JP5687230B2 - Wafer processing body, wafer processing member, wafer processing temporary adhesive, and thin wafer manufacturing method - Google Patents

Description

  The present invention relates to a wafer processed body, a wafer processing member, a temporary adhesive for wafer processing, and a method for manufacturing a thin wafer, which can effectively obtain a thin wafer.

  Three-dimensional semiconductor mounting has become indispensable for realizing higher density, larger capacity, higher speed, and lower power consumption. The three-dimensional semiconductor mounting technology is a semiconductor manufacturing technology in which one semiconductor chip is thinned and further laminated in multiple layers while being connected by through silicon vias (TSVs). In order to realize this, it is necessary to thin the substrate on which the semiconductor circuit is formed by grinding a non-circuit forming surface (also referred to as “back surface”) and to form an electrode including TSV on the back surface.

  Conventionally, in a back grinding process of a silicon substrate, a protective tape is applied to the opposite side of the grinding surface to prevent wafer damage during grinding. However, this tape uses an organic resin film as a base material and is flexible, but has insufficient strength and heat resistance, and is not suitable for performing a TSV forming process or a wiring layer forming process on the back surface.

  In view of this, a system that can sufficiently withstand the processes of back grinding, TSV and back electrode formation by bonding a semiconductor substrate to a support such as silicon or glass via an adhesive layer has been proposed. In this case, what is important is an adhesive layer when the substrate is bonded to the support. This requires that the substrate can be bonded to the support without any gap, and has sufficient durability to withstand the subsequent process, and finally, the thin wafer must be easily peeled from the support. Thus, since it peels at the end, in this specification, this contact bonding layer will be called a temporary adhesive layer.

  Conventionally known temporary adhesive layer and its peeling method are as follows. The adhesive layer containing the light-absorbing substance is irradiated with high-intensity light, and the adhesive layer is separated from the support by peeling the adhesive layer. A technique (Patent Document 1) and a technique (Patent Document 2) in which a hot-melt hydrocarbon compound is used as an adhesive and bonding / peeling in a heat-melted state are proposed. The former technique requires an expensive apparatus such as a laser, and further requires the use of a specific substrate such as a glass substrate that transmits laser light, and processing time per substrate. There was a problem such as becoming longer. In addition, the latter technique is simple because it is controlled only by heating, but its application range is narrow because the thermal stability at a high temperature exceeding 200 ° C. is insufficient. Further, these temporary adhesive layers were not suitable for forming a uniform film thickness of a high step substrate and for complete adhesion to a support.

  Moreover, the technique which uses a silicone adhesive for a temporary adhesive material layer is proposed (patent document 3). In this method, the substrate is bonded to the support using an addition-curing silicone adhesive, and the substrate is separated from the support by immersing in a chemical that dissolves or decomposes the silicone resin at the time of peeling. . Therefore, it takes a very long time for peeling, and application to an actual manufacturing process is difficult.

JP 2004-64040 A JP 2006-328104 A US Pat. No. 7,541,264

  As a technique for solving the above problems, a method of laminating a thermosetting resin layer and a thermoplastic resin layer as a temporary adhesive layer, or a single layer of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane high polymer The method used in is proposed. However, because the former has low elasticity at room temperature and fluidity, the former may cause resin deformation and equipment contamination during the process depending on the laminate substrate configuration. The latter is heated as a peeling method. Although it is suitable for all horizontal sliding methods, the method of fixing one side of the laminated substrate horizontally and lifting the other at a certain angle from the horizontal direction has strong adhesion to the support and wafer. In addition, since it is hard, it is difficult to peel off and is difficult to apply to an actual manufacturing process.

  The present invention has been made in view of the above circumstances, the temporary adhesion between the wafer and the support is easy, TSV formation, high process compatibility with the wafer backside wiring process, furthermore, easy peeling, An object of the present invention is to provide a wafer processed body, a wafer processing member, a temporary adhesive for wafer processing, and a method for manufacturing a thin wafer using the same, which can enhance productivity.

In order to solve the above problems, according to the present invention, a temporary adhesive layer is formed on a support, and a wafer having a circuit surface on the front surface and a back surface to be processed is laminated on the temporary adhesive layer. A processed wafer,
A first temporary adhesive layer comprising a non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A), wherein the temporary adhesive layer is releasably bonded to the surface of the wafer; A wafer processed body provided with a second temporary adhesive layer made of a thermosetting modified siloxane polymer layer (B) that is laminated to the support and is detachably bonded to the support.

Further, the present invention is a wafer processing member in which a temporary adhesive layer is formed on a support, a wafer having a circuit surface on the front surface, and a wafer whose back surface is to be processed is temporarily bonded on the temporary adhesive layer. And
The temporary adhesive layer is laminated on the second temporary adhesive layer, a second temporary adhesive layer made of a thermosetting modified siloxane polymer layer (B) releasably bonded to the support, and the wafer A wafer processing member provided with a first temporary adhesive layer comprising a non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) that can be peelably bonded to the surface of the wafer.

  According to the present invention, there is also provided a non-aromatic non-aromatic material having a circuit surface on a front surface and a wafer processing temporary adhesive for temporarily bonding a wafer to be processed to a support to a support. First temporary adhesive layer composed of an aromatic polysiloxane-containing organopolysiloxane polymer layer (A), and a thermosetting modified siloxane polymer which is laminated on the first temporary adhesive layer and can be bonded and peeled off from the support. Provided is a temporary adhesive for wafer processing having a second temporary adhesive layer composed of a layer (B).

  By using such a wafer processed body, a wafer processing member, and a wafer processing temporary adhesive, temporary bonding between the wafer and the support is easy, and formation of a high step substrate with a uniform film thickness is also possible. This is possible, has high process compatibility with TSV formation and wafer backside wiring processes, and is easy to be peeled off, thereby improving productivity.

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。） In this case, the polymer layer (A) is preferably a polymer layer of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane containing units represented by the following (I) to (III).
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )

  Thus, if the said polymer layer (A) is a layer formed from the non-aromatic saturated hydrocarbon group containing organopolysiloxane containing the unit shown by said (I)-(III), adhesiveness, Excellent heat resistance. Furthermore, since it is soluble in nonpolar organic solvents, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) remaining on the circuit-forming surface of the wafer peeled off from the support can be easily removed. can do. On the other hand, a polar organic solvent used when a photoresist is applied to or removed from the semiconductor (wafer) side of the bonded substrate (wafer processed body) is preferably a poorly soluble layer.

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。）
前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の２〜３０モル％が炭素数２〜７のアルケニル基であるアルケニル基含有オルガノポリシロキサン（Ａ１）と、
下記平均組成式（１）
Ｒ^７ _ａＲ^８ _ｂＨ_ｃＳｉＯ_{（４−ａ−ｂ―ｃ）／２} （１）
（式中Ｒ^７はアルケニル基を除く１価の有機基であり、Ｒ^８は２価の有機基である。ａ、ｂ、及びｃは０＜ａ≦２．５、０≦ｂ≦１、０．７５≦ａ＋ｂ≦２．５、０．００５≦ｃ≦１、かつ０．８≦ａ＋ｂ＋ｃ≦４を満たす正数である。）
で示され、１分子中に少なくとも２個のＳｉＨ基を有するヒドロシリル基含有化合物であって、前記アルケニル基含有オルガノポリシロキサン（Ａ１）の総アルケニル基に対して総ＳｉＨ基が０．４〜１．０倍となる量の前記ヒドロシリル基含有化合物（Ａ２）とを、白金族金属系触媒の存在下でヒドロシリル化反応させて得たオルガノポリシロキサンの重合体層であることが好ましい。 In this case, the polymer layer (A) is a non-aromatic saturated hydrocarbon group-containing organopolysiloxane containing units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
An alkenyl group-containing organopolysiloxane (A1) in which 2 to 30 mol% of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are alkenyl groups having 2 to 7 carbon atoms;
The following average composition formula (1)
_{^{R 7 a R 8 b H c}} SiO (4-a-b-c) / 2 (1)
(Wherein R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. A, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, (It is a positive number satisfying 0.75 ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4.)
A hydrosilyl group-containing compound having at least two SiH groups in one molecule, wherein the total SiH groups are 0.4 to 1 with respect to the total alkenyl groups of the alkenyl group-containing organopolysiloxane (A1). It is preferably a polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the hydrosilyl group-containing compound (A2) in an amount of 0.0 times in the presence of a platinum group metal catalyst.

  Such a high molecular weight organopolysiloxane layer is soluble in nonpolar organic solvents, while a photoresist is applied to the semiconductor (wafer) side of the bonded substrate (wafer processed body). In addition, it is difficult to dissolve in a polar organic solvent used for removal or removal, and it is preferable because it becomes an organopolysiloxane layer having further excellent adhesion and heat resistance.

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。）
前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の２〜２０モル％が水素原子であるヒドロシリル基含有オルガノポリシロキサン（Ａ３）と、
下記平均組成式（２）
Ｒ^９ _ｄＲ^１０ _ｅＲ^１１ _ｆＳｉＯ_{（４−ｄ−ｅ―ｆ）／２} （２）
（但し、式中Ｒ^９はアルケニル基を除く１価の有機基であり、Ｒ^１０は２価の有機基である。Ｒ^１１は炭素数２〜６のアルケニル基である。ｄ、ｅ、ｆは０＜ｄ≦２、０≦ｅ≦１、０．７５≦ｄ＋ｅ≦３、０．０１≦ｆ≦１、かつ０．８≦ｄ＋ｅ＋ｆ≦４を満たす正数である。）
で示され、１分子中に少なくとも２個のアルケニル基を有するアルケニル基含有化合物であって、前記ヒドロシリル基含有オルガノポリシロキサン（Ａ３）の総ＳｉＨ基に対して総アルケニル基が１．０〜２．５倍となる量の前記アルケニル基含有化合物（Ａ４）とを、白金族金属系触媒の存在下でヒドロシリル化反応させて得たオルガノポリシロキサンの重合体層であることが好ましい。 In this case, the polymer layer (A) is a non-aromatic saturated hydrocarbon group-containing organopolysiloxane containing units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
A hydrosilyl group-containing organopolysiloxane (A3) in which 2 to 20 mol% of all the organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are hydrogen atoms;
The following average composition formula (2)
_{^{R 9 d R 10 e R 11}} f SiO (4-d-e-f) / 2 (2)
(In the formula, R ⁹ is a monovalent organic group excluding an alkenyl group, R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. D, e, f) Is a positive number satisfying 0 <d ≦ 2, 0 ≦ e ≦ 1, 0.75 ≦ d + e ≦ 3, 0.01 ≦ f ≦ 1, and 0.8 ≦ d + e + f ≦ 4.)
An alkenyl group-containing compound having at least two alkenyl groups in one molecule, wherein the total alkenyl groups are 1.0 to 2 with respect to the total SiH groups of the hydrosilyl group-containing organopolysiloxane (A3). It is preferably an organopolysiloxane polymer layer obtained by hydrosilylating the alkenyl group-containing compound (A4) in an amount of 5 times in the presence of a platinum group metal catalyst.

