, 200 W high stability mercury xenon lamp L10852) was used, and light transmitted through a bandpass filter (manufactured by Asahi Spectrometer Co., Ltd., center transmission wavelength 365 nm, MC 365/10 nm 50 × 50) was 2000 mJ / cm The exposure amount was ² .

<< crimping >>
Wafer 2 was laminated on the adhesive layer of wafer 1 and pressure bonded at 190 ° C. and 1 N / cm ² for 180 seconds. Here, when the wafer 2 is a 4-inch Si wafer provided with a protective layer, the protective layer and the adhesive layer of the wafer 1 were overlapped and pressure-bonded as described above.

<Measurement of adhesive strength of adhesive test piece>
The adhesive strength of the test specimens prepared under the conditions shown in the following table was determined using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N) at 250 mm / min. The tensile measurement was performed in the direction along the surface. The results are shown in the table below.

<Peelability>
The test piece prepared under the conditions described in the following table was pulled in the vertical direction of the adhesive layer under the condition of 250 mm / min, and the peelability was confirmed. Moreover, after heating the produced test piece for 30 minutes at 250 degreeC, it pulled similarly to the orthogonal | vertical direction of the adhesive layer on 250 mm / min conditions, and confirmed the peelability after a thermal process. “A” if the maximum peel force is less than 5N, “B” if the maximum peel force is 5N or more and less than 10N, “C” if the maximum peel force is 10N or more and less than 15N, “C”, the maximum peel force Is 15N or more, or “D” when the wafer is damaged. In addition, the presence or absence of the damage of Si wafer was confirmed visually.

As described above, the temporary adhesive for semiconductor device production containing (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound according to the present invention is adhesive. It was found that not only good results were obtained with respect to the peelability but also good results were obtained with respect to the peelability after the high temperature process (Examples 1 to 33).
In this way, the temporary adhesive of the present invention does not damage the processed member even after undergoing a high temperature process when performing mechanical or chemical processing on the processing target member (such as a semiconductor wafer), The temporary support for the processed member can be easily released.
Furthermore, the adhesive layer formed through the exposure process had no adhesive property in the region irradiated with light. With this technique, an adhesive support that can be adhered to the member to be processed can be formed only by the peripheral portion of the adhesive layer. When detaching the support, it is possible to further reduce internal damage of the device.

11, 11 ', 21, 31 Adhesive layer 12 Carrier substrate 21A, 31A Low adhesion region 21B, 31B High adhesion region 40 Mask 41 Light transmission region 42 Light shielding region 50 Actinic ray or radiation 50' Actinic ray or radiation or heat 60 Device wafer 60 ′ Thin device wafer 61, 61 ′ Silicon substrate 62 Device chip 63 Bump 70 Tape 80 Protective layer 100, 100 ′, 110, 120 Adhesive support 160 Device wafer with protective layer 160 ′ Thin device wafer with protective layer

Claims (15)

  A temporary adhesive for manufacturing a semiconductor device comprising (A) a radical polymerizable monomer, (B) a polymer compound, (C) an aromatic ketone compound and (D) an amine compound.   2. The semiconductor according to claim 1, wherein (C) the aromatic ketone compound is at least one selected from an acetophenone compound, a benzophenone compound, a thioxanthone compound, an anthraquinone compound, a xanthone compound, and a benzoin compound. Temporary adhesive for manufacturing equipment.   (D) The temporary adhesive for semiconductor device manufacture according to claim 1 or 2, wherein the amine compound is at least one selected from dialkylaminobenzoates, aminoacetic acids, and aminoacetic esters.   Furthermore, the temporary adhesive for semiconductor device manufacture of any one of Claims 1-3 containing (E) thermal radical polymerization initiator.   (E) The temporary adhesive for semiconductor device manufacture of any one of Claims 1-4 whose thermal radical polymerization initiator is at least 1 sort (s) selected from an organic oxide and an azo compound.   The ratio (mass ratio) of (C) the aromatic ketone compound and (D) the amine compound is 1: 0.1 to 1:10, according to any one of claims 1 to 5, Temporary adhesive for manufacturing semiconductor devices. (C) The temporary adhesive for semiconductor device manufacture of any one of Claims 1-6 whose aromatic ketone compound is a compound represented by following formula (1).

(In the formula (1), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, an OH group or a monovalent organic group. R ¹ represents a hydrogen atom or The group represented by R ¹ may be linked to any of R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ to form a ring structure.   (D) The amine compound is a secondary or tertiary amine compound having a hydroxyl group, an ester (—C (═O) O—), and a carboxy group in the molecule. The temporary adhesive for semiconductor device manufacture of any one of Claims 1-7.   The adhesive support body which has a board | substrate and the adhesive layer formed with the temporary adhesive agent for semiconductor device manufacture of any one of Claims 1-8 on the said board | substrate. A step of bonding the first surface of the member to be processed and the substrate via an adhesive layer formed by the temporary adhesive for manufacturing a semiconductor device according to any one of claims 1 to 8;
Applying a mechanical or chemical treatment to a second surface opposite to the first surface of the member to be treated to obtain a treated member; and
The manufacturing method of the semiconductor device which has the said processed member which has the process of isolate | separating the said adhesive layer and the said processed member.   Before the step of bonding the first surface of the member to be processed and the substrate via the adhesive layer, the surface of the adhesive layer to be bonded to the first surface of the member to be processed The method of manufacturing a semiconductor device according to claim 10, further comprising a step of irradiating the actinic ray, radiation, or heat.   12. The method of manufacturing a semiconductor device according to claim 11, wherein the actinic ray or radiation is an actinic ray having a wavelength of 350 to 450 nm.   After the step of bonding the first surface of the member to be processed and the substrate through the adhesive layer, and with respect to the second surface opposite to the first surface of the member to be processed, 13. The method according to claim 10, further comprising a step of heating the adhesive layer at a temperature of 50 ° C. to 300 ° C. before the step of performing a mechanical or chemical treatment to obtain a treated member. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.   The method for manufacturing a semiconductor device according to claim 10, wherein the step of separating the processed member from the adhesive layer includes a step of bringing a release liquid into contact with the adhesive layer.   The semiconductor device according to claim 10, further comprising a protective layer on the first surface of the member to be processed and between the member to be processed and the adhesive layer. Production method.

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