JP6188614B2 - Laminate, composition for forming protective layer, kit, and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a laminate, a protective layer forming composition, a kit, and a method for manufacturing a semiconductor device. More specifically, a laminated body temporarily bonded to an adhesive support using a temporary adhesive for manufacturing a semiconductor device, in particular, an adhesive support in which a release layer is provided on a support substrate, a device via a protective layer. The present invention relates to a laminate provided with a wafer, a protective layer forming composition used for forming the protective layer, a kit including the protective layer forming composition, and a method for manufacturing a semiconductor device.

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

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

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

A semiconductor silicon wafer having a thickness of about 700 to 900 μm is widely known as a semiconductor silicon wafer used in a semiconductor device manufacturing process. However, in recent years, the thickness of a semiconductor silicon wafer has been reduced for the purpose of reducing the size of an IC chip. Attempts have been made to reduce the thickness to 200 μm or less.
However, since a semiconductor silicon wafer having a thickness of 200 μm or less is very thin, and a semiconductor device manufacturing member based on the wafer is also very thin, such a member may be further processed, or When such a member is simply moved, it is difficult to support the member stably and without causing damage.
In addition, there is a tape-shaped tape such as a back grind tape for polishing the device substrate, but it cannot withstand a high temperature processing process of about 220 ° C., which is later generated by polyethylene terephthalate (PET) used as a support substrate. .

  In order to solve the above problems, the device wafer before thinning with the device provided on the surface and the processing support substrate are temporarily fixed with a temporary adhesive, and the back surface of the device wafer is ground to reduce the thickness. After that, a technique for removing the processing support substrate from the device wafer is known (see Patent Document 1).

  Moreover, since the laminated body of the temporarily fixed device wafer and the processing support substrate is processed at a high temperature of about 220 ° C., an adhesive technology having heat resistance and easy attachment is disclosed (Patent Document 2). reference).

International Publication No. 2013/066541 Pamphlet International Publication Number 2013/153904 Pamphlet

  By the way, when the device surface of the device wafer and the support substrate (carrier substrate) are temporarily bonded using a layer made of the temporary adhesive composition described in Patent Document 1, the device wafer is thinned (for example, When the surface is polished (to a thickness of 200 μm or less), the surface opposite to the device surface of the device wafer (the surface of the device wafer on the silicon substrate side, corresponding to 61a in FIG. 1 to be described later, hereinafter sometimes referred to as “polishing surface”) In particular, problems such as the occurrence of uneven shapes tend to occur. Such a silicon substrate having a concavo-convex shape on the surface has low durability against a processing step, and it is difficult to form a good semiconductor device. The reason for this is that there are usually protrusions on the device surface of the device wafer (for example, bumps and pillars having a height of several to several hundreds of micrometers and a width of several to two hundreds of micrometers). Therefore, it is considered that the temporary adhesive composition provided on the device surface of the device wafer cannot be applied in a uniform amount in the film thickness direction, and stress caused by the temporary adhesive is locally generated. In particular, when the material of the temporary adhesive composition is hard, the above problem is likely to occur.

  On the other hand, as described above, in recent years, the TSV method is adopted. When the TSV method is adopted, in the processing of the device wafer, the chemical vapor deposition (CVD) is performed at a high temperature of about 200 ° C. after grinding the polished surface of the device wafer. A metal electrode is formed by a process. It has been found that when an uneven shape is generated on the polished surface of the silicon substrate of the device wafer, vapor deposition cannot be performed at an appropriate position and electrodes cannot be formed properly at the stage of CVD processing. In particular, it has been found that the problem becomes serious when the heat treatment time is long. The adhesive having improved heat resistance is described in Patent Document 2. However, in the adhesive described in Patent Document 2, when the adhesive is mechanically removed from the device wafer, the adhesive is used. Remains on the device wafer side. That is, means for imparting heat resistance other than that described in Patent Document 2 is required.

The present invention has been made in view of the above background, and after polishing the silicon substrate of the device wafer, the surface of the device wafer on the silicon substrate side (polishing surface) is less likely to generate unevenness and is CVD at a high temperature. It aims at forming an electrode appropriately according to a process.
More specifically, it aims at providing the composition for protective layer formation which can achieve the said subject. Furthermore, it aims at providing the manufacturing method of the laminated body which has a protective layer which uses the said composition for protective layer formation, the kit containing the said composition for protective layer formation, and a semiconductor device.

As a result of intensive studies to solve the above problems, the present inventors have found that the use of a predetermined protective layer forming composition makes it difficult for the surface of the device wafer on the silicon substrate side to form an uneven shape, and at a high temperature. The inventors have found that an electrode is appropriately formed by a CVD process, and have completed the present invention.
In general, in a semiconductor device processing step, a protective layer is heated to about 200 to 250 ° C., is subjected to high pressure, and a device wafer substrate and a carrier substrate (supporting substrate) having uneven portions (projections) on the surface. It plays the role of temporarily bonding. Therefore, unless the protective layer is soft at 200 ° C., the uneven stress of the substrate of the device wafer cannot be absorbed, and the smoothness of the substrate of the device wafer cannot be maintained. If the smoothness of the silicon substrate of the device wafer cannot be maintained, the silicon substrate of the device wafer is inclined at the time of polishing, so the uniformity of the film thickness of the substrate of the device wafer cannot be maintained, and the device after polishing An uneven shape is generated on the substrate of the wafer. Due to the uneven shape, a metal such as copper that becomes an electrode is not properly buried in the through hole of the substrate of the device during the TSV process. Therefore, the problem that an electrode does not flow into an electrode arises.
On the other hand, if the composition for forming the protective layer is too soft, the composition for forming the protective layer protrudes from the end portions of the device substrate and the support substrate during temporary bonding, thereby contaminating the inside of the apparatus.
In the present invention, these points were solved by giving an appropriate melt flow rate at 200 ° C.
Further, the polishing of the surface of the device wafer opposite to the device surface is usually performed at room temperature (for example, 20 to 38 ° C.) and at a low pressure (for example, 5 to 300 kPa). In the polishing process, the polishing pad moves in the surface direction of the substrate and polishes. Therefore, unlike the bonding step, stress is also applied in the surface direction. Therefore, the protective layer needs to have flexibility even at room temperature (for example, 25 ° C.). This softness was achieved by making the composition for forming a protective layer satisfy a predetermined Young's modulus.

Specifically, the above-mentioned problem has been solved by the following means <1>, more preferably <2> to <20>.
<1> A composition for forming a protective layer for bonding a device wafer and a support substrate, which includes a resin having a melt flow rate at 200 ° C. under a load of 10 kg in accordance with JIS K-7210 of 4 to 150 g / 10 min. The protective layer-forming composition has a Young's modulus based on JIS K-7127 of the protective layer-forming composition of 0.02 GPa or less.
<2> The protective resin for forming a protective layer according to <1>, wherein the resin includes a repeating unit derived from styrene, and the content of the repeating unit derived from styrene in the resin is 14 to 70% by mass. Composition.
<3> The composition for forming a protective layer according to <2>, wherein the block copolymer is a hydrogenated product.
<4> The composition for forming a protective layer according to <2> or <3>, wherein both ends of the block copolymer are repeating units derived from styrene.
<5> The composition for forming a protective layer according to any one of <2> to <4>, wherein the block copolymer is a hydrogenated product of a block copolymer of styrene and a conjugated diene.
<6> Furthermore, the composition for protective layer formation in any one of <1>-<5> containing 2 or more types of antioxidant.
<7> The composition for forming a protective layer according to <6>, comprising a phenol-based antioxidant and a sulfur-based antioxidant as the two or more types of antioxidants.
<8> At least one of the two or more types of antioxidants is an antioxidant having 2 to 6 groups represented by the following structure (A) in one molecule, <6> or <7> The composition for protective layer formation as described in 2.
Structure (A)
<9> The composition for forming a protective layer according to <6> or <7>, wherein at least one of the two or more antioxidants is the following compound.
<10> For forming a protective layer according to any one of <1> to <9>, wherein the resin has a melt flow rate at 200 ° C. under a load of 10 kg in accordance with JIS K-7210 of 20 g / 10 min or more. Composition.
<11> The composition for forming a protective layer according to any one of <1> to <10>, wherein the elongation at break of the resin according to JIS K-6251 is 1200% or less.
<12> The composition for forming a protective layer according to any one of <1> to <11>, wherein the elongation at break according to JIS K-6251 of the resin is 400 to 600%.
<13> The composition for forming a protective layer according to any one of <1> to <12>, wherein the elongation at break according to JIS K-6251 of the resin is 500% or less.
<14> The composition for forming a protective layer according to any one of <1> to <13>, further comprising a solvent.
<15> A device wafer, a protective layer, and a support substrate in this order,
A laminate comprising the protective layer forming composition according to any one of <1> to <14>.
<16> The laminate according to <15>, having a release layer or a separation layer between the protective layer and the support substrate.
<17> The laminate according to <16>, wherein the laminate includes a release layer containing a fluorine atom and / or a silicon atom.
<18> The laminate according to <17>, wherein the release layer is obtained by curing at least one of a bifunctional or higher functional radically polymerizable monomer or oligomer having a fluorine atom and an alkoxysilane compound having a fluorine atom. .
<19> A kit comprising the protective layer-forming composition according to any one of <1> to <14> and a release layer-forming composition comprising a material containing a fluorine atom and / or a silicon atom.
<20> A kit comprising a composition for forming a protective layer according to any one of <1> to <14> and a liquid for swelling or dissolving a protective layer formed using the composition for forming a protective layer.

  According to the present invention, after polishing the silicon substrate of the device wafer, the surface on the silicon substrate side (polishing surface) of the device wafer is less likely to generate unevenness, and the electrode can be appropriately formed by a CVD process at a high temperature. It has become possible to provide a layer forming composition. Furthermore, it became possible to provide a laminate having a protective layer using the protective layer forming composition, a kit containing the protective layer forming composition, and a method for manufacturing a semiconductor device.

1A, FIG. 1B, and FIG. 1C are respectively a schematic cross-sectional view illustrating temporary bonding between an adhesive support and a device wafer, a schematic plan view showing a device wafer temporarily bonded by the adhesive support, and bonding. It is a schematic sectional drawing which shows the state by which the device wafer temporarily bonded by the adhesive support body was thinned. FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of a group (atomic group) in this specification, the description which does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. In the present invention, “light” means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure by far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc. It also means drawing with particle beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous.The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a mass average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer, and a polymerizable group is a group involved in a polymerization reaction. In the present invention, the polymer compound means a compound having a mass average molecular weight of more than 2000.
Solid content means solid content at 25 ° C. unless otherwise specified.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.

  The composition for forming a protective layer of the present invention is used for manufacturing a semiconductor device, and usually forms a protective layer provided between a device wafer and a support substrate in a laminate having a device wafer and a support substrate. Used for.