  Such a high molecular weight organopolysiloxane layer is soluble in nonpolar organic solvents, while a photoresist is applied to the semiconductor (wafer) side of the bonded substrate (wafer processed body). In addition, it is difficult to dissolve in a polar organic solvent used for removal or removal, and it is preferable because it becomes an organopolysiloxane layer having further excellent adhesion and heat resistance.

（式中、ｎは０〜４００の正数、Ｒ^１２〜Ｒ^１４は、同一又は異なる、置換又は非置換の１価の有機基である。）

（式中、Ｒ^１５〜Ｒ^１７は、同一又は異なる、置換又は非置換の１価の有機基である。Ｗは２価の有機基である。） In this case, the hydrosilyl group-containing compound (A2) is an organohydrogenpolysiloxane containing SiH groups at both ends represented by the following structural formula (3), or both ends represented by the following structural formula (4). A bissilyl compound containing a SiH group is preferred.

(In the formula, n is a positive number of 0 to 400, and R ^{12 to} R ¹⁴ are the same or different, substituted or unsubstituted monovalent organic groups.)

(In the formula, R ^{15 to} R ¹⁷ are the same or different, substituted or unsubstituted monovalent organic groups. W is a divalent organic group.)

  With such a hydrosilyl group-containing compound (A2), the hydrosilylation reaction with the alkenyl group of the alkenyl group-containing organopolysiloxane (A1) is easy to proceed, and is compatible with the alkenyl group-containing organopolysiloxane (A1). Since it becomes a good hydrosilyl group containing compound (A2), it is preferable from a viewpoint of hydrosilylation reaction.

［式中、Ｒ^1８〜Ｒ^２１は同一でも異なっていてもよい炭素原子数１〜８の１価炭化水素基を示す。また、ｍは１〜１００の整数であり、Ａは正数、Ｂは０又は正数である。Ｘは下記一般式（７）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。また、Ｒ^２２、Ｒ^２３はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｋは０、１、２のいずれかである。）］

［式中、Ｒ^１８〜Ｒ^２１は同一でも異なっていてもよい炭素原子数１〜８の１価炭化水素基を示す。また、ｍは１〜１００の整数であり、ｇ、ｈ、ｉ、ｊは０又は正数であり、但し、ｉ及びｊが同時に０になることはなく、かつ、０＜（ｉ＋ｊ）／（ｇ＋ｈ＋ｉ＋ｊ）≦１．０である。更に、Ｘは下記一般式（７）で示される２価の有機基、Ｙは下記一般式（８）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。また、Ｒ^２２、Ｒ^２３はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｋは０、１、２のいずれかである。）

（式中、Ｖは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。また、Ｒ^２４、Ｒ^２５はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｑは０、１、２のいずれかである。）］ In this case, the polymer layer (B) is a silphenylene-containing polymer compound having a repeating unit represented by the following general formula (5) and having a weight average molecular weight of 3,000 to 500,000, or the following general formula ( 6) Formalin or formalin as a crosslinking agent with respect to 100 parts by mass of a thermosetting modified siloxane polymer comprising an epoxy group-containing silicone polymer compound having a repeating unit represented by 6) and having a weight average molecular weight of 3,000 to 500,000 -An alcohol-modified amino condensate, a melamine resin, a urea resin, an average of two or more methylol groups or alkoxymethylol groups in one molecule, and an average of two or more in one molecule A composition containing 0.1 to 50 parts by mass of any one or more selected from epoxy compounds having an epoxy group It is preferably a cured product layer.

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, A is a positive number, and B is 0 or a positive number. X is a divalent organic group represented by the following general formula (7).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. ]]

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, and g, h, i, and j are 0 or a positive number, provided that i and j are not 0 at the same time, and 0 <(i + j) / ( g + h + i + j) ≦ 1.0. Furthermore, X is a divalent organic group represented by the following general formula (7), and Y is a divalent organic group represented by the following general formula (8).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ²⁴ and R ²⁵ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. q is 0, 1, or 2. ]]

  Such a polymer layer (B) is more preferable because it is more excellent in heat resistance and becomes a temporary adhesive layer having good film thickness uniformity.

In the present invention,
(A) a step of grinding or polishing a non-circuit-formed surface of the wafer with respect to the wafer workpiece;
(B) a step of processing the non-circuit-formed surface of the wafer;
(C) There is provided a method for producing a thin wafer, comprising a step of peeling the processed wafer from the support.

  In such a thin wafer manufacturing method, a thin wafer having a through electrode structure or a bump connection structure is obtained by using the temporary adhesive material layer composed of the two-layer system in the present invention for joining the wafer and the support. Can be easily manufactured.

In this case, the step (c) of peeling the processed wafer from the support is as follows:
A dicing tape is bonded to the processed surface of the processed wafer, the dicing tape surface is vacuum-adsorbed to the suction surface, and the temperature of the suction surface is in a temperature range of 10 ° C. to 100 ° C., and the support is processed. It is preferable to peel off the applied wafer by peel-off.

  According to such a peeling process, the support can be easily peeled from the processed wafer, and the subsequent dicing process can be easily performed.

Moreover, in this case, after the step of peeling the processed wafer (c) from the support,
(D) It is preferable to perform a step of removing the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) remaining on the circuit forming surface of the peeled wafer.

  A part of the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) may remain on the circuit forming surface of the wafer peeled from the support in step (c). The aromatic saturated hydrocarbon group-containing organopolysiloxane polymer (A) can be removed, for example, by washing the wafer.

  Since the temporary adhesive layer in the present invention has high heat resistance, it can be applied to a wide range of semiconductor film forming processes, and an adhesive layer with high film thickness uniformity can be formed even on a wafer having a step. Because of the uniformity, it is possible to easily obtain a uniform thin wafer of 50 μm or less, and furthermore, after the thin wafer is manufactured, this wafer can be easily peeled off from the support at room temperature, so that it is easy to break. Can be easily manufactured.

It is sectional drawing which shows an example of the wafer processed body of this invention.

As a result of intensive studies to achieve the above object, the present inventors
(A) non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (first temporary adhesive layer);
(B) Thermosetting modified siloxane polymer layer (second temporary adhesive layer)
By using a temporary adhesive layer consisting of two layers for bonding the wafer and the support, a thin wafer having a through-electrode structure or a bump connection structure can be easily obtained using this temporary adhesive layer. A method of manufacturing was found.

As shown in FIG. 1, a wafer processing body 10 of the present invention includes a wafer 1 to be processed, a support 2 that supports the wafer 1 when the wafer 1 is processed, and a gap between the wafer 1 and the support 2. An interim temporary adhesive layer 3 is provided. The temporary adhesive layer 3 is composed of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) (first temporary adhesive layer) and a thermosetting modified siloxane polymer. Layer (B) (second temporary adhesive layer), the first temporary adhesive layer has a circuit surface on the surface, and the back surface is detachably bonded to the surface of the wafer to be processed, and the second temporary adhesive layer is supported It is adhered to the body in a peelable manner.
The member for wafer processing of the present invention comprises the support 2, the thermosetting modified siloxane polymer layer (B) laminated thereon, and the non-aromatic saturated hydrocarbon group laminated thereon. It has an organopolysiloxane polymer layer (A), and the temporary adhesive for wafer processing of the present invention comprises a laminate of the above layers (A) and (B).

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。） The present invention will be described in detail below.
<Temporary adhesive layer>
-Temporary adhesive layer (A) / non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer-
Examples of the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) include non-aromatic saturated hydrocarbon group-containing organopolysiloxane layers containing units represented by the following (I) to (III). .
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )

R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom. Further, 50 mol% or more, preferably 60 mol% or more of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are non-aromatic saturated hydrocarbon groups having 3 to 20 carbon atoms, and R ¹ to R ³ in 40 mol% or more of all organic groups and hydrogen atoms indicated, preferably 50 mol% or more, more preferably 60 mol% or more, identical or different, including the cyclic structure of 5 to 7 carbon atoms It is a non-aromatic saturated hydrocarbon group. Moreover, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atom or substituted or unsubstituted monovalent carbon having 1 to 7 carbon atoms. It is a hydrogen group.

Like the above-mentioned organopolysiloxane, by making the organic group a non-aromatic saturated hydrocarbon group, a polar organic solvent used when applying or removing photoresist on the semiconductor side of the bonded substrate, etc. Is hardly soluble and soluble in nonpolar organic solvents. That is, the polarities described above are obtained by making 50 mol% or more of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ of T, D, and M units into non-aromatic saturated hydrocarbon groups having 3 to 20 carbon atoms. It becomes an organopolysiloxane that is poorly soluble in organic solvents, soluble in nonpolar hydrocarbon solvents such as hexane, octane, and isododecane, and also excellent in heat resistance. Moreover, it becomes organopolysiloxane more excellent in heat resistance by increasing content of a non-aromatic saturated hydrocarbon group, especially the non-aromatic saturated hydrocarbon group containing the said cyclic structure of C5-C7.

Specific examples of the non-aromatic saturated hydrocarbon group include n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, An octyl group, an n-decyl group, an n-dodecyl group, a norbornyl group, a norbornylethyl group, and an adamantyl group are exemplified, and more preferably an n-propyl group, an n-hexyl group, a cyclopentyl group, a cyclohexyl group, and a norbornyl group. Is good. In particular, the content of a cyclic hydrocarbon group (a non-aromatic saturated hydrocarbon group containing a cyclic structure) is important for having high heat resistance. When the cyclic hydrocarbon group content as the non-aromatic saturated hydrocarbon group is 40 mol% or more of all the organic groups and hydrogen atoms represented by R ^{1 to} R ³ , durability at a high temperature of 260 ° C. or more It becomes an organopolysiloxane that is superior in heat resistance and heat resistance. As these cyclic hydrocarbon groups, the following monovalent and / or divalent cyclopentyl skeleton, cyclohexyl skeleton, bicyclo [2.2.1] skeleton, and bicyclo [3.1.1] skeleton are preferable. .

The non-aromatic saturated hydrocarbon group-containing organopolysiloxane contains 40 to 99 mol% of a siloxane unit (T unit) represented by (I) R ¹ SiO _3/2 , and (II) R ² R ³ SiO _2/2. 59 mol% or less, and (III) R ⁴ R ⁵ R ⁶ SiO _1/2 siloxane units (M units) are contained in an amount of 1 to 30 mol%. The organopolysiloxane having the above structure can be produced by controlling the hydrolysis and condensation reaction of the hydrolyzable silane used as a raw material. In addition, as the non-aromatic saturated hydrocarbon group-containing organopolysiloxane in the present invention, those having a solid shape at a temperature not exceeding 40 ° C. are preferable for handling.

  Examples of hydrolyzable silanes that can be used as raw materials include methyltrichlorosilane, phenyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, and isopentyltrichlorosilane. Silane, cyclopentyltrichlorosilane, n-hexyltrichlorosilane, cyclohexyltrichlorosilane, n-octyltrichlorosilane, n-decyltrichlorosilane, n-dodecylchlorosilane, bicyclo [2.2.1] heptyltrichlorosilane (C1), bicyclo [2.2.1] Nonyltrichlorosilane (C2), bicyclo [3.1.1] decyltrichlorosilane (C3, C4), dimethyldichlorosilane, n-propylmethyl Dichlorosilane, isopropylmethyldichlorosilane, n-butylmethyldichlorosilane, isobutylmethyldichlorosilane, n-hexylmethyldichlorosilane, cyclohexylmethyldichlorosilane, diphenyldichlorosilane, and their hydrolyzable groups are methoxy. And those which are ethoxy groups.

In particular, the following (C1) to (C4) having a plurality of cyclic structures include endo isomers and exo isomers, and these can be used regardless.

  By containing 40 to 99 mol% of T units, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane tends to be solid at 40 ° C. or lower and is soluble in non-polar organic solvents. It is hardly soluble in polar organic solvents used when applying or removing photoresist on the semiconductor side of the substrate. Moreover, it is preferable from a viewpoint of the thermal stability mentioned later that the reactive terminal group, ie, a silanol and a hydrolysable residue, does not remain in the said non-aromatic saturated hydrocarbon group containing organopolysiloxane. Therefore, a structure in which an M unit is introduced at the terminal is preferable, and the content of the M unit is preferably 1 mol% or more.

  By containing 59 mol% or less of D units, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane of the present invention tends to be solid at 40 ° C. or less, and when used in a temporary adhesive composition, a wafer and a supporting substrate Can be fully joined. In other words, there is no risk of becoming a fluid sticky substance or liquid, so that the bonding between the support substrate and the wafer having the semiconductor circuit is sufficient, and the laminated wafer is displaced by backside grinding or subsequent processing. This is preferable because there is no fear of occurrence.

  By containing 1 to 30 mol% of M units, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane has a polarity used when applying or removing a photoresist on the semiconductor side of the bonded substrate. It becomes insoluble in organic solvents and has a structure with sufficiently reduced reactive end groups. Moreover, when it is 30 mol% or less, since there is no fear that a molecular weight may become relatively small because a terminal group increases, it is preferable.

  When there are hydrolyzable residues such as molecular end groups not sealed with M units, that is, silanol groups or alkoxysilyl groups, the content of these reactive end groups is preferably as low as possible. If the silanol group and the terminal residue of the alkoxysilyl group are small in the molecule, it is preferable because crosslinking due to a condensation reaction is generated when heat is applied, and the peelability of the substrate can be largely prevented from changing. . In addition, OH group of silanol group and OR group of alkoxysilyl group (Si-OR: R is an alkoxy group residue, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, etc. of alkoxysilane used as a raw material) The total amount of is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total resin solid content. By introducing M units, such reactive end groups can be reduced to the desired amount.

The molecular weight distribution of the non-aromatic saturated hydrocarbon group-containing organopolysiloxane in the present invention is important. That is, the value of the weight average molecular weight obtained by GPC (gel permeation chromatography) along a calibration curve prepared with a polystyrene standard is preferably 2,000 or more. It is preferable if the weight average molecular weight of the non-aromatic saturated hydrocarbon group-containing organopolysiloxane is 2,000 or more because of excellent heat resistance. The range of the weight average molecular weight of the more preferable non-aromatic saturated hydrocarbon group-containing organopolysiloxane is preferably about 3,000 to 200,000, more preferably about 5,000 to 150,000.
As a GPC apparatus capable of such analysis and analysis, HLC-8120GPC, HLC-8220GPC, and HLC-8230GPC manufactured by Tosoh Corporation can be used.

  Such a non-aromatic saturated hydrocarbon group-containing organopolysiloxane can be produced by a known method. For example, an organochlorosilane and / or an organoalkoxysilane capable of forming the above siloxane units (T, D, M units) or a partial hydrolysis-condensation product thereof can be obtained by a hydrolysis condensation reaction. For example, an excess amount of water to hydrolyze all hydrolyzable groups (chloro group, alkoxy group, etc.) is mixed into a mixed solution of an organic solvent capable of dissolving the raw material silane compound and the resulting organopolysiloxane. It can be obtained by hydrolytic condensation reaction. The organopolysiloxane having a desired weight average molecular weight can be obtained by adjusting the reaction temperature and time, the amount of water, and the organic solvent. For example, when the organopolysiloxane produced in this manner is used as a temporary adhesive, it may be used after removing unnecessary organic solvent components and solidifying it once.

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。）
前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の２〜３０モル％が炭素数２〜７のアルケニル基であるアルケニル基含有オルガノポリシロキサン（Ａ１）と、
下記平均組成式（１）
Ｒ^７ _ａＲ^８ _ｂＨ_ｃＳｉＯ_{（４−ａ−ｂ―ｃ）／２} （１）
（式中Ｒ^７はアルケニル基を除く１価の有機基であり、Ｒ^８は２価の有機基である。ａ、ｂ、及びｃは０＜ａ≦２．５、０≦ｂ≦１、０．７５≦ａ＋ｂ≦２．５、０．００５≦ｃ≦１、かつ０．８≦ａ＋ｂ＋ｃ≦４を満たす正数である。）
で示され、１分子中に少なくとも２個のＳｉＨ基を有するヒドロシリル基含有化合物であって、前記アルケニル基含有オルガノポリシロキサン（Ａ１）の総アルケニル基に対して総ＳｉＨ基が０．４〜１．０倍となる量の前記ヒドロシリル基含有化合物（Ａ２）とを、白金族金属系触媒の存在下でヒドロシリル化反応させた高分子量化したオルガノポリシロキサンが挙げられる。 In addition, the polymer layer (A) in the present invention may be a layer of organopolysiloxane having a high molecular weight using the above non-aromatic saturated hydrocarbon group-containing organopolysiloxane as a raw material. Hereinafter, such high molecular weight organopolysiloxane will be described.
As such a high molecular weight organopolysiloxane, among non-aromatic saturated hydrocarbon group-containing organopolysiloxanes containing units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
An alkenyl group-containing organopolysiloxane (A1) in which 2 to 30 mol% of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are alkenyl groups having 2 to 7 carbon atoms;
The following average composition formula (1)
_{^{R 7 a R 8 b H c}} SiO (4-a-b-c) / 2 (1)
(Wherein R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. A, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, (It is a positive number satisfying 0.75 ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4.)
A hydrosilyl group-containing compound having at least two SiH groups in one molecule, wherein the total SiH groups are 0.4 to 1 with respect to the total alkenyl groups of the alkenyl group-containing organopolysiloxane (A1). An organopolysiloxane having a high molecular weight obtained by hydrosilylating the hydrosilyl group-containing compound (A2) in an amount of 0.0 times in the presence of a platinum group metal catalyst.

In this case, the content of the alkenyl group is 2 mol% to 30% of all organic groups and hydrogen atoms represented by at least ^R 1 to R ^6. If the alkenyl group content is 2 mol% or more, the molecular weight increase due to the hydrosilylation reaction is increased, and the organopolysiloxane is excellent in physical properties such as heat resistance. Moreover, if it is 30 mol% or less, the solubility to the polar organic solvent used when apply | coating or removing a photoresist to the semiconductor side of a joining board | substrate etc. will become further low, and it is preferable.

  Examples of such an alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and a norbornenyl group. From the viewpoint of reactivity, a vinyl group is preferable.

In the average composition formula (1), R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. R ⁷ is not particularly limited as long as it is a monovalent organic group, and examples thereof include a methyl group, an n-propyl group, an isopropyl group, a hexyl group, a cyclohexyl group, and a phenyl group. R ⁸ is not particularly limited as long as it is a divalent organic group, and examples include methylene group, ethylene group, butanylene group, hexylene group, cyclohexylene group, and phenylene group.

  Further, in the above average composition formula (1), a and b represent the contents of organic groups in the molecule, and a, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, 0.75. ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4. When a + b is smaller than 0.75, the value of c, that is, the content of SiH groups is relatively increased. Considering the hydrosilylation reaction between the alkenyl group of the alkenyl group-containing organopolysiloxane (A1) and the SiH group of the hydrosilyl group-containing compound (A2), if the amount of SiH is large, the degree of crosslinking is too high and the organopolysiloxane is increased in molecular weight Siloxane tends to gel. Further, when a large amount of SiH groups remain, the possibility of gas generation due to thermal deterioration is increased. Moreover, if a + b is 2.5 or less, the amount of SiH groups is appropriate, and high molecular weight by reaction proceeds appropriately. Furthermore, if a is 2.5 or less, the amount of SiH groups involved in crosslinking is appropriate, the molecular weight is increased to a target value, and heat resistance is excellent. Therefore, a, b, and c are preferably in the above range. Further, the value of c is preferably 1.0 or less in view of the availability of silicon raw materials, and is preferably 0.005 or more in order to sufficiently advance the crosslinking reaction.