  Here, the laminated body of this invention has a device wafer, a protective layer, and a support substrate in this order, and the said protective layer uses the predetermined composition for protective layer formation, It is characterized by the above-mentioned. By softening the protective layer at a high temperature (for example, at a high temperature of 200 ° C. or higher, or at a high temperature of 200 to 250 ° C.), the device-side structure (projections) of the device wafer is less likely to be damaged. The surface structure can be effectively protected. Moreover, in this invention, mechanical peeling can be easily performed because a protective layer has moderate hardness at room temperature.

Below, according to FIG. 1, embodiment of the laminated body of this invention is described. It goes without saying that the present invention is not limited to these configurations.
The stacked body shown in FIG. 1 has a configuration including a device wafer 60, a protective layer 71, a release layer 11, and a support substrate 100 in this order. In FIG. 1, the protective layer 71 contacts only the device wafer 60 and the release layer 11 and does not contact other members, and the release layer 11 contacts only the protective layer 71 and the support substrate 12 and contacts other members. It has no composition. Here, each of the protective layer and the release layer may be composed of only one layer, or may be composed of two or more layers. Each of the protective layer and the release layer is preferably a single layer.
In FIG. 1, the device wafer 60, the protective layer 71, the release layer 13, and the support substrate 12 have substantially the same projected area when viewed from the film surface direction of the laminate, They do not have to be the same size. However, in the laminate of the present invention, the device wafer, the protective layer, and the release layer each have a projected area of ± 10% or less of the projected area of the support substrate when viewed from the film surface direction of the laminate. Preferably, it is within ± 5%.
Returning to FIG. 1 again, the device wafer 60 includes, for example, a substrate 60 and a structure 62 provided on the surface thereof, as will be described in detail later.
In the present invention, the protective layer is preferably in contact with only the device wafer and the release layer without being in contact with the adhesive, and the release layer is also in contact with only the protective layer and the supporting substrate without being in contact with the adhesive. By adopting such a configuration, the device wafer and the support substrate after the semiconductor processing are easily separated. Further, by providing the protective layer, the support substrate can be easily peeled while appropriately protecting the device wafer having a structure such as a bump.
Therefore, according to the laminate of the present invention, when the device wafer is subjected to mechanical or chemical treatment, the device wafer can be provisionally supported easily and even after being processed at a high temperature. Temporary support for the processed device wafer can be released without damaging the device wafer.
The laminate for manufacturing a semiconductor device in the present invention is preferably for forming a silicon through electrode. The formation of the through silicon via will be described in detail later.
Further, a mode in which a separation layer described later is used instead of the release layer is also preferable.

<Protective layer>
The protective layer is used for the purpose of protecting the surface of the surface not subjected to the processing of the device wafer.
The protective layer in the present invention includes a device wafer containing a resin (hereinafter sometimes referred to as “specific resin”) having a melt flow rate at 200 ° C. under a load of 10 kg in accordance with JIS K-7210 of 4 to 150 g / 10 min. A protective layer forming composition for bonding a protective substrate to a support substrate, wherein the protective layer forming composition has a Young's modulus of 0.02 GPa or less in accordance with JIS K-7127. It is formed using.
With such a configuration, the unevenness of the surface of the laminate can be reduced, and the electrical characteristics of the device after being subjected to a chemical vapor deposition (CVD) process at 220 ° C. can be maintained high.

The lower limit of the melt flow rate of the specific resin is preferably 20 g / 10 min or more, more preferably 40 g / 10 min or more, further preferably 60 g / 10 min or more, and 80 g / 10 min or more. Is particularly preferably 90 g / 10 min or more, and the upper limit is preferably 120 g / 10 min or less, and more preferably 110 g / 10 min or less.
The specific resin has a melt flow rate at 230 ° C. under a load of 2.16 kg in accordance with JIS K-7210, preferably 4 to 150 g / 10 min, more preferably 50 to 90 g / 10 min, and 60 to 80 g / min. More preferably, it is 10 minutes.

Further, the viscosity of the specific resin when dissolved in toluene at 25 ° C. and 15% by mass is preferably 10 mPa · s or more and 40 mPa · s or less, and 15 mPa · s or more and 30 mPa · s or less. More preferably, it is more preferably 24 mPa · s or more and 26 mPa · s. By setting it as such a structure, the film thickness which can cover a protrusion at the time of coating-film formation at room temperature can be formed more easily.
Furthermore, the specific resin preferably has a breaking elongation according to JIS K-6251 of 1200% or less, more preferably 600% or less, and even more preferably 500% or less. The lower limit is not particularly defined, but can be, for example, 30% or more. More preferably, it can be 400% or more. By setting the elongation at break to such a value, the resin at the portion of the projection where stress concentrates at the time of bonding at a high temperature of 200 ° C. tends to more easily absorb the uneven stress of the projection.

The composition for forming a protective layer used in the present invention has a Young's modulus based on JIS K-7127 of 0.02 GPa or less, and more preferably 0.016 GPa or less. The lower limit is not particularly defined, but is, for example, 0.001 GPa or more.
As a method for preparing such a protective layer forming composition, for example, by selecting a resin that satisfies the Young's modulus when the composition is the specific resin, It can prepare by selecting so that the said Young's modulus may be satisfy | filled with the combination with resin of this, and an additive.

  The softening point of the protective layer is preferably lower than 250 ° C., which is the upper limit of the bonding temperature between a general device wafer and a support. This is because it becomes easier to flatten the surface of the protective layer during bonding. From this viewpoint, the softening point of the protective layer is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, and particularly preferably 200 ° C. or lower. By setting such a softening point, the protective layer becomes soft at the time of heat processing, and even if the release layer is hard, irregularities on the surface of the protective layer and the release layer can be reduced. The lower limit is not particularly defined but is 180 ° C. or higher.

The softening point of the protective layer is measured as a temperature at which the loss tangent (tan δ) measured using a viscoelasticity measuring device under a constant temperature rise is maximized.
The loss tangent (tan δ) is calculated by the following equation.
tan δ = G ″ / G ′
In the above formula, G ″ represents the loss shear modulus and G ′ represents the storage shear modulus.
The rate of temperature rise is preferably in the range of 0.5 to 20 ° C./min, more preferably in the range of 1 to 10 ° C./min, and in the range of 2 to 5 ° C./min. Is particularly preferred.

The average thickness of the protective layer is preferably 1 to 500 μm, more preferably 10 to 75 μm, and particularly preferably 15 to 60 μm. In particular, it is preferably thicker than the height of the device wafer structure described later.
The storage elastic modulus at 25 ° C. of the protective layer is preferably 1 M to 1 GPa, more preferably 10 M to 1 GPa, and further preferably 100 M to 1 GPa. By setting the protective layer to an elastic modulus as described later, the uneven shape of the substrate surface generated when the device wafer is polished can be more effectively suppressed, and the strong adhesion when the device wafer is thinned as described later, and the Debye wafer It is possible to more effectively achieve easy peeling at the time of separation.

As an example of the embodiment of the composition for forming a protective layer, an embodiment having a low content of metal ions is exemplified. By adopting such a configuration, it becomes difficult for the metal component to touch the electrode portion of the semiconductor device, and better electrical characteristics can be achieved. In the present embodiment, the total content of metal ions is preferably 200 ppm or less, more preferably 10 ppm or less, and even more preferably 50 ppb or less.
In particular, when the amount of sodium ions as the metal ions is in the above range, the electrical characteristics tend to be better.

  On the other hand, the aspect which mix | blends a metal ion in trace amount is illustrated as another example of embodiment of the composition for protective layer formation. By setting it as such a structure, when dissolving resin contained in the composition for protective layer formation in a solvent, aggregation of resin can be suppressed more effectively. Therefore, when dissolved in the composition for forming a protective layer, it is preferable that metal ions are contained. In this case, sodium ion is preferable as the metal ion. In the present embodiment, the total amount of metal ions is preferably 0.01 to 200 ppm, more preferably 1 to 200 ppm, and even more preferably 10 to 200 ppm in terms of the total metal ions.

<< Specific resin component >>
The resin (specific resin) having a melt flow rate at 200 ° C. under a load of 10 kg in accordance with JIS K-7210 of 4 to 150 g / 10 min is not particularly defined as long as this melt flow rate is satisfied. It is preferable to include a repeating unit.
The lower limit of the content of the repeating unit derived from styrene in the resin containing the repeating unit derived from styrene is preferably 14% by mass or more, more preferably 20% by mass or more, and further 40% by mass or more. Preferably, it is more preferably 55% by mass or more, and the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less.
The specific resin is preferably a block copolymer of styrene and another resin, and the block copolymer is more preferably a hydrogenated product. Furthermore, it is preferable that the both ends of the said block copolymer are repeating units derived from styrene, and it is more preferable that the repeating units derived from styrene are continuously polymerized. More preferably, the block copolymer is a hydrogenated product of a block copolymer of styrene and conjugated diene.
When both ends of the specific resin are repeating units derived from styrene, the thermal stability tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance is present at the end of the specific resin. In particular, the block part of the repeating unit derived from styrene is preferably a reactive polystyrene hard block, which tends to be more excellent in heat resistance and chemical resistance. Further, when these specific resins are block copolymers, it is considered that phase separation between hard blocks and soft blocks is performed at 200 ° C. or higher. The shape of the phase separation is considered to contribute to the suppression of the occurrence of irregularities on the substrate surface of the device wafer. In addition, such a resin is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.
On the other hand, when the specific resin is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  The weight average molecular weight of the specific resin is preferably 10,000 to 200,000, more preferably 150,000 to 200,000.

  In this specification, the “repeating unit derived from styrene” is a structural unit derived from styrene contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

  The specific resin in the present invention preferably has a content of repeating units derived from styrene in the range of 14 to 70% by mass and a weight average molecular weight in the range of 10,000 to 200,000. With such a configuration, the protective layer can be easily and quickly removed because it is easily dissolved in a hydrocarbon-based solvent described later. In addition, by using the specific resin, the resist wafer (eg, PGMEA, PGME, etc.), acid (hydrofluoric acid, etc.), alkali (TMAH, etc.) exposed when the device wafer is subjected to the resist lithography process. It exhibits particularly excellent resistance to it.

  Examples of the specific resin include resins sold under the trade names of elastomers and impact modifiers, such as polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer. Polymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), ethylene-propylene terpolymer (EPT), and hydrogenated products thereof Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene- Both styrene block Copolymer (SEEPS), styrene block is a reactively crosslinked styrene-ethyleneethylenepropylene-styrene block copolymer (Septon V9461 (manufactured by Kuraray), Septon V9475 (manufactured by Kuraray)), styrene block is a reactively crosslinked styrene- An ethylene butylene-styrene block copolymer (having a reactive polystyrene hard block, Septon V9827 (manufactured by Kuraray Co., Ltd.)) and the like can be selected, and a styrene-ethylene-propylene-styrene block copolymer (styrene- Isoprene-styrene block copolymer) (SEPS) is more preferred.

  Examples of commercially available products that can be used as the specific resin contained in the composition for forming a protective layer according to the present invention include, for example, “Septon (registered trademark)” manufactured by Kuraray Co., “Hibler (registered trademark)” manufactured by Kuraray Co., Ltd., Asahi Kasei Co., Ltd. “Tuftec (registered trademark)” manufactured by JSR, “Dynalon (registered trademark)” manufactured by JSR, and the like can be mentioned.

The addition amount of the specific resin component in the protective layer forming composition is preferably 1 to 100% by mass, more preferably 70 to 100% by mass, based on the total solid content (excluding the solvent) of the protective layer forming composition. Preferably, 90-100 mass% is especially preferable.
Only one type of specific resin component may be used, or two or more types may be used. When two or more types of resins are used, the total is preferably within the above range.

<< Other resin components >>
In the present invention, a resin other than the specific resin can be blended as a resin component that can be contained in the protective layer-forming composition.
For example, terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified Phenol resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, olefin copolymer (for example, methylpentene copolymer) , Cycloolefin copolymer (for example, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), novolac resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin , Polyure Resin, polyimide resin, polyethylene resin, polypropylene resin, ethylene propylene copolymer (EPDM rubber), polyvinyl chloride resin, polystyrene resin, polystyrene copolymer resin (except those corresponding to the specific resins mentioned above), methyl methacrylate Styrene copolymer resin (MS resin)), polyvinyl acetate resin, tetrafluoroethylene resin (PTFE resin), copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (PFA resin), tetrafluoroethylene hexafluoro Propylene copolymer (FEP resin), ethylene-TFE copolymer resin, polyvinylidene fluoride (PVDF resin), polychlorotrifluoroethylene (PCTFE resin), ethylene-chlorotrifluoroethylene resin (CTFE resin), TFE-perfluoro Jime Ludioxole copolymer resin, vinyl fluoride resin (PVF resin), acrylic resin, cellulose resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polysulfone, polyethersulfone resin And synthetic resins such as polybenzimidazole resin, polyarylate resin, polyetherketone resin, and polyamideimide resin, and natural resins such as natural rubber. Among them, polystyrene resin, polystyrene copolymer resin, polycarbonate resin, polyethersulfone resin, polyimide resin, polyester resin, polybenzimidazole resin, and polyamideimide resin are preferable, polystyrene resin, polystyrene copolymer resin, polycarbonate resin, and polyethersulfone resin. Polyimide resin, polyester resin, polybenzimidazole resin, polyamideimide resin, and polyetherketone resin are more preferable, and polystyrene resin, polystyrene copolymer resin, and polycarbonate resin are particularly preferable.

The addition amount of the other resin component in the protective layer is preferably 5 to 30% by mass of the specific resin when blended. There may be only one type of other resin component, or two or more types. When two or more types of resins are used, the total is preferably within the above range.
Preferred are olefin copolymers (eg, methylpentene copolymer), cycloolefin copolymers (eg, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), and cycloolefin copolymers (eg, norbornene copolymer). (Combined polymer, dicyclopentadiene copolymer, tetracyclododecene copolymer) are more preferable.

  Commercially available products of specific resins and other resins that can be used in the present invention include APEC 9379 (manufactured by BAYER), Estyrene MS200NT (manufactured by Nippon Steel Chemical Co., Ltd.), SEPTON S2104, SEPTON S2063, SEPTON S8104, SEPTON S2004, SEPTON S2007, SEPTON S8104, SEPTON S2002 (manufactured by Kuraray), TOPAS8007 (manufactured by Polyplastics), APEL8008 (manufactured by Mitsui Chemicals) L-70 (manufactured by Daicel Chemical), Ultrason E2020 (manufactured by BASF), Durimide 284 (Fujifilm) Product), Tuftec P2000, Tuftec H1043 (manufactured by Asahi Kasei) and the like can be suitably used.

<< Solvent >>
When the protective layer forming composition is layered by coating, it is preferable to add a solvent.
Any known solvent can be used without limitation as long as a protective layer can be formed. Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, PGMEA (1-methoxy 2-propyl acetate) and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl Butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate etc., and ketones such as methyl amyl ketone, methyl ethyl ketone, 2-butanone, cyclohexano And 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like are preferable.
Examples of saturated aliphatic hydrocarbons include straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, branched hydrocarbons having 3 to 15 carbon atoms, Examples thereof include p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tsujang, kalan, longifolene and the like.
Examples of aromatic hydrocarbons include toluene, xylene, anisole, mesitylene, limonene, and the like, N, N-dimethylacetamide.
Moreover, condensed polycyclic hydrocarbons are mentioned. The condensed polycyclic conducting hydrocarbons are condensed ring hydrocarbons formed by two or more monocycles supplying only one side of each ring to each other. In the present invention, two monocycles are condensed. It is preferable to use the following hydrocarbon. Such fused polycyclic hydrocarbons also include combinations of 5-membered and 6-membered rings, or combinations of two 6-membered rings. More specifically, examples of the condensed polycyclic hydrocarbons include indene, pentalene, indane, tetrahydroindene and the like, and examples of hydrocarbons in which two six-membered rings are combined include naphthalene, tetrahydronaphthalene (tetralin). ) And decahydronaphthalene (decalin).

Among them, anisole, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methyl amyl ketone, limonene, mesitylene, methyl ethyl ketone, PGMEA (1-methoxy-2-propyl acetate) and the like can be used. -Methyl-2-pyrrolidone, N, N-dimethylacetamide, methyl amyl ketone or limonene, p-menthane are preferred.
These solvents are also preferably in the form of a mixture of two or more from the viewpoint of improving the coated surface.
A preferable form of mixing two or more solvents is a combination of aromatic hydrocarbons and condensed polycyclic hydrocarbons, saturated aliphatic hydrocarbons and condensed polycyclic hydrocarbons. Particularly preferred combinations are decahydronaphthalene (decalin) and mesitylene, decahydronaphthalene (decalin) and p-menthane.
The preferred ratio is 0.1 to 30 parts by weight of the condensed polycyclic hydrocarbon, more preferably 1 to 20 parts by weight, still more preferably 100 parts by weight of the aromatic hydrocarbon or saturated aliphatic hydrocarbon. Is a ratio of 1 to 10 parts by weight When the protective layer forming composition has a solvent, the solvent should be used so that the solid content concentration of the protective layer forming composition is 5 to 60% by mass. Is preferred.
When there are two or more solvents, the total is preferably in the above range.

<< Surfactant >>
Various protective agents may be added to the composition for forming a protective layer from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the protective layer of the composition for forming a protective layer of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Thickness uniformity and liquid saving properties can be further improved.
That is, when forming a film using a protective layer-forming composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. As a result, the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the protective layer-forming composition. .

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

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

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

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
When the protective layer forming composition has a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass with respect to the total solid content of the protective layer forming composition. More preferably, it is 0.005 mass%-1.0 mass%.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.

<< Antioxidant >>
Various antioxidants may be added to the composition for forming a protective layer of the present invention from the viewpoint of preventing the molecular weight and gelation of the protective layer resin due to oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, a nitrogen-based antioxidant, and the like can be used.

Examples of phenolic antioxidants include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Sumitomo Chemical Co., Ltd. "Sumilizer MDP-S", "Sumilizer GA-80", etc. are mentioned.
As the phenolic antioxidant, an antioxidant having 2 to 6 groups represented by the following structure (A) in one molecule (hereinafter referred to as antioxidant A) is preferable, and the following structure (A An antioxidant having 2 to 4 groups represented by The molecular weight of the antioxidant A is preferably 250 to 1000. The following structure (A) is more preferably the following structure (B). The antioxidant A is preferably composed only of carbon atoms, hydrogen atoms, and oxygen atoms. Examples of antioxidant A include Irganox 1010, Irganox 1330, Irganox 3114, and Irganox 1035 described above.
Structure (A)
Structure (B)

  Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.

  Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.

Examples of amine-based antioxidants include dimethylaniline and phenothiazine. Among the above-mentioned antioxidants, the above-mentioned antioxidant A (in particular, Irganox 1010, Irganox 1330, Irganox 3114), 3,3′-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable. Irganox 1010 whose composition is shown below is particularly preferable.

The composition for forming a protective layer of the present invention preferably contains a phenol-based antioxidant and a sulfur-based antioxidant. In semiconductor processing, a high-temperature processing step of about 200 ° C. is performed over 30 minutes or more. In the high temperature process as described above, a reaction such as formation of a gel by the resin in the protective layer forming composition may occur. Since the gel portion has a different elastic modulus and thermal expansion coefficient from the non-gelled portion, it is difficult to maintain the flatness of the substrate due to the generation of the gel. By using the combination of antioxidants described above, the protective layer-forming composition can be prevented from being modified in the high-temperature processing step. The sulfur-based antioxidant absorbs the damage caused by the high heat of the phenol-based antioxidant, so that the protective layer-forming composition can be prevented from being deteriorated even during a long process time of 30 minutes or longer. It takes a minimum of 1 hour for the temperature in the apparatus to rise to 200 ° C., to pass through the processing steps, and cool to room temperature.
As the combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-o, Ir30x TP-D, 13g More preferred are Irganox 1010 and Sumilizer TP-D.
The ratio of the phenolic antioxidant and sulfur antioxidant added is preferably in the range of 2: 1 to 1: 2, more preferably 1: 1, by mass ratio.

The molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more from the viewpoint of preventing sublimation during heating. The upper limit is not particularly defined, but can be, for example, 2000 or less.
When the protective layer-forming composition has an antioxidant, the addition amount of the antioxidant is preferably 0.001% by mass to 20.0% by mass with respect to the total solid content of the protective layer-forming composition, More preferably, it is 0.005 mass%-10.0 mass%. When the high temperature process of 180 ° C. or higher is performed, 5.0 to 9.0% by mass is particularly preferable.
In particular, the sulfur-based antioxidant is preferably 1.0 to 10.0% by mass, more preferably 3.0 to 10.0% by mass, and particularly preferably 3.0 to 6.0% by mass.
One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.

<< Plasticizer >>
The composition for forming a protective layer of the present invention preferably contains a plasticizer in order to enhance the deformability at high temperature and improve the adhesion flatness.
As the plasticizer, phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.

Examples of the phthalic acid ester include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical), PL-200, DOIP (above, made by CG Esther), Sunsizer DUP (new) Nippon Rika).
Examples of fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (above, NOF Corporation), DBA, DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (manufactured by Daihachi Chemical Co., Ltd.) and the like.
Examples of the aromatic polycarboxylic acid ester include TOTM (manufactured by Daihachi Chemical), monosizer W-705 (manufactured by Daihachi Chemical), UL-80, UL-100 (manufactured by ADEKA), and the like.
Examples of the polyester include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (manufactured by DIC), BAA-15 (Daihachi Chemical).
Among the plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL, and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.
Only one type of plasticizer may be used, or two or more types may be combined.

  From the viewpoint of preventing sublimation during heating, the molecular weight of the plasticizer is preferably 250 ° C. or more when the mass is reduced by 1% by mass when measured under a nitrogen stream under a constant rate temperature rising condition of 20 ° C./min. 270 ° C. or higher is more preferable, and 300 ° C. or higher is particularly preferable. The upper limit is not particularly defined, but can be, for example, 500 ° C. or less.