  Further, the total SiH amount of the component (A2) relative to the total alkenyl groups of the component (A1) is preferably 0.4 to 1.0. If it is 0.4 or more, the increase in molecular weight is sufficient, and desired heat resistance and adhesiveness can be obtained. Moreover, if it is 1.0 or less, it is preferable because crosslinking of the resin is moderate and hardly gelled, SiH groups remaining in the resin can be reduced, and foaming can be suppressed during a heat resistance test after bonding.

（式中、ｎは０〜４００の正数、Ｒ^１２〜Ｒ^１４は、同一又は異なる、置換又は非置換の１価の有機基である。）

（式中、Ｒ^１５〜Ｒ^１７は、同一又は異なる、置換又は非置換の１価の有機基である。Ｗは２価の有機基である。） As more specific examples of the hydrosilyl group-containing compound (A2), linear polysiloxane, polysilylalkylene, and polysilylarylene having SiH groups at both ends can be used. In particular, an organohydrogenpolysiloxane containing SiH groups at both ends represented by the following structural formula (3) or a bissilyl compound containing SiH groups at both ends represented by the following structural formula (4) is preferable. .

(In the formula, n is a positive number of 0 to 400, and R ^{12 to} R ¹⁴ are the same or different, substituted or unsubstituted monovalent organic groups.)

(In the formula, R ^{15 to} R ¹⁷ are the same or different, substituted or unsubstituted monovalent organic groups. W is a divalent organic group.)

R ^{12 to} R ¹⁷ are the same or different substituted or unsubstituted monovalent organic groups. The R ¹² to R ^17, but are not limited to, a monovalent hydrocarbon group, specifically a methyl group having 1 to 8 carbon atoms, a propyl group, a hexyl group, a cyclohexyl group, a phenyl group and the like. Particularly preferred are a methyl group, a cyclohexyl group and a phenyl group.

  The degree of polymerization n of the organohydrogenpolysiloxane represented by the structural formula (3) is 0 to 400. Those having a degree of polymerization n of 200 or more within the range of n are preferably used in combination with siloxane having a degree of polymerization of 0 to 40, because the hydrosilylation reaction with the alkenyl group of (A1) is difficult to proceed. In addition, it is preferable that n is 200 or less because the compatibility between the organohydrogenpolysiloxane and the alkenyl group-containing organopolysiloxane (A1) is good and the reactivity of the terminal SiH group is not lowered.

  The linking group W of the bissilyl compound represented by the structural formula (4) is a divalent organic group. Although it does not specifically limit as W, A C1-C10 bivalent hydrocarbon group and a phenylene group are illustrated. In particular, a phenylene group is preferable from the viewpoint of heat resistance of the high molecular weight organopolysiloxane.

  Such a high molecular weight organopolysiloxane is soluble in non-polar organic solvents, while it is used when applying or removing photoresist on the semiconductor side of the bonding substrate. The organopolysiloxane is hardly soluble in a polar organic solvent and has excellent adhesion and heat resistance.

  Furthermore, the polymer layer (A) in the present invention is a combination of compounds obtained by exchanging reactive groups, in addition to an addition reaction product of an alkenyl group-containing organopolysiloxane (A1) and a hydrosilyl group-containing compound (A2). An organopolysiloxane layer obtained by addition reaction of hydrosilyl group-containing organopolysiloxane (A3) and alkenyl group-containing compound (A4) can also be used.

さらに、前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の非芳香族飽和炭化水素基以外は、同一又は異なる、水素原子又は炭素数１〜７の置換又は非置換の１価炭化水素基である。）
前記Ｒ^１〜Ｒ^６で示される全有機基及び水素原子中の２〜２０モル％が水素原子であるヒドロシリル基含有オルガノポリシロキサン（Ａ３）と、
下記平均組成式（２）
Ｒ^９ _ｄＲ^１０ _ｅＲ^１１ _ｆＳｉＯ_{（４−ｄ−ｅ―ｆ）／２} （２）
（但し、式中Ｒ^９はアルケニル基を除く１価の有機基であり、Ｒ^１０は２価の有機基である。Ｒ^１１は炭素数２〜６のアルケニル基である。ｄ、ｅ、ｆは０＜ｄ≦２、０≦ｅ≦１、０．７５≦ｄ＋ｅ≦３、０．０１≦ｆ≦１、かつ０．８≦ｄ＋ｅ＋ｆ≦４を満たす正数である。）
で示され、１分子中に少なくとも２個のアルケニル基を有するアルケニル基含有化合物であって、前記ヒドロシリル基含有オルガノポリシロキサン（Ａ３）の総ＳｉＨ基に対して総アルケニル基が１．０〜２．５倍となる量の前記アルケニル基含有化合物（Ａ４）とを、白金族金属系触媒の存在下でヒドロシリル化反応させて高分子量化したオルガノポリシロキサンが挙げられる。 As such an organopolysiloxane, among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes containing units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
A hydrosilyl group-containing organopolysiloxane (A3) in which 2 to 20 mol% of all the organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are hydrogen atoms;
The following average composition formula (2)
_{^{R 9 d R 10 e R 11}} f SiO (4-d-e-f) / 2 (2)
(In the formula, R ⁹ is a monovalent organic group excluding an alkenyl group, R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. D, e, f) Is a positive number satisfying 0 <d ≦ 2, 0 ≦ e ≦ 1, 0.75 ≦ d + e ≦ 3, 0.01 ≦ f ≦ 1, and 0.8 ≦ d + e + f ≦ 4.)
An alkenyl group-containing compound having at least two alkenyl groups in one molecule, wherein the total alkenyl groups are 1.0 to 2 with respect to the total SiH groups of the hydrosilyl group-containing organopolysiloxane (A3). An organopolysiloxane obtained by hydrosilylating the alkenyl group-containing compound (A4) in an amount of 5 times in the presence of a platinum group metal catalyst to increase the molecular weight.

In this case, the content of hydrogen atoms is 2 mol% to 20% of all organic groups and hydrogen atoms represented by at least ^R 1 to R ^6. A hydrogen atom content of 2 mol% or more is preferred because the increase in molecular weight due to the hydrosilylation reaction is increased, and the organopolysiloxane is excellent in physical properties such as heat resistance. Moreover, if it is 20 mol% or less, the solubility to the polar organic solvent used when apply | coating a photoresist on the semiconductor side of a joining board | substrate or removing it etc., and it is preferable.

In the average composition formula (2), R ⁹ is a monovalent organic group excluding an alkenyl group, and R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. R ⁹ is not particularly limited as long as R ⁹ is a monovalent organic group excluding an alkenyl group, and examples thereof include a methyl group, an n-propyl group, an isopropyl group, a hexyl group, a cyclohexyl group, and a phenyl group. R ¹⁰ is a divalent organic group and is not particularly limited, and examples thereof include a methylene group, an ethylene group, a butanylene group, a hexylene group, a cyclohexylene group, and a phenylene group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms and is not particularly limited, and examples thereof include a vinyl group, an allyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and a norbornenyl group. A vinyl group is preferred.

  In the average composition formula (2), d, e, and f indicate the contents of organic groups in the molecule, and d, e, and f are 0 <d ≦ 2, 0 ≦ e ≦ 1, and 0.75 ≦ d + e ≦. 3, a positive number satisfying 0.01 ≦ f ≦ 1 and 0.8 ≦ d + e + f ≦ 4.

  The total alkenyl group of the component (A4) is preferably 1.0 to 2.5 times the total SiH amount of the component (A3). If it is 1.0 times or more, the increase in molecular weight is sufficient, and desired heat resistance and adhesiveness can be obtained. Moreover, if it is 2.5 times or less, since bridge | crosslinking of resin becomes moderate and it is hard to gelatinize, since the SiH group which remains in resin can also be reduced and foaming can also be suppressed in the heat test after joining, it is preferable.

  Such a high molecular weight organopolysiloxane is soluble in non-polar organic solvents, while it is used when applying or removing photoresist on the semiconductor side of the bonding substrate. The organopolysiloxane is hardly soluble in a polar organic solvent and has excellent adhesion and heat resistance.

  The reaction between the alkenyl group-containing organopolysiloxane (A1) and the hydrosilyl group-containing compound (A2) involves dissolving the alkenyl group-containing organopolysiloxane (A1) in an organic solvent and adding a platinum-based metal catalyst as a hydrosilylation catalyst. Thereafter, the hydrosilyl group-containing compound (A2) is dropped while being heated to 50 to 150 ° C., whereby an organopolysiloxane having a high molecular weight can be obtained. The platinum-based metal catalyst is a catalyst for accelerating the hydrosilylation addition reaction with the SiH group. Examples of the addition reaction catalyst include platinum black, second platinum chloride, chloroplatinic acid, chloroplatinic acid and monohydric alcohol. And platinum group metal catalysts such as platinum-based catalysts such as platinum bisacetoacetate, palladium-based catalysts, and rhodium-based catalysts. In addition, although the compounding quantity of this addition reaction catalyst can be made into a catalyst quantity, it is preferable normally to mix | blend about 1-800 ppm, especially about 2-300 ppm with respect to the weight of (A1) component as a platinum group metal.

In addition, the reaction between the hydrosilyl group-containing organopolysiloxane (A3) and the alkenyl group-containing compound (A4) can also be carried out by heating and mixing them in the presence of an addition reaction catalyst, as described above. An organopolysiloxane can be obtained.
The molecular weight of the organopolysiloxane after these hydrosilylation addition reactions affects the properties of the temporary adhesive, in particular, thermal deformation during heating, generation of voids at the bonding interface, and the like.

  The weight average molecular weight Mw of the high molecular weight polyorganosiloxane after the addition reaction is a value of a weight average molecular weight obtained in accordance with a calibration curve prepared with a polystyrene standard using GPC (gel permeation chromatography). 000 or more is preferable. When the weight average molecular weight is 15,000 or more, the organopolysiloxane is excellent in heat resistance. A more preferable range of the weight average molecular weight is about 20,000 to 200,000, more preferably about 30,000 to 150,000.

  Even if this non-aromatic saturated hydrocarbon group-containing organopolysiloxane is used as a film in advance and bonded to a wafer using a roll laminator or the like, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane The solution may be formed on a wafer by a method such as spin coating or roll coater. When the layer (A) is formed on the wafer by a method such as spin coating, it is preferable to coat the resin as a solution, and then heat-dry, but this solution includes pentane, hexane, cyclohexane, decane. Hydrocarbon solvents such as isododecane and limonene are preferably used.