  When the composition for protective layer formation in this invention has a plasticizer, 1 mass%-50.0 mass% are preferable with respect to the total solid of the composition for protective layer formation, and the addition amount of a plasticizer is 5 The mass% to 20 mass% is more preferable.

<High molecular compound having non-three-dimensional cross-linked fluorine atom>
The protective layer of the present invention preferably contains a polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure. The non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. It is preferable that it is contained substantially.
As the polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure, a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester. Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers, copolymers of ethylene with one or more of the fluorine-containing monofunctional monomers, Examples thereof include at least one fluorine-containing resin selected from a copolymer of one or more functional monomers and chlorotrifluoroethylene.

  The polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.

Specifically, the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
Formula (101)

In general formula (101), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represent. Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.

In the general formula (101), examples of the alkyl group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. An example of the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Among them, R ^{101 to} R ¹⁰³ are preferably a hydrogen atom or a methyl group.

Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and further preferably 1 to 10. 1 to 8 is more preferable, and 1 to 4 is particularly preferable. Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Y ¹⁰¹ is preferably an aliphatic group having a divalent linear structure.

Although it does not specifically limit as a monovalent organic group which has a fluorine atom represented by Rf, A C1-C30 fluorine-containing alkyl group is preferable, C1-C20 is more preferable, C1-C1 Fifteen fluorine-containing alkyl groups are particularly preferred. This fluorine-containing alkyl group is a straight chain {for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc. }, A branched structure {eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.}
Further, it may have an alicyclic structure (preferably a 5-membered or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these), and an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc. ). Further, it may be a perfluoroalkyl group.

That is, the perfluoroalkyl group-containing (meth) acrylic resin specifically has a repeating unit represented by the following formula (102).
Formula (102)

In General Formula (102), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , Y ¹⁰¹ , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.

  In addition to the perfluoroalkyl group-containing (meth) acrylic acid ester, the perfluoroalkyl group-containing (meth) acrylic resin can be arbitrarily selected from the viewpoint of peelability. Examples of the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.

  More specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic Butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerylnuri Tall monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylates (eg Methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, etc.) such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms). Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate , Glycidyl methacrylate, furfuryl methacrylate, tetrahydrofur Silyl methacrylate), aryl methacrylate (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrene such as styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, Butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene) , Dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichloro) Low styrene, tetrachlorostyrene, pentachlorostyrene, prom styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc. ), Radically polymerizable compounds containing acrylonitrile, methacrylonitrile acrylic acid, carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxylstyrene, and these acid groups Metal salts, ammonium salt compounds, etc.), and (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are preferred from the viewpoint of peelability, such as methyl (meth) acrylate, butyl , 2-ethylhexyl, lauri , Stearyl, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.

  Commercially available polymer compounds having a fluorine atom having a non-three-dimensional cross-linked structure described above include Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass), Halar (SolvaySolexis ), Heiler (SolvaySolexis), Lumiflon (Asahi Glass), Afras (Asahi Glass), Cefral Soft (Central Glass), Cefral Coat (Central Glass), etc., Vuitton (DuPont), Kalrez (DuPont) ), SIFEL (manufactured by Shin-Etsu Chemical Co., Ltd.), and other types of fluororubber, perfluoropolyether oils such as Krytox (DuPont), Fomblin (Daitotech), and Demnam (Daikin Industries) Fluorine oil, Daifree FB series (Daikin Industries), Megafu Fluorine-containing mold release agents with trade names such as the uck series (DIC Corporation), etc., are not limited to these, and any polymer compound having a fluorine atom with a non-three-dimensional crosslinked structure may be used. It can be used suitably.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) method of the polymer compound having a fluorine atom having a non-three-dimensional cross-linked structure is preferably 100,000 to 2,000, more preferably 50,000 to 2,000, and 10,000 to 10000. Most preferred is 2000.

The content of the polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure is preferably from 1 to 99% by mass, and from 3 to 50% by mass, based on the total solid content of the protective layer, from the viewpoint of good releasability. % Is more preferable, and 5 to 30% by mass is more preferable.
The polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure may be only one type or two or more types. When there are two or more kinds of polymer compounds having a fluorine atom having a non-three-dimensional crosslinked structure, the total is preferably in the above range.

<< Other additives >>
The composition for forming a protective layer in the present invention is various additives such as a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, and the like, as long as the effects of the present invention are not impaired. An ultraviolet absorber, an aggregation inhibitor, a polymerizable monomer, and the like can be blended. When mix | blending these additives, it is preferable that the total compounding quantity shall be 5 mass% or less of solid content of the composition for protective layer formation.
In the present invention, the total amount of additives is more preferably 3% by mass or less, and more preferably 1% by mass or less. Moreover, it can also be set as the aspect which does not contain an additive substantially. “Substantially free” means, for example, 0.1% by mass or less, and further 0% by mass of the specific resin used in the present invention. By setting it as such a structure, it can suppress more effectively that an additive decomposes | disassembles by a high temperature process (especially 200 degreeC or more). In particular, an embodiment in which the additive having a mass reduction degree of 5% by mass or more after heating at 200 ° C. for 60 minutes is substantially not included is an example of a preferable embodiment. Of course, it is needless to say that an embodiment containing an additive having a mass reduction degree of 5% by mass or more after heating at 200 ° C. for 60 minutes is also included in the scope of the present invention.
From the viewpoint of preventing sublimation during heating, the molecular weight of the additive is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more. The upper limit is not particularly defined, but can be, for example, less than 2000.

  When the composition for forming a protective layer contains a solvent, the viscosity is preferably 20 mPa · s or more and 100 mPa · s or less, and more preferably 20 mPa · s or more and 40 mPa · s or less.

The method for forming the protective layer is not particularly limited, but can be suitably achieved by appropriately changing the type and content of the specific resin component and other resins, and preferred specific examples of the resin This is achieved by selecting from the above, and obtaining a more preferable concentration.
Specifically, the protective layer is a protective layer forming composition, using a conventionally known spin coating method, spray method, screen printing method, roller coating method, flow coating method, doctor coating method, dipping method, etc. It can be formed by applying to a device wafer and then drying. Among these, the spin coat method, the spray method, and the screen printing method are preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.

<Peeling layer>
The release layer is used for the purpose of easily separating the protective layer and the support substrate. Therefore, the release layer is required to have a low surface energy and a small change in adhesion to heat. The release layer preferably contains a fluorine atom and / or a silicon atom, contains a fluorine atom and / or a silicon atom, and is in contact only with the protective layer and the supporting substrate, and does not come into contact with other members. . That is, the release layer has all one surface in contact with the protective layer and the other surface in contact with the support substrate.

The release layer is a low surface energy layer containing fluorine atoms and / or silicon atoms, and preferably has a material containing fluorine atoms and / or silicon atoms. The fluorine content in the release layer is preferably 80% by mass to 30% by mass, more preferably 76% by mass to 40% by mass, and particularly preferably 75% by mass to 60% by mass.
The fluorine content is defined by the mass of fluorine atoms in one molecule / the mass of all atoms in one molecule.
It is preferable that a peeling layer contains a three-dimensional crosslinked material from a heat resistant viewpoint. Among these, it is preferable to include at least one of a radical polymer of a bifunctional or higher functional radically polymerizable monomer or oligomer having a fluorine atom and a condensate of an alkoxysilane compound having a fluorine atom, and a fluorine-containing polyfunctional monomer / oligomer. Of these, a three-dimensionally crosslinked product or a three-dimensionally crosslinked product of a fluorine-containing silane coupling agent is particularly preferable. As the fluorine-containing silane coupling agent, a non-halogen silane coupling agent having a low risk to human body and low metal corrosivity is preferable, and a fluorine-containing alkoxysilane compound is particularly preferable. Examples of the halogen-based silane coupling agent include a fluorinated chlorosilane compound.
Below, the material containing a fluorine atom and / or a silicon atom which can be contained in the composition for peeling layer formation is described.

[Polymerizable monomer having fluorine atom or silicon atom]
The polymerizable monomer in the present invention is particularly preferably a polymerizable monomer having a fluorine atom or a silicon atom. The polymerizable monomer having a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and two or more fluorine atoms are contained in one molecule. Particularly preferred is a polymerizable monomer having a group generally called a perfluoro group.

  The radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but is an unsaturated group (such as an ethylenically unsaturated bond group). Preferably).

  The radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom preferably has two or more radically polymerizable functional groups, so that the laminate is subjected to a process at a high temperature, to the treated member. The peelability of the temporary support can be further improved.

[[Polymerizable monomer having a fluorine atom]]
The polymerizable monomer having a fluorine atom can be selected from known monomers, and is preferably a crosslinking agent having a polymerizable group as a crosslinkable group. Examples of the crosslinkable group include a silyl group having a hydroxyl group or a hydrolyzable group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, β-ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.

The radical polymerizable monomer having a fluorine atom is preferably a compound that can be represented by the following general formula (1).
General formula (I): Rf {-LY} n
(In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more. L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)

  In the above general formula (I), Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond. Groups having (meth) acryloyl groups, allyl groups, vinyloxy groups, etc., ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups) Carbamoyl group, mercapto group, β-ketoester group, hydrosilyl group, silanol group, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like are preferable.

  More preferably, Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond. Specifically, T preferably represents a radical polymerizable functional group represented by the following general formula (9).

(In general formula (9), R ^{901 to} R ⁹⁰³ each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to L.)

Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, Examples include 2-methylhexyl group and cyclopentyl group. An example of the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R ^{901 to} R ⁹⁰³ are preferably a hydrogen atom or a methyl group.

L represents a single bond or a divalent linking group. As a divalent linking group, a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, and a combination of two or more thereof are obtained. Represents a divalent linking group. However, said R represents a hydrogen atom or a C1-C5 alkyl group.
When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.

  Rf represents a chain or cyclic n-valent group that contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom. Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.

  As such a monomer having a fluorine atom, compounds described in paragraph numbers 0019 to 0033 of JP 2011-48358 A can be preferably used, and the contents thereof are incorporated in the present specification.

  The radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.

_{^{CH 2 = CR 1 COOR 2 R}} f ··· structural formula (1)
(In the structural formula (1), R ¹ is, .R ² represents a hydrogen atom or a methyl group, _{is, -C p H 2p -, -} C (C p H 2p + 1) H -, - CH 2 C ( _{C p H 2p + 1) H-} , or an -CH ₂ CH ₂ O-.
R ^f _{is, -C n F 2n + 1,} - (CF 2) n H, -C n F 2n + 1 -CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - ( _{CF 2) p OC m H 2m} C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, _{or, -N (C p H 2p +} 1) SO 2 C n F 2n + Represents ₁ . However, p represents an integer of 1 to 10, n represents an integer of 1 to 16, m represents an integer of 0 to 10, and i represents an integer of 0 to 16, respectively. )

CF ₂ = CFOR ^g. Structural formula (2)
(In Structural Formula (2), R ^g represents a C 1-20 fluoroalkyl group.)

CH ₂ = CHR ^g ... Structural formula (3)
(In Structural Formula (3), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

_{^{CH 2 = CR 3 COOR 5 R}} j R 6 OCOCR 4 = CH 2 ··· structural formula (4)
(In Structural Formula (4), R ³ and R ⁴ represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ represent —C _q H _2q —, —C (C _q H _{2q + 1} ) H— _{, -CH 2 C (C q H} 2q + 1) H- or -CH ₂ CH ₂ O-, R ^j is .q representing the -C _t F _2t is an integer of from 1 to 10, t is 1 to 16 Is an integer.)

CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R ^k ) CHOCOCR ⁸ = CH _2. Structural formula (5)
(In the structural formula (5), R ⁷ and R ⁸ are, .R ^k representing a hydrogen atom or a methyl group, is .y is -CyF _{2y + 1} is 1 to 16 integer.)

Examples of the monomer represented by the structural formula (1) include CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) _{4. CH 2 CH 2 OCOC (CH 3} ) = CH 2, C 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 2) CH ₂ CH ₂ OCOCH═CH ₂ , CF ₂ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOC (CH _{3 ) = CH 2, CF 3 (} CF 2) 4 CH (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 _{H 2 OCOCH = CH 2, C} 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH _{= CH 2, H (CF 2} ) 6 C (C 2 H 5) OCOC (CH 3) = CH 2, H (CF 2) 8 CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH ₂ , H (CF ₂ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF _{2 7} SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅₎ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH═CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH═CH ₂ , and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the fluoroalkylated olefin represented by the structural formula (2) or (3) include C ₃ F ₇ CH═CH ₂ , C ₄ F ₉ CH═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , _{C 3 F 7 OCF = CF 2} , C 7 F 15 OCF = CF 2, C 8 F 17 OCF = CF 2, and the like.

Examples of the monomer represented by the structural formula (4) or (5), for _{example, CH 2 = CHCOOCH 2 (CF} 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH ₂ OCOCH═CH ₂ , CH ₂ = CHCOOCH ₂ CH (CH ₂ C ₈ F ₁₇ ) OCOCH═CH ₂ , and the like.

  Moreover, as the radically polymerizable monomer or oligomer having a fluorine atom, an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radically polymerizable functional group can also be preferably used.

The repeating unit having a fluorine atom is preferably selected from at least one repeating unit represented by the following formulas (6), (7) and (10).

In the formula (6), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and R ¹ , R ² , R ³ , At least one of R ⁴ is a fluorine atom or a monovalent organic group having a fluorine atom.
In formula (7), R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
In formula (10), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, Y ² and Y ³ represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. . Rf represents a divalent organic group having a fluorine atom.

Although it does not specifically limit as a monovalent organic group which has a fluorine atom in Formula (6) and Formula (7), A C1-C30 fluorine-containing alkyl group is preferable, and C1-C20 is more preferable. A fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferable. This fluorine-containing alkyl group is a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc. ) even, branched structure (e.g. _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). May have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , — CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). Further, it may be a perfluoroalkyl group.

Although it does not specifically limit as a bivalent organic group which has a fluorine atom in Formula (10), A C1-C30 fluorine-containing alkylene group is preferable, C1-C20 is more preferable, C1-C1 Fifteen fluorine-containing alkylene groups are particularly preferred. This fluorine-containing alkylene group is a straight chain (for example, —CF ₂ CF ₂ —, —CH ₂ (CF ₂ ) ₄ —, —CH ₂ (CF ₂ ) ₈ CF ₂ —, —CH ₂ CH ₂ (CF ₂ ) _4. - even etc.), a branched structure (e.g. _{-CH (CF 3) CF 2 -} , - CH 2 CF (CF 3) CF 2 -, - CH (CH 3) CF 2 CF 2 -, - CH (CH ₃ ) (CF ₂ ) ₅ CF _2- and the like, and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl group or substituted therewith. A linking group having an alkyl group or the like, or an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₂ —, —CH ₂ CH ₂ OCH ₂ C ₄ F ₈ —, —CH ₂ CH ₂ OCH ₂ CH _{2). C 8 F 16 -, - CH} 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, _{-CH 2 CF 2 OCF 2 CF 2} OCF 2 CF 2 -, poly perfluoroalkylene ether chains, etc.) may have. Further, it may be a perfluoroalkylene group.

The monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements.
As a more specific example, an organic group composed of the following structures alone or in combination can be exemplified.
The monovalent organic group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group. Alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group, and the like. The organic group may contain an ether bond, an ester bond, or a ureido bond.

  The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, 2- A methylhexyl group, a cyclopentyl group, etc. are mentioned. An alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group. The alkynyl group is preferably an alkynyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Furthermore, the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.

R ¹ , R ² , R ³ and R ⁴ in formula (6), R ⁵ , R ⁶ , R ⁷ in formula ( ⁷ ), R ⁸ , R ⁹ , R ¹⁰ , R in formula (10) ^{As the} monovalent organic group represented by ¹¹ , R ¹² and R ¹³ , an alkyl group or an aryl group is preferable.
Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, Examples include 2-methylhexyl group and cyclopentyl group. An example of the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R ^{901 to} R ⁹⁰³ are preferably a hydrogen atom or a methyl group.

Y ¹ in formula (7) and —CO—, —O—, —NH—, a divalent aliphatic group, and a divalent aromatic group represented by Y ² and Y ³ in formula (10) Specific examples of the divalent linking group selected from the group consisting of these and combinations thereof are given below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to Rf.

L1: -CO-NH-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L2: -CO-NH-2 valent aliphatic group -O-CO-
L3: —CO-2 valent aliphatic group —O—CO—
L4: -CO-O-2 valent aliphatic group -O-CO-
L5: -valent aliphatic group -O-CO-
L6: -CO-NH-2 valent aromatic group -O-CO-
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 valent aromatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L19: -2 valent aromatic group -2 valent aliphatic group L20: -2 valent aromatic group -2 valent aliphatic group -O-2 valent aliphatic group-
L21: -valent bivalent aromatic group -divalent aliphatic group -O-2 valent aliphatic group -O-
L22: -CO-O-2 valent aliphatic group-
L23: -CO-O-2 valent aliphatic group -O-

Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and further preferably 1 to 10. 1 to 8 is more preferable, and 1 to 4 is particularly preferable.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.

  Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.

  The content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.

  The repeating unit having a radical polymerizable functional group is preferably a repeating unit represented by the following formula (8).

(In General Formula (8), R ^{801 to} R ⁸⁰³ each independently represents a hydrogen atom, an alkyl group, or a halogen atom. Y ⁸ represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and T represents a structure having a radical polymerizable functional group.

The alkyl group as R ^{801 to} R ⁸⁰³ is preferably an alkyl group having 1 to 6 carbon atoms.
T preferably represents a radical polymerizable functional group represented by the general formula (9).

(In general formula (9), R ^{901 to} R ⁹⁰³ each independently represents a hydrogen atom, an alkyl group or an aryl group. The dotted line represents a bond to a group linked to Y ^8. )

Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, Examples include 2-methylhexyl group and cyclopentyl group. An example of the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R ^{901 to} R ⁹⁰³ are preferably a hydrogen atom or a methyl group.

Y ⁸ represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represent. Specific examples of comprising the combination Y ⁸ below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).

L1: -CO-NH-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L2: -CO-NH-2 valent aliphatic group -O-CO-
L3: —CO-2 valent aliphatic group —O—CO—
L4: -CO-O-2 valent aliphatic group -O-CO-
L5: -valent aliphatic group -O-CO-
L6: -CO-NH-2 valent aromatic group -O-CO-
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 valent aromatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-

Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and further preferably 1 to 10. 1 to 8 is more preferable, and 1 to 4 is particularly preferable.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.

  Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.

  The content of the repeating unit having a radical polymerizable functional group is preferably 2 mol% to 98 mol% with respect to all repeating units of the radical polymerizable oligomer having a fluorine atom, and is preferably 10 mol% to 90 mol%. It is more preferable that

  The polystyrene-equivalent weight average molecular weight of the radically polymerizable oligomer having a fluorine atom by gel permeation chromatography (GPC) method is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.

  The polystyrene-reduced weight average molecular weight of the radically polymerizable oligomer having a fluorine atom by gel permeation chromatography (GPC) method is preferably 2000 to 10,000, more preferably 8000 to 2000, and more preferably 6000 to 2000. Most preferred.

When the release layer forming composition has a radical polymerizable monomer or oligomer having a fluorine atom, the content of the radical polymerizable monomer or oligomer having a fluorine atom is not particularly limited, and is preferably a release layer forming composition. It is preferable that it is 0.01 to 15 mass% with respect to the total solid content of a thing. If it is less than 0.01% by mass, the peelability tends to be insufficient. On the other hand, when it exceeds 15 mass%, there exists a tendency for adhesiveness to fall.
There may be only one kind of radically polymerizable monomer or oligomer having a fluorine atom, or two or more kinds. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.

[Radical polymerizable monomer or oligomer having a silicon atom]
In the present invention, the radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer. The compound which is a saturated group is mentioned, The compound which has a (meth) acryloyl group is preferable.

  It is preferable that the number average molecular weight of polystyrene conversion by the gel permeation chromatography method of the radically polymerizable oligomer which has a silicon atom is 1,000-10,000. When the number average molecular weight in terms of polystyrene by a gel permeation chromatography method of a radically polymerizable oligomer having a silicon atom is less than 1,000 or 10,000 or more, properties such as releasability due to a silicon atom are hardly expressed.

  As the radically polymerizable monomer having a silicon atom in the present invention, it is preferable to use a compound represented by the general formula (11) or (12).

(In the general formulas (11) and (12), R ^{11 to} R ¹⁹ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group. Z ¹¹ , Z ¹² , and Z ¹³ each independently represents a radically polymerizable group, L ¹¹ , L ¹² and L ¹³ each independently represents a single bond or a divalent linking group, and n and m each independently represent 0 or more. Represents an integer.)

In general formulas (11) and (12), R ^{11 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.

The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, or n-propyl. Group, isopropyl group and the like. The alkoxy group means —OR ²⁰ , and R ²⁰ represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group. And a butoxy group. An alkoxycarbonyl group means —C (═O) R ²¹ , where R ²¹ represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), specifically, methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.

L ¹¹ , L ¹² and L ¹³ each independently represents a single bond or a divalent linking group. The divalent linking group represents a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. .

  n and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.

Z ¹¹ , Z ¹² , and Z ¹³ each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.

(In general formula (i), R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or a monovalent organic group. X ¹⁰¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁰⁴ ) —, R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group.)

In the general formula (i), R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or a monovalent organic group. R ¹⁰¹ preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R ¹⁰² and R ¹⁰³ are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

X ¹⁰¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁰⁴ ) —, and R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R ¹⁰⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.

  Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

(In the general formula (ii), R ²⁰¹ ~R ²⁰⁵ are each independently, .Y ²⁰¹ represents a hydrogen atom or a monovalent organic group, an oxygen atom, a sulfur atom or -N, (R ²⁰⁶⁾ - representing the R ²⁰⁶ represents a hydrogen atom or a monovalent organic group.)