  Moreover, this (A) layer is formed and used between 0.1-30 micrometers in film thickness, Preferably it is 0.5-10 micrometers. When the thickness is 0.1 μm or more, the step of the device wafer can be sufficiently covered, and when the thickness is 30 μm or less, there is no possibility of cracking in the film, which is preferable. In addition, in order to further improve heat resistance, the non-aromatic saturated hydrocarbon group-containing organopolysiloxane may contain 50 parts by mass or less of a filler such as silica.

-Second temporary adhesive layer (B) / thermosetting modified siloxane polymer layer-
A layer of a cured product of a thermosetting composition mainly composed of a thermosetting modified siloxane polymer represented by any one of the following general formulas (5) and (6) is used as the temporary adhesive layer (B). Can do.

［式中、Ｒ^1８〜Ｒ^２１は同一でも異なっていてもよい炭素原子数１〜８のアルキル基等の１価炭化水素基を示す。また、ｍは１〜１００の整数であり、Ａは正数、Ｂは０又は正数である。Ｘは下記一般式（７）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。また、Ｒ^２２、Ｒ^２３はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｋは０、１、２のいずれかである。）］
この場合、Ｒ^1８〜Ｒ^２１の具体例としては、メチル基、エチル基、フェニル基等が挙げられ、ｍは、好ましくは３〜６０、より好ましくは８〜４０の整数である。また、Ｂ／Ａは０〜２０、特に０．５〜５である。 Polymer of general formula (5):
A silphenylene-containing polymer compound having a repeating unit represented by the following general formula (5) and having a weight average molecular weight of 3,000 to 500,000.

[In formula, R < ¹⁸ > -R < ²¹ > shows monovalent hydrocarbon groups, such as a C1-C8 alkyl group which may be same or different. M is an integer of 1 to 100, A is a positive number, and B is 0 or a positive number. X is a divalent organic group represented by the following general formula (7).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. ]]
In this case, specific examples of R ^{18 to} R ²¹ include a methyl group, an ethyl group, and a phenyl group, and m is preferably an integer of 3 to 60, more preferably 8 to 40. Moreover, B / A is 0-20, especially 0.5-5.

［式中、Ｒ^1８〜Ｒ^２１は同一でも異なっていてもよい炭素原子数１〜８のアルキル基等の１価炭化水素基を示す。また、ｍは１〜１００の整数であり、ｇ、ｈ、ｉ、ｊは０又は正数であり、但し、ｉ及びｊが同時に０になることはなく、かつ、０＜（ｉ＋ｊ）／（ｇ＋ｈ＋ｉ＋ｊ）≦１．０、好ましくは０．１≦（ｉ＋ｊ）／（ｇ＋ｈ＋ｉ＋ｊ）≦０．８である。更に、Ｘは下記一般式（７）で示される２価の有機基、Ｙは下記一般式（８）で示される２価の有機基である。

（式中、Ｚは

のいずれかより選ばれる２価の有機基であり、ｎは０又は１である。また、Ｒ^２２、Ｒ^２３はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｋは０、１、２のいずれかである。）

（式中、Ｖは

のいずれかより選ばれる２価の有機基であり、ｐは０又は１である。また、Ｒ^２４、Ｒ^２５はそれぞれ炭素原子数１〜４のアルキル基又はアルコキシ基であり、相互に同一でも異なっていてもよい。ｑは０、１、２のいずれかである。）］
この場合、Ｒ^1８〜Ｒ^２１、ｍの具体例は上記と同様である。 Polymer of general formula (6):
An epoxy group-containing silicone polymer compound having a repeating unit represented by the following general formula (6) and having a weight average molecular weight of 3,000 to 500,000.

[In formula, R < ¹⁸ > -R < ²¹ > shows monovalent hydrocarbon groups, such as a C1-C8 alkyl group which may be same or different. M is an integer of 1 to 100, and g, h, i, and j are 0 or a positive number, provided that i and j are not 0 at the same time, and 0 <(i + j) / ( g + h + i + j) ≦ 1.0, preferably 0.1 ≦ (i + j) / (g + h + i + j) ≦ 0.8. Furthermore, X is a divalent organic group represented by the following general formula (7), and Y is a divalent organic group represented by the following general formula (8).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ²⁴ and R ²⁵ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. q is 0, 1, or 2. ]]
In this case, specific examples of R ^{18 to} R ²¹ and m are the same as described above.

  The thermosetting composition based on the thermosetting modified siloxane polymer of the formula (5) or (6) is an amino condensate modified with formalin or formalin-alcohol for the thermosetting, Any one selected from a melamine resin, a urea resin, a phenol compound having an average of two or more methylol groups or an alkoxymethylol group in one molecule, and an epoxy compound having an average of two or more epoxy groups in one molecule Or one or more cross-linking agents.

In particular, a bifunctional, trifunctional, tetrafunctional or higher polyfunctional crosslinking agent, especially an epoxy resin such as EOCN-1020, EOCN-102S, XD-1000, NC-2000-L, EPPN manufactured by Nippon Kayaku Co., Ltd. -201, GAN, NC6000, and a crosslinking agent like the following formula can be contained.

  The amount of the crosslinking agent is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the thermosetting modified siloxane polymer. Two or more types may be mixed and blended.

  In addition, the composition can contain a curing catalyst such as an acid anhydride in an amount of 5 parts by mass or less.

  On the other hand, this composition may be formed as a film on the (A) layer formed on the wafer, or on the support side for producing a thin wafer. Alternatively, the composition may be dissolved in a solution and formed on the layer (A) or the support by coating, specifically, a method such as spin coating, roll coater, or die coater. Examples of the solvent that can be used in this case include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2 Alcohols such as propanol and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxy Examples include esters such as methyl propionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. Or 2 or more types can be used together.

  In addition, in order to further improve heat resistance, you may add 50 mass parts or less of well-known antioxidant, fillers, such as a silica.

  The polymer layer (B) is preferably formed with a film thickness of 10 to 200 μm, preferably 20 to 120 μm at the time of curing. If the film thickness is 10 μm or more, it is possible to sufficiently withstand the grinding process for thinning the wafer, and if it is 200 μm or less, there is no risk of resin deformation in the heat treatment process such as the TSV forming process, which is sufficient for practical use. Can withstand.

<Manufacturing method of thin wafer>
The thin wafer manufacturing method of the present invention uses a temporary adhesive layer composed of the above-mentioned two layers (A) and (B) as an adhesive layer between a wafer having a semiconductor circuit and the support. Features. The thickness of the thin wafer obtained by the production method of the present invention is typically 5 to 300 μm, more typically 10 to 100 μm.

The manufacturing method of the thin wafer of this invention has the following process (a)-(c).
(A) a step of grinding or polishing a non-circuit-formed surface of the wafer with respect to the wafer processed body described above;
(B) a step of processing the non-circuit-formed surface of the wafer;
(C) A step of peeling the processed wafer from the support.

In addition, after the step (c) of peeling the processed wafer from the support,
(D) It is preferable to perform a step of removing the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) remaining on the circuit forming surface of the peeled wafer.

[Wafer processed body manufacturing method]
The wafer processed body has a circuit forming surface of a wafer having a circuit forming surface on the front surface and a circuit non-forming surface on the back surface. It can be obtained by bonding to a support via a temporary adhesive layer.
A wafer having a circuit formation surface and a circuit non-formation surface is a wafer in which one surface is a circuit formation surface and the other surface is a circuit non-formation surface. A wafer to which the present invention is applicable is usually a semiconductor wafer. Examples of the semiconductor wafer include not only a silicon wafer but also a germanium wafer, a gallium-arsenic wafer, a gallium-phosphorus wafer, a gallium-arsenic-aluminum wafer, and the like. The thickness of the wafer is not particularly limited, but is typically 600 to 800 μm, more typically 625 to 775 μm.
As the support, a substrate such as a silicon wafer, glass, or quartz wafer can be used. In the present invention, it is not necessary to irradiate the temporary adhesive layer through the support with radiant energy rays, and the light transmittance of the support is not necessary.

  The temporary adhesive layers (A) and (B) are each a film and can be formed on a wafer or a support, or each solution can be formed on a wafer or a support by a method such as spin coating. In this case, after spin coating, pre-baking is performed in advance at a temperature of 80 to 190 ° C. according to the volatilization conditions of the solvent, and then used. Furthermore, after the first temporary adhesive layer (A) and the second temporary adhesive layer (B) are bonded together in advance, the first temporary adhesive layer (A) is placed on the wafer side, the second temporary adhesive layer ( It is also possible to use B) as a support side for joining.

The wafer and the support on which the temporary adhesive layers (A) and (B) are formed are formed as a bonded substrate through the temporary adhesive layers (A) and (B). At this time, the laminate substrate in which the wafer is bonded to the support is obtained by uniformly pressing the substrate under reduced pressure at this temperature in a temperature range of preferably 40 to 230 ° C., more preferably 40 to 200 ° C. It is formed.
Examples of the wafer bonding apparatus include commercially available wafer bonding apparatuses such as EVG520IS and 850TB manufactured by EVG, and XBC300 manufactured by SUSS.
Thereafter, the thermosetting modified siloxane polymer layer (B) is cured by heating at 100 to 260 ° C., preferably 140 to 220 ° C. for 10 minutes to 5 hours, preferably 30 minutes to 2 hours to process the wafer. The body is preferable.

[Step (a)]
Step (a) is a step of grinding or polishing the non-circuit-formed surface of the wafer bonded to the support, that is, grinding or polishing the wafer back side of the wafer workpiece obtained by bonding as described above, This is a step of reducing the thickness of the wafer. There is no particular limitation on the method of grinding the back surface of the wafer, and a known grinding method is adopted. The grinding is preferably performed while cooling the wafer and a grindstone (such as diamond) with water. Examples of the apparatus for grinding the back surface of the wafer include DAG-810 (trade name) manufactured by DISCO Corporation.

[Step (b)]
Step (b) is a step of processing the wafer non-circuited surface of the non-circuit-formed surface, that is, the non-circuit-formed surface of the wafer processed body thinned by back surface grinding. This process includes various processes used at the wafer level. Examples include electrode formation, metal wiring formation, protective film formation, and the like. More specifically, metal sputtering for forming electrodes, etc., wet etching for etching a metal sputtering layer, application of a resist to form a mask for forming a metal wiring, pattern formation by exposure and development, resist peeling Conventionally known processes such as dry etching, metal plating, silicon etching for TSV formation, and formation of an oxide film on the silicon surface can be mentioned.