In formula (ii), R ²⁰¹ ~R ²⁰⁵ each independently represent a hydrogen atom or a monovalent organic group. R ²⁰¹ to R ²⁰⁵ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, a substituent An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.

Examples of the substituent that can be introduced include the same substituents as those described in formula (i).
^Y201 represents an oxygen atom, a sulfur atom, or -N ( ^R206 )-. R ²⁰⁶ has the same meaning as R ^{104 in} formula (i), and preferred examples thereof are also the same.

(In General Formula (iii), R ^{301 to} R ³⁰³ each independently represents a hydrogen atom or a monovalent organic group. Z ³⁰¹ represents an oxygen atom, a sulfur atom, —N (R ³⁰⁴ ) — or a substituent. Represents a phenylene group which may have R. ³⁰⁴ has the same meaning as R ^{104 in} formula (i).

In General Formula (iii), R ^{301 to} R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ³⁰¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity. R ³⁰² and R ³⁰³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent. An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.

Examples of the substituent that can be introduced include the same substituents as those described in formula (i). Z ³⁰¹ represents an oxygen atom, a sulfur atom, —N (R ³⁰⁴ ) — or a phenylene group which may have a substituent. R ³⁰⁴ has the same meaning as R ¹⁰⁴ in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.

When the release layer forming composition has a radical polymerizable monomer or oligomer having a silicon atom, the content of the radical polymerizable monomer or oligomer having a silicon atom is based on the total solid content of the release layer forming composition. It is preferable that it is 0.01 mass% or more and 15 mass% or less. If it is less than 0.01% by mass, the peelability tends to decrease. On the other hand, when it exceeds 15 mass%, there exists a tendency for adhesiveness to fall.
There may be only one kind of radically polymerizable monomer or oligomer having a silicon atom, or two or more kinds. When there are two or more types of radically polymerizable monomers or oligomers having a silicon atom, the total is preferably in the above range.

  Examples of the radical polymerizable monomer having a fluorine atom or a silicon atom include RS-75, RS-72-K, RS-76-E, RS-72-K manufactured by DIC Corporation, and OPTOOL manufactured by Daikin Industries, Ltd. DAC-HP, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, manufactured by Shin-Etsu Chemical Co., Ltd., Daicel Cytec Co., Ltd. Examples thereof include EBECRYL350 and EBECRYL1360 manufactured by Degussa, TEGORad2700 manufactured by Degussa, and UV-3500B (manufactured by BYK).

  As materials having fluorine atoms or silicon atoms, in addition to those described above, heptadecafluoro-1,1,2-tetrahydradecyl) trichlorosilane, (fluoro) alkyl phosphate, parylene fluoride, silicon acrylate copolymer, tetrafluoroethylene And copolymers of 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxole, polymers with pendant perfluoroalkoxy groups, fluorinated ethylene-propylene copolymers, and the like.

The content of the material containing fluorine atoms and / or silicon atoms is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content of the release layer, from the viewpoint of good releasability. 90 to 100% by mass is more preferable.
There may be only one type of material containing fluorine atoms and / or silicon atoms, or two or more types. In the case where two or more kinds of materials containing fluorine atoms and / or silicon atoms are used, the total is preferably within the above range.

<High molecular compound of non-three-dimensional cross-linked structure having fluorine atom>
The release layer of the present invention preferably contains a polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms. In addition, preferred embodiments of the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom are preferred because those described in the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom contained in the protective layer can be referred to. The range is the same.

The content of the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom is preferably 1 to 99% by mass, preferably 3 to 95% by mass, based on the total solid content of the release layer, from the viewpoint of good releasability. Is more preferable, and 5-90 mass% is further more preferable.
The polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure may be only one type or two or more types. When there are two or more kinds of polymer compounds having a fluorine atom having a non-three-dimensional crosslinked structure, the total is preferably in the above range.

  In this invention, it is preferable that ratio (mass ratio) of the high molecular compound which has a fluorine atom of the three-dimensional crosslinked material containing a fluorine atom and a non-three-dimensional crosslinked structure in a peeling layer is 5: 95-50: 50, It is more preferable that it is 10: 90-40: 60, and it is preferable that it is 15: 85-30: 70.

<< Solvent >>
When the release agent layer forming composition of the present invention is layered by coating, it is preferable to blend a solvent. Any known solvent can be used without limitation as long as a release layer can be formed.

As long as the release layer can be formed, any known solvent can be used without limitation, and the same solvent as the solvent in the protective layer described above can be used, and perfluoroalkane can also be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone, limonene, PGMEA (1-methoxy-2-propyl acetate), perfluoroalkane, methyl ethyl ketone, and the like can be used, and N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone or limonene, PGMEA (1-methoxy-2-propyl acetate) are preferred.
These solvents are also preferably in the form of a mixture of two or more from the viewpoint of improving the coated surface.

When the composition for forming the release layer has a solvent, the solvent is preferably used so that the solid content concentration of the composition for forming the release layer is 3 to 40% by mass, so that the composition is 5 to 40% by mass. More preferably it is used.
One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.

<< Other additives >>
In addition to the above components, the composition for forming a release layer can contain various compounds depending on the purpose within a range not impairing the effects of the present invention. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used.
Specific examples and preferred examples of the surfactant that the release layer-forming composition may have are the same as those of the surfactant that the protective layer-forming composition described above may have.
Specific examples and preferred examples of the antioxidant that the release layer-forming composition may have are the same as those of the antioxidant that the protective layer-forming composition may have.

  The release layer is formed on the support substrate by using a conventionally known spin coat method, spray method, roller coat method, flow coat method, doctor coat method, dipping method, or the like. It can be formed by applying to and then drying. Among these, the spin coat method, the spray method, and the screen printing method are preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.

The peeling layer is a 300 mm wafer with a protective layer attached, and the maximum adhesive force during peeling is preferably 20 N or less, more preferably 15 N or less, and even more preferably 10 N or less.
Moreover, 0.07 N / mm or less is preferable, as for the line peeling adhesive strength of a peeling layer, 0.05 N / mm or less is more preferable, and 0.03 N / mm or less is further more preferable.

  The average thickness of the release layer is preferably 1 nm to 20 μm, more preferably 1 nm to 10 μm, still more preferably 1 nm to 5 μm, and particularly preferably 1 nm to 1 μm.

The storage elastic modulus at 25 ° C. of the release layer is preferably 1 M to 10 GPa, more preferably 10 M to 10 GPa, and further preferably 100 M to 10 GPa. By making the release layer hard, it is possible to prevent adhesion of the release layer to the protective layer, which is preferable.
The ratio of the storage elastic modulus of the release layer and the protective elastic modulus of the protective layer is preferably 2: 1 to 1000: 1, more preferably 5: 1 to 1000: 1, and 10: 1 to More preferably, it is 1000: 1.

<Separation layer>
In the present invention, the following separation layer may be used in place of the release layer.
The separation layer is a layer formed of a material that changes in quality by absorbing light irradiated through the support substrate. In this specification, the “deterioration” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer is reduced. As a result of the alteration of the separation layer caused by absorbing light, the separation layer loses its strength or adhesion prior to light irradiation. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken and the support substrate and the device wafer can be easily separated.

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

  The separation layer is provided on the surface of the support substrate on the side where the device wafer is bonded via the protective layer. That is, the separation layer is provided between the support substrate and the protective layer.

  The thickness of the separation layer is, for example, more preferably 0.05 to 50 μm, and further preferably 0.3 to 1 μm. If the thickness of the separation layer is within the range of 0.05 to 50 μm, desired alteration can be caused in the separation layer by short-time light irradiation and low-energy light irradiation. The thickness of the separation layer is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

  Note that in the stacked body, another layer may be further formed between the separation layer and the support substrate. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thus, a layer imparting preferable properties to the laminate can be appropriately added without hindering the incidence of light on the separation layer. The wavelength of light that can be used differs depending on the type of material constituting the separation layer. Therefore, the material constituting the other layer does not need to transmit all the light, and can be appropriately selected from materials capable of transmitting light having a wavelength that can alter the material constituting the separation layer.

  In addition, the separation layer is preferably formed only from a material having a structure that absorbs light. However, a material that does not have a structure that absorbs light is used as long as the essential characteristics of the present invention are not impaired. It may be added to form a separation layer. In addition, it is preferable that the surface of the separation layer facing the protective layer is flat (no irregularities are formed), so that the separation layer can be easily formed and evenly pasted. It becomes possible.

  The separation layer may be used by pasting the material constituting the separation layer as shown below into a support substrate and applying the material constituting the separation layer on the support substrate. A solidified film may be used. The method of applying the material constituting the separation layer on the support substrate may be appropriately selected from conventionally known methods such as deposition by chemical vapor deposition (CVD), depending on the type of material constituting the separation layer. it can.

  The separation layer may be altered by absorbing light emitted from the laser. That is, the light applied to the separation layer in order to change the quality of the separation layer may be emitted from a laser. Examples of lasers that emit light to irradiate the separation layer include solid-state lasers such as YAG lasers, Libby lasers, glass lasers, YVO4 lasers, LD lasers, fiber lasers, liquid lasers such as dye lasers, CO2 lasers, excimer lasers, Ar Examples thereof include a gas laser such as a laser and a He—Ne laser, a laser beam such as a semiconductor laser and a free electron laser, or a non-laser beam. A laser that emits light to irradiate the separation layer can be selected as appropriate according to the material constituting the separation layer, and a laser that emits light of a wavelength that can alter the material constituting the separation layer. Just choose.

(Polymer containing light absorbing structure in its repeating unit)
The separation layer may contain a polymer containing a light-absorbing structure in its repeating unit. The polymer is altered by irradiation with light. Alteration of the polymer is caused by absorbing light irradiated by the structure. The separation layer loses its strength or adhesion before being irradiated with light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken, and the support substrate and the wafer can be easily separated.

  The structure having light absorption is a chemical structure that absorbs light and alters the polymer containing the structure as a repeating unit. The above structure is an atomic group including a conjugated π electron system composed of, for example, a substituted or unsubstituted benzene ring, condensed ring or heterocyclic ring. More specifically, the structure may be a cardo structure or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), a diphenyl structure or a diphenylamine structure present in the side chain of the polymer.

  The structure when the structure is present in the side chain of the polymer can be represented by the following group S:

Group (S)

In the formula, each R is independently an alkyl group, aryl group, halogen atom, hydroxyl group, ketone group, sulfoxide group, sulfone group, or N (R ¹ ) (R ² ) (where R ¹ and R ² Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent, or is —CO—, —SO ₂ —, —SO— or —NH—, and n is It is 0 or an integer of 1-5.

  In addition, the polymer includes, for example, a repeating unit represented by any one of (a) to (d) among the following formulas, represented by (e), or represented by (f) Contains structure in its main chain.