[Step (c)]
In step (c), the wafer processed in step (b) is peeled off from the wafer processed body, that is, after various processing is performed on the thinned wafer, it is peeled off from the wafer processed body before dicing. It is a process. As a peeling method, a method of separating the two by sliding in the opposite direction along the horizontal direction while mainly heating the wafer and the support (preferably 200 to 250 ° C.), the wafer or the support of the wafer processed body One side is fixed horizontally, the other is lifted at a certain angle from the horizontal direction, and a protective film is attached to the processed surface of the processed wafer, and the wafer and the protective film are processed by a peel method. Although the method etc. which peel from a body are mentioned, it can employ | adopt without a restriction | limiting in particular.
The present invention can be applied to all of these peeling methods, but one of the wafer and the support of the wafer processed body is fixed horizontally and the other is lifted at a certain angle from the horizontal direction, and A method of attaching a protective film to the processed surface of the processed wafer and peeling the wafer and the protective film by a peel method is more suitable. These peeling methods are usually performed at room temperature.

  Further, a dicing tape is adhered to the processed surface of the processed wafer, the dicing tape surface is vacuum-adsorbed to the adsorption surface, and the temperature of the adsorption surface is in a temperature range of 10 ° C. to 100 ° C. By peeling off the processed wafer by peel-off, the support can be easily peeled from the processed wafer, and the subsequent dicing process can be easily performed.

[Step (d)]
Step (d) is a step of removing a part of the temporary adhesive layer (A) remaining on the circuit forming surface of the peeled wafer. A part of the first temporary adhesive layer (A) may remain on the circuit forming surface of the wafer peeled from the support in the step (c), and the removal of the first temporary adhesive layer (A) For example, it can be performed by cleaning the wafer.
Any cleaning liquid that dissolves the non-aromatic saturated hydrocarbon group-containing organopolysiloxane that is the (A) layer in the temporary adhesive layer can be used for the cleaning in the step (d). Specifically, May include cleaning liquids such as pentane, hexane, cyclohexane, decane, isododecane and limonene. These solvents may be used alone or in combination of two or more. Moreover, when it is difficult to remove, bases and acids may be added to the solvent. Examples of bases that can be used include amines such as ethanolamine, diethanolamine, triethanolamine, triethylamine, and ammonia, and ammonium salts such as tetramethylammonium hydroxide. As the acids, organic acids such as acetic acid, oxalic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid can be used. The addition amount is 0.01 to 10% by mass, preferably 0.1 to 5% by mass in the concentration in the cleaning liquid. In order to improve the removability of the residue, an existing surfactant may be added. As a cleaning method, a method of performing cleaning with a paddle using the above liquid, a cleaning method of spraying, and a method of immersing in a cleaning liquid tank are possible. The temperature is preferably 10 to 80 ° C., preferably 15 to 65 ° C. If necessary, the layer (A) is dissolved with these solutions, and finally washed with water or rinsed with alcohol, followed by drying treatment. Thus, a thin wafer can be obtained.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
(Synthesis Example 1)
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 234 g (13 mol) of water and 35 g of toluene, and heated to 80 ° C. in an oil bath. In a dropping funnel, 183.6 g (0.8 mol) of norbornyltrichlorosilane, 12.9 g (0.1 mol) of dimethyldichlorosilane, and 10.9 g (0.1 mol) of trimethylchlorosilane were charged. The mixture was added dropwise with stirring for 1 hour. After completion of the addition, the mixture was further aged and stirred at 80 ° C. for 1 hour. Allow to stand while cooling to room temperature to remove the separated aqueous phase, then mix with 10% aqueous sodium sulfate solution and stir for 10 minutes, then leave for 30 minutes to remove the separated aqueous phase. The operation was repeated until the toluene phase became neutral to stop the reaction. An ester adapter was attached, and the toluene phase containing the organopolysiloxane was heated to reflux to remove water from the toluene phase. After the internal temperature reached 110 ° C., the mixture was further continued for 1 hour, and then cooled to room temperature. The obtained organopolysiloxane solution was filtered to remove insoluble matters, and subsequently toluene was removed by distillation under reduced pressure to obtain 134 g of solid organopolysiloxane (resin 1).
The obtained organopolysiloxane (resin 1) contains 80 mol% of T units, 10 mol% of D units and 10 mol% of M units, and the terminal has 0.1 silanol group per 100 g of organopolysiloxane (resin 1). It contained in moles, and the appearance was a colorless transparent solid with a weight average molecular weight of 7,100. The norbornyl group content in all organic groups and hydrogen atoms was 61%. Further, 80% of all organic groups and hydrogen atoms represented by R ^{1 to} R ³ were norbornyl groups. This organopolysiloxane (resin 1) was dissolved in an isododecane solution at a solid concentration of 20% and filtered through a 0.2 μm membrane filter to obtain a resin solution (A-1).

(Synthesis Example 2)
Similarly to Synthesis Example 1, 234 g (13 mol) of water and 35 g of toluene were charged into a 1 L flask and heated to 80 ° C. in an oil bath. Except that 206.6 g (0.9 mol) of norbornyltrichlorosilane, 7.1 g (0.05 mol) of methylvinyldichlorosilane, and 5.4 g (0.05 mol) of trimethylchlorosilane were charged into the dropping funnel. Prepared in the same manner as in Synthesis Example 1 to obtain 140 g of solid organopolysiloxane (resin 2).
The obtained organopolysiloxane contains 90 mol% of T units, 5 mol% of D units, and 5 mol% of M units, and the terminal is 0.1 mol of silanol groups and 0.034 mol of vinyl groups per 100 g of organopolysiloxane. Contains mol. The appearance was a colorless and transparent solid, and the weight average molecular weight was 5,900. The norbornyl group content in all organic groups and hydrogen atoms was 78 mol%, and the vinyl group was 4.3 mol%. In addition, 90% of all organic groups and hydrogen atoms represented by R ^{1 to} R ³ were norbornyl groups.

（式中、Ｍｅはメチル基を示す。） (Synthesis Example 3)
As the alkenyl group-containing organopolysiloxane (A1), 100 g of the solid organopolysiloxane (resin 2) obtained in Synthesis Example 2 was dissolved in 100 g of toluene to prepare a solution having a solid content concentration of 50%. In this solution, a platinum catalyst was added in an amount of 20 ppm by platinum atom with respect to the resin and heated to 60 ° C., and as a hydrosilyl group-containing compound (A2), a compound represented by the following formula (9) (SiH equivalent: 1473 g / mol) 27.5 g was dropped, and an exotherm due to the reaction was observed. This amount corresponds to 0.55 in terms of H / Vi ratio (ratio of SiH groups to total alkenyl groups). The reaction was performed at 100 ° C. for 2 hours to complete the reaction. Thereafter, the reaction product was concentrated by distillation under reduced pressure, and toluene was distilled off to solidify the reaction product, and then redissolved with isododecane, filtered through a 0.2 μm membrane filter, and a resin having a solid content concentration of 20%. A solution (A-2) was obtained. Further, an isododecane solution having a solid content concentration of 65% was filtered through a 1.0 μm membrane filter to obtain a resin solution (A-3). Further, when the weight average molecular weight Mw of this resin was measured by GPC, it was 30,000.

(In the formula, Me represents a methyl group.)

(Synthesis Example 4)
In a flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 9,3′-9,9′-bis (3-allyl-4-hydroxyphenyl) fluorene (M-1) 43.1 g, average structural formula (M 3) 29.5 g of organohydrogensiloxane, 135 g of toluene, and 0.04 g of chloroplatinic acid were charged, and the temperature was raised to 80 ° C. Thereafter, 17.5 g of 1,4-bis (dimethylsilyl) benzene (M-5) was dropped into the flask over 1 hour. At this time, the temperature in the flask rose to 85 ° C. After completion of the dropwise addition, the mixture was further aged at 80 ° C. for 2 hours, and then toluene was distilled off and 43 g of cyclohexanone was added to obtain a resin solution containing cyclohexanone having a resin solid content concentration of 65% by mass as a solvent. When the molecular weight of the resin content of this solution was measured by GPC, the weight average molecular weight was 45,000 in terms of polystyrene. Furthermore, 5 g of hexamethoxymethylol melamine (manufactured by Sanwa Chemical Co., Ltd., Nicalak MW-390) and bis (t-butylsulfonyl) diazomethane (manufactured by Wako Pure Chemical Industries, Ltd., BSDM) are added to 50 g of this resin solution. 0.2g was added and it filtered with a 1.0 micrometer membrane filter, and obtained the resin solution (B-1).

(Synthesis Example 5)
A compound (M-1) 396.9 g and a compound (M-2) 45.0 g were dissolved in 1,875 g of toluene in a 5 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, and then the compound ( M-3) 949.6 g and compound (M-4) 6.1 g were added and heated to 60 ° C. Thereafter, 2.2 g of a carbon-supported platinum catalyst (5 mass%) was added, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C., the mixture was further heated to 90 ° C. for 3 hours and then again to 60 ° C. After cooling, 2.2 g of a carbon-supported platinum catalyst (5 mass%) was added, and 107.3 g of the compound (M-5) was dropped into the flask over 1 hour. At this time, the temperature in the flask rose to 78 ° C. After completion of dropping, the mixture was further aged at 90 ° C. for 3 hours, then cooled to room temperature, 1,700 g of methyl isobutyl ketone (MIBK) was added, and the platinum catalyst was removed by pressure filtration of the reaction solution through a filter. . Furthermore, 760 g of pure water was added to the obtained polymer compound solution, and the mixture was stirred and allowed to stand for separation to remove the lower aqueous layer. This separation water washing operation was repeated 6 times to remove trace acid components in the polymer compound solution. While the solvent in this resin solution was distilled off under reduced pressure, 767 g of cyclopentanone was added to obtain a resin solution containing cyclopentanone having a solid concentration of 60% by mass as a solvent. When the molecular weight of the resin in the resin solution is measured by GPC, the weight average molecular weight is 62,000 in terms of polystyrene, and (i + j) / (g + h + i + j) in formula (6) is 0.10. Further, 16 g of epoxy resin of cresol novolak (manufactured by Nippon Kayaku Co., Ltd., EOCN1020-55) and 0.2 g of tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid HH-A) are added to 100 g of this resin solution. And it filtered with a 1.0 micrometer membrane filter, and obtained the resin solution (B-2).