In the formula, l is an integer of 1 or more, m is 0 or an integer of 1 to 2, and X is any one of the structures exemplified as the group (S) in (a) to (e). And (f) is any one of the above-mentioned group (S) or is not present, and Y ₁ and Y ₂ are each independently —CO— or —SO ₂ —. l is preferably an integer of 10 or less. Aryl is an aryl group.

  Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above group (S) include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluoride, substituted fluoride, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene, and substituted pyrene. When the exemplified substituent has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, carboxylic acid Selected from esters, sulfonic acids, sulfonate esters, alkylamino and arylamino.

Of the substituents shown in the above group (S), the fifth substituent having two phenyl groups and Z is —SO ₂ — includes bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, and the like.

  Of the substituents shown in the above group (S), as an example of the fifth substituent having two phenyl groups and Z being —SO—, bis (2,3 -Dihydroxyphenyl) sulfoxide, bis (5-chloro-2,3-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (5 -Chloro-2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-dihydroxyphenyl) sulfoxide, bis (2,3 , 4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methylpheny ) -Sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-trihydroxy) Phenyl) sulfoxide and the like.

  Of the substituents shown in the above group (S), the fifth substituent having two phenyl groups and Z is —C (═O) — , 4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2 ' -Dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethyl Ruamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone, and 4 -Dimethylamino-3 ', 4'-dihydroxybenzophenone and the like.

  When the structure is present in the side chain of the polymer, the ratio of the repeating unit containing the structure to the polymer is such that the light transmittance of the separation layer is 0.001 to 10%. Is in range. If the polymer is prepared so that the ratio falls within such a range, the separation layer can absorb light sufficiently and can be surely and rapidly altered. That is, the support substrate can be easily removed from the laminate, and the light irradiation time necessary for the removal can be shortened.

  The said structure can absorb the light which has a wavelength of a desired range by selection of the kind. For example, the wavelength of light that can be absorbed by the above structure is more preferably 100 to 2000 nm. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, 100 to 500 nm. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength of about 300-370 nm.

  The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm to 436 nm), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F2 excimer laser (wavelength: 157 nm), or XeCl. Light emitted from laser (308 nm), XeF laser (wavelength: 351 nm) or solid-state UV laser (wavelength: 355 nm), or g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) or i-line (wavelength: 365 nm) Etc.

  Although the separation layer described above contains a polymer containing the structure as a repeating unit, the separation layer may further contain components other than the polymer. As said component, the component etc. which can improve the peelability of a filler, a plasticizer, and a support substrate are mentioned. These components are appropriately selected from conventionally known substances or materials that do not hinder or promote the absorption of light by the above structure and the alteration of the polymer.

(Inorganic)
The separation layer may be made of an inorganic material. Since the separation layer is composed of an inorganic material, the separation layer is altered by absorbing light, and as a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken and the support substrate and the device wafer can be easily separated.

The said inorganic substance should just be the structure which changes in quality by absorbing light, for example, can use 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon suitably. The metal compound refers to a compound containing a metal atom, and can be, for example, a metal oxide or a metal nitride. Examples of such inorganic materials include, but are not limited to, gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more inorganic substances selected from the group consisting of: Carbon is a concept that may include an allotrope of carbon, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.

  The inorganic material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the inorganic material used in the separation layer, the inorganic material can be suitably altered.

The light applied to the separation layer made of an inorganic material may be, for example, a solid-state laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser, depending on the wavelength that the inorganic material can absorb. A liquid laser, a CO ₂ laser, an excimer laser, an Ar laser, a He—Ne laser or the like, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate.

  The separation layer made of an inorganic substance can be formed on the support substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer made of an inorganic material is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used. For example, a film thickness of 0.05 to 10 μm is more preferable. Alternatively, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer, and may be attached to the support substrate and the wafer.

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

(Compound having infrared absorbing structure)
The separation layer may be formed of a compound having an infrared absorbing structure. The above compounds are altered by absorbing infrared rays. The separation layer loses its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken, and the support substrate and the wafer can be easily separated.

  Examples of the compound having an infrared absorptive structure or a compound having an infrared absorptive structure include alkanes and alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, ring Formula), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, peroxide ether, ketone, dialkylcarbonyl, aromatic Carbonyl, 1,3-diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer Carboxylate anion), formate ester, acetate ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride ( Conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), secondary Tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, Isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, Acid ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and sulfur compounds such as thiophenol and thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary Secondary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A1 bond (A1 is H, C, O or halogen), P-A2 bond (A2 is H, C or O), Or it may be a Ti-O bond.

As a structure containing halogen bond, for _{example, -CH 2 Cl, -CH 2 Br} , -CH 2 I, -CF 2 - - the _{carbon, - CF 3, -CH = CF} 2, -CF = CF 2, fluoride Aryl chloride, and aryl chloride.

As a structure including the Si-A1 _{bonds, SiH, SiH 2, SiH 3} , Si-CH 3, Si-CH 2 -, Si-C 6 H 5, SiO _{aliphatic, Si-OCH 3, Si-} OCH 2 CH ₃ , Si—OC ₆ H ₅ , Si—O—Si, Si—OH, SiF, SiF ₂ , SiF _{3 and the} like can be mentioned. As a structure including a Si-A1 bond, it is particularly preferable that a siloxane skeleton and a silsesquioxane skeleton are formed.

Examples of the structure containing the P—A2 bond include PH, PH ₂ , P—CH ₃ , P—CH ₂ —, P—C ₆ H ₅ , A33-PO (A3 is aliphatic or aromatic), ( A4O) ₃ -P-O (A4 _{alkyl), P-OCH 3, P} -OCH 2 CH 3, P-OC 6 H 5, P-O-P, such as P-OH, and O = P-OH is Can be mentioned.

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. Specifically, the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 to 20 μm, and the range of 2 to 15 μm can be more suitably absorbed. Furthermore, in the case where the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, it can be in the range of 9 to 11 μm. In addition, those skilled in the art can easily understand the infrared wavelength that can be absorbed by each structure. For example, as an absorption band in each structure, SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR, UV” (published in 1992), pages 146- The description on page 151 can be referred to.

  As the compound having an infrared absorbing structure used for forming the separation layer, among the compounds having the structure as described above, it can be dissolved in a solvent for coating and solidified to form a solid layer. If it is a thing, it will not specifically limit. However, in order to effectively alter the compound in the separation layer and facilitate separation of the support substrate and the wafer, the absorption of infrared rays in the separation layer is large, that is, the infrared rays when the separation layer is irradiated with infrared rays. It is preferable that the transmittance is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

  For example, as the compound having a siloxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit derived from an acrylic compound can be used.

(In the chemical formula (2), R ₁ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms)
Among them, as a compound having a siloxane skeleton, a copolymer of tert-butylstyrene (TBST) -dimethylsiloxane which is a copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3). A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the following chemical formula (3) at 1: 1 (molar ratio) is further preferable. .

  Moreover, as the compound having a silsesquioxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (4) and a repeating unit represented by the following chemical formula (5) can be used. .

(In the chemical formula (4), R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in the chemical formula (5), R ₃ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. .)
Other compounds having a silsesquioxane skeleton are disclosed in JP 2007-258663 A, JP 2010-120901 A, JP 2009-263316 A, and JP 2009-263596 A. Each silsesquioxane resin can be suitably utilized and the contents thereof are incorporated herein.

  Among these, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (6) and a copolymer of repeating units represented by the following chemical formula (7) are more preferable. A copolymer containing the repeating unit represented by the formula (7) and the repeating unit represented by the following chemical formula (7) at 7: 3 (molar ratio) is more preferable.

  The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage structure, but any structure may be used.

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. alkoxy titanium such as, (ii) di -i- propoxy bis (acetylacetonato) titanium, and propane di oxytitanium bis (ethylacetoacetate) chelate titanium such _{as, (iii) i-C 3} H 7 O - [- _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, and _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O -] n-n-C ₄ titanium polymers such as H _9, (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearyl Rate, and (2-n-butoxycarbonyl benzoyloxy) tributoxy acylate titanium such as titanium, and the like (v) di -n- butoxy bis (triethanolaminato) a water-soluble titanium compound such as titanium.

Among them, as a compound containing a Ti—O bond, di-n-butoxy bis (triethanolaminato) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ ) is preferred.

  Although the separation layer described above contains a compound having an infrared absorbing structure, the separation layer may further contain components other than the above compound. As said component, the component etc. which can improve the peelability of a filler, a plasticizer, and a support substrate are mentioned. These components are appropriately selected from conventionally known substances or materials that do not prevent or promote the absorption of infrared rays by the above structure and the alteration of the compound.

(Fluorocarbon)
The separation layer may be made of a fluorocarbon. Since the separation layer is composed of fluorocarbon, the separation layer is altered by absorbing light, and as a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken, and the support substrate and the wafer can be easily separated.

Further, from one viewpoint, the fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD method. In addition, fluorocarbon includes CxFy (perfluorocarbon) and CxHyFz (x, y, and z are integers), but is not limited thereto, for example, CHF ₃ , CH ₂ F ₂ , C ₂ H ₂ F ₂ , C ₄ F ₈ , C ₂ F ₆ , C ₅ F _{8 and the} like. In addition, an inert gas such as nitrogen, helium or argon, a hydrocarbon such as alkane or alkene, and oxygen, carbon dioxide or hydrogen may be added to the fluorocarbon used for constituting the separation layer. Also good. Further, a mixture of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.). Further, the separation layer may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.

  The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

As light to irradiate the separation layer, depending on the wavelength that can be absorbed by the fluorocarbon, for example, YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, liquid laser such as fiber laser, liquid laser such as dye laser, A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

(Infrared absorbing material)
The separation layer may contain an infrared absorbing material. The separation layer is configured to contain an infrared ray absorbing substance, so that the separation layer is altered by absorbing light, and as a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support substrate), the separation layer is broken, and the support substrate and the wafer can be easily separated.

  The infrared absorbing material only needs to have a structure that is altered by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be suitably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

<Support substrate>
The laminate of the present invention has a support substrate. The material of the support substrate is not particularly limited, and examples include a silicon substrate, a glass substrate, a metal substrate, a sapphire substrate, a SiC substrate, and a GaN substrate. In view of difficulty, an electrostatic chuck widely used in the manufacturing process of the semiconductor device, and the like can be used, the silicon substrate is preferable.
The thickness of the support substrate is not particularly limited, and is preferably 300 μm to 5 mm.

<Device wafer>
The laminate of the present invention has a device wafer. The device wafer is covered with the protective layer on the entire surface in contact with the protective layer.
A well-known thing can be used for a device wafer without a restriction | limiting, For example, (MEMS, the device for sensors) etc. are mentioned.
The device wafer preferably has a structure (for example, a metal bump). The height of the structure is preferably 5 to 100 μm.
The metal bump preferably uses solder or copper, and more preferably uses copper.