(Examples 1 to 3 and Comparative Examples 1 and 2)
A 200 mm silicon wafer (thickness: 725 μm) on which a copper post having a height of 50 μm and a diameter of 60 μm is formed on the entire surface is spin coated (A-1) and (A-2) with the film thicknesses shown in Table 1. The film was formed on the wafer bump formation surface. At this time, after coating the resin, it was heated on a hot plate at 150 ° C. for 2 minutes. On the other hand, a glass plate having a diameter of 200 mm (thickness: 700 μm) was used as a support, and (B-1) and (B-2) were spin-coated on this support to form a film having the thickness shown in Table 1. At this time, after coating the resin, it was heated on a hot plate at 120 ° C. for 2 minutes. A silicon wafer having a resin layer on one or both sides and a glass plate were bonded in a vacuum bonding apparatus so that the resin surfaces were aligned, and a laminated substrate was produced (pressure bonding condition). The 200 mm wafer bonding was performed using a wafer bonding apparatus EVG520IS manufactured by EVG. The bonding temperature was as shown in Table 1, the pressure in the chamber at the time of bonding was 10 ⁻³ mbar or less, and the load was 5 kN.
Then, the following test was done. The results are shown in Table 1.

-Adhesion test-
After joining, once the substrate is heated using an oven at 180 ° C. for 1 hour, and the second temporary adhesive layer (B) is cured, the adhesion state of the interface after cooling to room temperature is visually confirmed, The case where no abnormality such as bubbles at the interface did not occur was evaluated as good and indicated by “◯”, and the case where abnormality occurred was evaluated as defective and indicated by “x”.

-Back grinding resistance test-
The back surface of the silicon wafer was ground using a diamond grindstone with a grinder (manufactured by DISCO, DAG810). After grinding to a final substrate thickness of 50 μm, the optical microscope (100 times) was examined for the presence of abnormalities such as cracks and peeling. A case where no abnormality occurred was evaluated as good and indicated by “◯”, and a case where abnormality occurred was evaluated as poor and indicated by “x”.

-Heat resistance test-
The laminate after the back grinding of the silicon wafer was placed in a 250 ° C. oven in a nitrogen atmosphere for 2 hours, and then examined for abnormal appearance after heating on a 270 ° C. hot plate for 10 minutes. When the appearance abnormality did not occur, it was evaluated as good and indicated by “◯”, and when the appearance abnormality occurred, it was evaluated as defective and indicated by “x”.

-Peelability test-
With respect to the peelability of the substrate, a dicing tape was attached to the wafer side thinned to 50 μm using a dicing frame, and the surface of the dicing tape was set on an adsorption plate by vacuum suction. Thereafter, the glass substrate was peeled off by lifting one point of the glass with tweezers at room temperature. A case where the glass support and the 50 μm wafer could be peeled without being broken was indicated by “◯”, and a case where an abnormality such as a crack occurred was evaluated as defective and indicated by “X”.

-Detergency test-
A 200 mm wafer (exposed to heat resistance test conditions) mounted on a dicing frame through a dicing tape after completion of the above peelability test is set on a spin coater with the adhesive layer facing upward, and isododecane is used as a cleaning solvent. After spraying for 3 minutes, isopropyl alcohol (IPA) was rinsed by spraying while rotating the wafer. Thereafter, the appearance was observed and the presence or absence of the remaining adhesive resin was visually checked. Those with no residual resin were evaluated as good and indicated with “◯”, and those with residual resin were evaluated as poor and indicated with “x”.

  When the (B) layer does not exist as in Comparative Example 1, in addition to the necessity of a high temperature of 260 ° C. that may damage the wafer during bonding, the (A) layer, the glass support, and the wafer The glass support was broken at the time of peeling. Further, when the (A) layer was not present as in Comparative Example (2), the peeling itself was not possible, and the wafer was detached from the vacuum suction table. On the other hand, in Examples 1 to 3, the wafers could be bonded together at a low temperature without damage, and the peeling could be carried out neatly from the interface between the (A) layer and the (B) layer.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

  DESCRIPTION OF SYMBOLS 1 ... Wafer, 2 ... Support body, 3 ... Temporary adhesive material layer, (A) ... Non-aromatic saturated hydrocarbon group containing organopolysiloxane polymer layer, (B) ... Thermosetting modified siloxane polymer layer, 10 ... Wafer processed body.

Claims (24)

Temporary adhesive layer is formed on a support, the provisional adhesive layer has a circuit surface having a circuit surface, Ri wafer to be processed back surface is Na are stacked, grinding or polishing the back surface A wafer processed body for thinning the wafer,
A first temporary adhesive layer comprising a non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A), wherein the temporary adhesive layer is releasably bonded to the surface of the wafer; A wafer processed body comprising a second temporary adhesive layer made of a thermosetting modified siloxane polymer layer (B) which is laminated on the support and is detachably bonded to the support. The polymer layer (A) is a polymer layer of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane containing units represented by the following (I) to (III). Wafer processed body.
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. ) Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
An alkenyl group-containing organopolysiloxane (A1) in which 2 to 30 mol% of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are alkenyl groups having 2 to 7 carbon atoms;
The following average composition formula (1)
_{^{R 7 a R 8 b H c}} SiO (4-a-b-c) / 2 (1)
(Wherein R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. A, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, (It is a positive number satisfying 0.75 ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4.)
A hydrosilyl group-containing compound having at least two SiH groups in one molecule, wherein the total SiH groups are 0.4 to 1 with respect to the total alkenyl groups of the alkenyl group-containing organopolysiloxane (A1). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the hydrosilyl group-containing compound (A2) in an amount of 0.0 times in the presence of a platinum group metal catalyst. 2. The wafer processed body according to 1. Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
A hydrosilyl group-containing organopolysiloxane (A3) in which 2 to 20 mol% of all the organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are hydrogen atoms;
The following average composition formula (2)
_{^{R 9 d R 10 e R 11}} f SiO (4-d-e-f) / 2 (2)
(In the formula, R ⁹ is a monovalent organic group excluding an alkenyl group, R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. D, e, f) Is a positive number satisfying 0 <d ≦ 2, 0 ≦ e ≦ 1, 0.75 ≦ d + e ≦ 3, 0.01 ≦ f ≦ 1, and 0.8 ≦ d + e + f ≦ 4.)
An alkenyl group-containing compound having at least two alkenyl groups in one molecule, wherein the total alkenyl groups are 1.0 to 2 with respect to the total SiH groups of the hydrosilyl group-containing organopolysiloxane (A3). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the alkenyl group-containing compound (A4) in an amount of 5 times in the presence of a platinum group metal catalyst. 2. The wafer processed body according to 1. The hydrosilyl group-containing compound (A2) contains an organohydrogenpolysiloxane containing SiH groups at both ends represented by the following structural formula (3), or contains SiH groups at both ends represented by the following structural formula (4). The processed wafer according to claim 3, wherein the processed wafer is a bissilyl compound.

(In the formula, n is a positive number of 0 to 400, and R ^{12 to} R ¹⁴ are the same or different, substituted or unsubstituted monovalent organic groups.)

(In the formula, R ^{15 to} R ¹⁷ are the same or different, substituted or unsubstituted monovalent organic groups. W is a divalent organic group.) The polymer layer (B) is a silphenylene-containing polymer compound having a weight average molecular weight of 3,000 to 500,000 having a repeating unit represented by the following general formula (5), or represented by the following general formula (6): Modified with formalin or formalin-alcohol as a crosslinking agent for 100 parts by mass of a thermosetting modified siloxane polymer composed of an epoxy group-containing silicone polymer compound having a weight average molecular weight of 3,000 to 500,000 having a repeating unit. Amino condensates, melamine resins, urea resins, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and an average of two or more epoxy groups in one molecule It is a cured product layer of a composition containing 0.1 to 50 parts by mass of any one or more selected from epoxy compounds Wafer processing body according to any one of claims 1 to 5, characterized in that.

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, A is a positive number, and B is 0 or a positive number. X is a divalent organic group represented by the following general formula (7).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. ]]

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, and g, h, i, and j are 0 or a positive number, provided that i and j are not 0 at the same time, and 0 <(i + j) / ( g + h + i + j) ≦ 1.0. Furthermore, X is a divalent organic group represented by the following general formula (7), and Y is a divalent organic group represented by the following general formula (8).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ²⁴ and R ²⁵ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. q is 0, 1, or 2. ]] The wafer processed body according to claim 1, wherein the wafer has a thickness of 600 to 800 μm. (A) grinding or polishing a non-circuit-formed surface of the wafer with respect to the processed wafer according to any one of claims 1 to 7 ;
(B) a step of processing the non-circuit-formed surface of the wafer;
(C) A method for producing a thin wafer, comprising a step of peeling the processed wafer from the support. The step of peeling the processed wafer (c) from the support,
A dicing tape is bonded to the processed surface of the processed wafer, the dicing tape surface is vacuum-adsorbed to the suction surface, and the temperature of the suction surface is in a temperature range of 10 ° C. to 100 ° C., and the support is processed. The method for producing a thin wafer according to claim 8 , wherein peeling is performed by peeling off the applied wafer. After the step of peeling the processed wafer (c) from the support,
(D) in claim 8 or claim 9, characterized in that a step of the removal of the non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer remaining on the circuit forming surface of the peeled wafer (A) The manufacturing method of the thin wafer of description. A temporary adhesive layer is formed on a support, and a wafer having a circuit surface on the surface is temporarily bonded on the temporary adhesive layer, and a wafer to be processed on the back surface is temporarily bonded, and the back surface is ground or polished. A wafer processing member for thinning the wafer,
The temporary adhesive layer is laminated on the second temporary adhesive layer, a second temporary adhesive layer made of a thermosetting modified siloxane polymer layer (B) releasably bonded to the support, and the wafer The wafer processing member provided with the 1st temporary adhesion layer which consists of a non-aromatic saturated hydrocarbon group containing organopolysiloxane polymer layer (A) which can adhere | attach to the surface of this. The polymer layer (A), according to claim 11, characterized in that a polymer layer of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane comprising units represented by the following (I) ~ (III) Wafer processing member.
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. ) Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
An alkenyl group-containing organopolysiloxane (A1) in which 2 to 30 mol% of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are alkenyl groups having 2 to 7 carbon atoms;
The following average composition formula (1)
_{^{R 7 a R 8 b H c}} SiO (4-a-b-c) / 2 (1)
(Wherein R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. A, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, (It is a positive number satisfying 0.75 ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4.)
A hydrosilyl group-containing compound having at least two SiH groups in one molecule, wherein the total SiH groups are 0.4 to 1 with respect to the total alkenyl groups of the alkenyl group-containing organopolysiloxane (A1). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the hydrosilyl group-containing compound (A2) in an amount of 0.0 times in the presence of a platinum group metal catalyst. 11. A member for processing a wafer according to 11 . Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
A hydrosilyl group-containing organopolysiloxane (A3) in which 2 to 20 mol% of all the organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are hydrogen atoms;
The following average composition formula (2)
_{^{R 9 d R 10 e R 11}} f SiO (4-d-e-f) / 2 (2)
(In the formula, R ⁹ is a monovalent organic group excluding an alkenyl group, R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. D, e, f) Is a positive number satisfying 0 <d ≦ 2, 0 ≦ e ≦ 1, 0.75 ≦ d + e ≦ 3, 0.01 ≦ f ≦ 1, and 0.8 ≦ d + e + f ≦ 4.)
An alkenyl group-containing compound having at least two alkenyl groups in one molecule, wherein the total alkenyl groups are 1.0 to 2 with respect to the total SiH groups of the hydrosilyl group-containing organopolysiloxane (A3). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the alkenyl group-containing compound (A4) in an amount of 5 times in the presence of a platinum group metal catalyst. 11. A member for processing a wafer according to 11 . The hydrosilyl group-containing compound (A2) contains an organohydrogenpolysiloxane containing SiH groups at both ends represented by the following structural formula (3), or contains SiH groups at both ends represented by the following structural formula (4). The wafer processing member according to claim 13 , wherein the wafer processing member is a bissilyl compound.

(In the formula, n is a positive number of 0 to 400, and R ^{12 to} R ¹⁴ are the same or different, substituted or unsubstituted monovalent organic groups.)

(In the formula, R ^{15 to} R ¹⁷ are the same or different, substituted or unsubstituted monovalent organic groups. W is a divalent organic group.) The polymer layer (B) is a silphenylene-containing polymer compound having a repeating unit represented by the following general formula (5) and having a weight average molecular weight of 3,000 to 500,000, or represented by the following general formula (6). 100 parts by mass of a thermosetting modified siloxane polymer composed of an epoxy group-containing silicone polymer compound having a repeating unit and a weight average molecular weight of 3,000 to 500,000 is modified with formalin or formalin-alcohol as a crosslinking agent. Amino condensates, melamine resins, urea resins, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and epoxy having an average of two or more epoxy groups in one molecule It is a cured product layer of a composition containing 0.1 to 50 parts by mass of any one or more selected from compounds For wafer processing member according to any one of claims 11 to 15, characterized in.

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, A is a positive number, and B is 0 or a positive number. X is a divalent organic group represented by the following general formula (7).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. ]]

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, and g, h, i, and j are 0 or a positive number, provided that i and j are not 0 at the same time, and 0 <(i + j) / ( g + h + i + j) ≦ 1.0. Furthermore, X is a divalent organic group represented by the following general formula (7), and Y is a divalent organic group represented by the following general formula (8).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ²⁴ and R ²⁵ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. q is 0, 1, or 2. ]] The wafer processing member according to claim 11, wherein a thickness of the wafer is 600 to 800 μm. A temporary adhesive for wafer processing, which has a circuit surface having a circuit on the front surface, temporarily bonds a wafer to be processed on the back surface to a support , and grinds or polishes the back surface to make the wafer thinner. A first temporary adhesive layer comprising a non-aromatic saturated hydrocarbon group-containing organopolysiloxane polymer layer (A) that can be bonded and peeled to the surface of the wafer, and the first temporary adhesive layer, A temporary adhesive for wafer processing, comprising: a second temporary adhesive layer comprising a thermosetting modified siloxane polymer layer (B) that can be bonded and peeled off from the body. The polymer layer (A), according to claim 18, characterized in that a polymer layer of a non-aromatic saturated hydrocarbon group-containing organopolysiloxane comprising units represented by the following (I) ~ (III) Temporary adhesive for wafer processing.
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. ) Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
An alkenyl group-containing organopolysiloxane (A1) in which 2 to 30 mol% of all organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are alkenyl groups having 2 to 7 carbon atoms;
The following average composition formula (1)
_{^{R 7 a R 8 b H c}} SiO (4-a-b-c) / 2 (1)
(Wherein R ⁷ is a monovalent organic group excluding an alkenyl group, and R ⁸ is a divalent organic group. A, b and c are 0 <a ≦ 2.5, 0 ≦ b ≦ 1, (It is a positive number satisfying 0.75 ≦ a + b ≦ 2.5, 0.005 ≦ c ≦ 1, and 0.8 ≦ a + b + c ≦ 4.)
A hydrosilyl group-containing compound having at least two SiH groups in one molecule, wherein the total SiH groups are 0.4 to 1 with respect to the total alkenyl groups of the alkenyl group-containing organopolysiloxane (A1). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the hydrosilyl group-containing compound (A2) in an amount of 0.0 times in the presence of a platinum group metal catalyst. The temporary adhesive for wafer processing as described in Item 18 . Among the non-aromatic saturated hydrocarbon group-containing organopolysiloxanes, the polymer layer (A) includes units represented by the following (I) to (III):
(I) Siloxane unit represented by R ¹ SiO _3/2 (T unit): 40 to 99 mol%
(II) Siloxane unit represented by R ² R ³ SiO _2/2 (D unit): 59 mol% or less (III) Siloxane unit represented by R ⁴ R ⁵ R ⁶ SiO _1/2 (M unit): 1-30 mol%
(The R ^{1 to} R ⁶ are a monovalent organic group or a hydrogen atom, and 50 mol% or more of all the organic groups and hydrogen atoms represented by the R ^{1 to} R ⁶ are non-aromatic having 3 to 20 carbon atoms. A non-aromatic group that is a saturated hydrocarbon group, and that contains 40% by mole or more of all the organic groups represented by R ^{1 to} R ³ and the hydrogen atom is the same or different and has the following cyclic structure having 5 to 7 carbon atoms. A saturated hydrocarbon group,

Further, except for the all organic groups represented by R ^{1 to} R ⁶ and the non-aromatic saturated hydrocarbon group in the hydrogen atom, the same or different hydrogen atoms or substituted or unsubstituted monovalent carbon atoms having 1 to 7 carbon atoms. It is a hydrogen group. )
A hydrosilyl group-containing organopolysiloxane (A3) in which 2 to 20 mol% of all the organic groups and hydrogen atoms represented by R ^{1 to} R ⁶ are hydrogen atoms;
The following average composition formula (2)
_{^{R 9 d R 10 e R 11}} f SiO (4-d-e-f) / 2 (2)
(In the formula, R ⁹ is a monovalent organic group excluding an alkenyl group, R ¹⁰ is a divalent organic group. R ¹¹ is an alkenyl group having 2 to 6 carbon atoms. D, e, f) Is a positive number satisfying 0 <d ≦ 2, 0 ≦ e ≦ 1, 0.75 ≦ d + e ≦ 3, 0.01 ≦ f ≦ 1, and 0.8 ≦ d + e + f ≦ 4.)
An alkenyl group-containing compound having at least two alkenyl groups in one molecule, wherein the total alkenyl groups are 1.0 to 2 with respect to the total SiH groups of the hydrosilyl group-containing organopolysiloxane (A3). A polymer layer of an organopolysiloxane obtained by hydrosilylation reaction of the alkenyl group-containing compound (A4) in an amount of 5 times in the presence of a platinum group metal catalyst. The temporary adhesive for wafer processing as described in Item 18 . The hydrosilyl group-containing compound (A2) contains an organohydrogenpolysiloxane containing SiH groups at both ends represented by the following structural formula (3), or contains SiH groups at both ends represented by the following structural formula (4). The temporary adhesive for wafer processing according to claim 20 , wherein the temporary adhesive is a bissilyl compound.

(In the formula, n is a positive number of 0 to 400, and R ^{12 to} R ¹⁴ are the same or different, substituted or unsubstituted monovalent organic groups.)

(In the formula, R ^{15 to} R ¹⁷ are the same or different, substituted or unsubstituted monovalent organic groups. W is a divalent organic group.) The polymer layer (B) is a silphenylene-containing polymer compound having a weight average molecular weight of 3,000 to 500,000 having a repeating unit represented by the following general formula (5), or represented by the following general formula (6): Modified with formalin or formalin-alcohol as a crosslinking agent for 100 parts by mass of a thermosetting modified siloxane polymer composed of an epoxy group-containing silicone polymer compound having a weight average molecular weight of 3,000 to 500,000 having a repeating unit. Amino condensates, melamine resins, urea resins, phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and an average of two or more epoxy groups in one molecule It is a cured product layer of a composition containing 0.1 to 50 parts by mass of any one or more selected from epoxy compounds For wafer processing temporary adhesive according to any one of claims 18 to claim 22, characterized in that.

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, A is a positive number, and B is 0 or a positive number. X is a divalent organic group represented by the following general formula (7).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. ]]

[In formula, R < ¹⁸ > -R < ²¹ > shows the C1-C8 monovalent hydrocarbon group which may be same or different. M is an integer of 1 to 100, and g, h, i, and j are 0 or a positive number, provided that i and j are not 0 at the same time, and 0 <(i + j) / ( g + h + i + j) ≦ 1.0. Furthermore, X is a divalent organic group represented by the following general formula (7), and Y is a divalent organic group represented by the following general formula (8).

(Where Z is

A divalent organic group selected from any one of the following: n is 0 or 1; R ²² and R ²³ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. k is 0, 1, or 2. )

(Where V is

And a p is 0 or 1. R ²⁴ and R ²⁵ are each an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other. q is 0, 1, or 2. ]] The temporary adhesive for wafer processing according to any one of claims 18 to 23, wherein the wafer has a thickness of 600 to 800 µm.

Images