The device wafer preferably has a film thickness of 500 μm or more, preferably 600 μm or more, and more preferably 700 μm or more.
Although details will be described later, the device wafer is preferably thinned to a thickness of less than 500 μm by subjecting the surface opposite to the surface in contact with the protective layer to mechanical or chemical treatment. A more preferable film thickness is 400 μm or less, and a more preferable film thickness is 300 μm or less.

kit:
The present invention relates to a kit comprising the protective layer-forming composition of the present invention and a release layer-forming composition containing a material containing fluorine atoms and / or silicon atoms.
The laminate of the present invention can be produced by applying the release layer forming composition on the support substrate, applying the release layer forming composition, and then applying the protective layer forming composition.
Moreover, this invention relates to the kit containing the liquid which swells or melt | dissolves the protective layer which uses the composition for protective layer formation of this invention, and the said composition for protective layer formation. The liquid that swells or dissolves the protective layer is the same as that described later.
The respective compositions, preferred ranges, and the like of the release layer forming composition and the protective layer forming composition are the same as those described in the section of the release layer forming composition and the protective layer forming composition.

Method for producing the laminate:
The laminate of the present invention is preferably formed on a supporting substrate so as to have a release layer or separation layer, a protective layer, and a device wafer in this order. The laminate of the present invention is a method for bonding a support substrate having a release layer and a protective layer to a device wafer, a method for bonding a support substrate having a release layer and a device wafer having a protective layer, or a support substrate and a release layer. It can be produced by a method in which a layer and a device wafer having a protective layer are bonded. From the viewpoint of adhesiveness and easy peelability, a method of adhering a support substrate having a release layer and a protective layer and a device wafer, or a method of adhering a support substrate having a release layer and a device wafer having a protective layer is preferable. A method of bonding a support substrate having a release layer and a device wafer having a protective layer is most preferable so as not to cause defects called voids (voids) in the laminate.

Semiconductor device manufacturing method:
Subsequently, the adhesive support body and the manufacturing method of a semiconductor device using the laminated body in this invention demonstrated above are demonstrated.

A method for manufacturing a semiconductor device includes a step of bonding a first surface of a member to be processed and a substrate so that the laminate of the present invention is interposed, and the member to be processed is 130 ° C. or higher, particularly 200 ° C. It is preferable to have a step of performing a heat treatment having a maximum temperature not lower than ° C. to obtain a processed member, and a step of detaching the processed member from the bonding layer laminate. The upper limit of the heat treatment temperature is not particularly defined, but can be 370 ° C. or lower, preferably 350 ° C. or lower.
Moreover, in this invention, it is possible to isolate | separate a device wafer and a support substrate, without performing the process by a solvent.

The method for manufacturing a semiconductor device includes a step of performing a heat treatment. The step of performing the heat treatment is not particularly limited as long as it is a step of heating in the manufacturing process of the semiconductor device. For example, it may be a step of heating the thinned silicon substrate supported by the adhesive support. Preferably, it is a step of performing a heat treatment at the time of forming the silicon through electrode.
Hereinafter, the semiconductor manufacturing method of the present invention will be described in more detail.

    1A, 1B, and 1C are a schematic cross-sectional view illustrating temporary bonding between an adhesive support and a device wafer, a schematic cross-sectional view illustrating a device wafer temporarily bonded by the adhesive support, and adhesion, respectively. It is a schematic sectional drawing which shows the state by which the device wafer temporarily bonded by the adhesive support body was thinned.

As shown in FIG. 1A, a device wafer 60 (member to be processed) is formed by providing a plurality of device chips 62 on a surface 61 a of a silicon substrate 61. Further, a protective layer 71 is provided on the surface of the device wafer 60 on the structure 62 side.
The device wafer 60 preferably has an average film thickness of 500 μm or more. The structure 62 is called a device chip or a bump, and the average height is preferably in the range of 5 to 100 μm.

  As shown in FIG. 1A, an adhesive support 100 in which a release layer 11 is provided on a support substrate 12 is prepared.

The release layer 11 is formed on the support substrate 12 by using the conventionally known spin coat method, spray method, roller coat method, flow coat method, doctor coat method, dipping method and the like. It can be formed by coating and then drying.
Next, temporary bonding between the support 100 obtained as described above and the device wafer, thinning of the device wafer, and detachment of the device wafer from the support will be described in detail.
Then, the surface of the protective layer 71 is pressed against the release layer 11 of the adhesive support 100. Thereby, as shown in FIG. 1B, the surface of the protective layer 71 and the release layer 11 are bonded to each other, and the temporary bonding layer 80 having the protective layer 71 and the release layer 11 is formed.

Next, as shown in FIG. 1C, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment, specifically, thinning treatment such as grinding or chemical mechanical polishing (CMP). The thickness of the silicon substrate 61 is reduced (for example, the average thickness is preferably less than 500 μm, more preferably 1 to 200 μm) to obtain a thin device wafer 60 ′.
Further, as a mechanical or chemical treatment, a through-hole (not shown) penetrating the silicon substrate is formed from the back surface 61b ′ of the thin device wafer 60 ′ after the thinning process, and silicon is penetrated into the through-hole. A process of forming an electrode (not shown) is performed. Specifically, the highest temperature achieved in the heat treatment is in the range of 130 ° C. to 370 ° C., and preferably in the range of 180 ° C. to 350 ° C. The maximum temperature reached in the heat treatment is lower than the softening point of the protective layer. The heat treatment is preferably 30 seconds to 30 minutes at the maximum temperature, and more preferably 1 minute to 10 minutes at the maximum temperature.

Next, the surface 61 a of the thin device wafer 60 ′ is detached from the release layer 11 of the adhesive support 100.
The separation of the release layer is preferably performed by a physical action such as peeling off. That is, it is preferable to slide the thin device wafer 60 ′ with respect to the adhesive support 100 or peel the thin device wafer 60 ′ from the adhesive support 100. By the above method, the temporary adhesion between the release layer 11 and the surface 61a of the thin device wafer 60 ′ can be easily released. Moreover, you may peel using the peeling liquid mentioned later.

After the thin device wafer 60 ′ is detached from the adhesive support 100, the protective layer is removed as necessary. As a method for removing the protective layer 71, a method of peeling and removing in the form of a film, a method of peeling and removing after swelling with an aqueous solution or an organic solvent, a method of destroying and removing by spraying an aqueous solution or an organic solvent, an aqueous solution or an organic solvent And a method of dissolving and removing by dissolution, a method of removing by decomposition and vaporization by irradiation with actinic rays, radiation, or heat, or a method of removing by combining two or more of the above methods.
Among the above removal methods, a method of peeling and removing in the form of a film is preferably used.
As the aqueous solution or the organic solvent, any solution that can dissolve and remove the protective layer can be arbitrarily used. Specifically, the following stripping solutions can be preferably used.

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

  As the stripping solution, water and a solvent (organic solvent) can be used. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), halogenated compounds, and the like. Examples include hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine) , N- phenyldiethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.

Furthermore, from the viewpoint of peelability, the stripping solution may contain an alkali, an acid, and a surfactant. When mix | blending these components, it is preferable that a compounding quantity is 0.1-5.0 mass% of stripping solution, respectively.
Further, from the viewpoint of peelability, a form in which two or more organic solvents and water, two or more alkalis, an acid and a surfactant are mixed is also preferable.

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

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

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

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

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

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

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

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

  Various known processes are performed on the thin device wafer 60 'to manufacture a semiconductor device having the thin device wafer 60'.

In the present invention, the bonding method is configured in the order of device wafer-protective layer-release layer-support, as long as the protective layer is in contact only with the device wafer and the release layer is in contact only with the protective layer and the support. There is no particular limitation, and a laminated body in which a peeling layer and a protective layer are provided on a support may be prepared in advance, and a device wafer may be bonded to the protective layer that is the uppermost part of the laminated body.
In the present invention, from the viewpoint of protecting the surface of the device wafer, the protective layer preferably covers the entire surface of the device wafer.

Next, a conventional embodiment will be described.
FIG. 2 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 2, an adhesive support 100 in which a release layer 11 ′ formed of a conventional temporary adhesive is provided on a support substrate 12 as an adhesive support. Otherwise, the adhesive support 100 ′ and the device wafer are temporarily bonded in the same manner as described with reference to FIGS. 1A and 1B, and the thinning process of the silicon substrate on the device wafer is performed. Next, the thin device wafer 60 ′ having the silicon substrate 61 is peeled off from the adhesive support 100 ′.

However, according to the conventional temporary adhesive, the target member can be temporarily supported easily and easily, and it is difficult to easily release the temporary support for the processed member without damaging the processed member. . For example, in order to make sufficient temporary adhesion between the device wafer and the support substrate, when a highly temporary adhesive is used among conventional temporary adhesives, the temporary adhesion between the device wafer and the support substrate tends to be too strong. Become. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. 2, a tape (for example, dicing tape) 70 is attached to the back surface 61b ′ of the thin device wafer 60 ′, and the adhesive support 100 ′ is used. In the case of peeling the thin device wafer 60 ′, the structure 63 having the device chip 62 is detached, and the structure 63 is easily damaged.
On the other hand, when a conventional temporary adhesive having low adhesiveness is employed, the temporary adhesion between the device wafer and the support substrate is too weak, and a problem that the device wafer cannot be reliably supported by the support substrate is likely to occur.

  However, the release layer and the protective layer formed by the laminate of the present invention exhibit sufficient adhesion and can be easily released. That is, according to the laminated body in the present invention, the device wafer 60 can be temporarily supported easily and easily, and the temporary support to the thin device wafer 60 ′ can be easily released without damaging the thin device wafer 60 ′.

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

  In the embodiment described above, the release layer has a single layer structure, but the release layer may have a multilayer structure.

Furthermore, in the above-described embodiment, the silicon substrate is exemplified as the member to be processed supported by the adhesive support. However, the present invention is not limited to this, and in the semiconductor device manufacturing method, mechanical or chemical Any member to be processed that can be subjected to various processing may be used.
For example, the member to be processed can include a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate. Can be mentioned.

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

  In addition, the shape, size, number, arrangement location, and the like of the device chip in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited as long as the present invention can be achieved.

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

<Formation of release layer-support substrate (formation of wafer 1)>
After a release layer forming composition 1 having the composition shown in the following table was applied to a 4-inch Si wafer using a spin coater (Opticat MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa), baking was performed at 120 ° C. for 30 seconds and 190 ° C. for 3 minutes. Then, a wafer 1 provided with a release layer having a thickness of 0.10 μm was formed.

The compounds described in Table 1 are as follows.
[Compound containing fluorine atom and / or silicon atom]
A-1: Optool DSX (manufactured by Daikin Industries, Ltd., fluorine compound)
A-2: RS-72-K (DIC Corporation, fluorine compound)
A-3: RS-76-E (DIC Corporation, fluorine compound)
A-4: UV-3500B (manufactured by BYK, silicon-based compound)
A-5: (Heptadecafluoro-1,1,2,2-tetrahydradecyl) trichlorosilane (manufactured by TCI)
A-6: CHEMINOX FHP-2-OH (Unimatec Corp., fluorine compound)
A-7: TEFLON (registered trademark) AF (manufactured by Mitsui DuPont Fluorochemical Co., Ltd., fluorine-based compound)
A-8: CYTOP (Asahi Glass Co., Ltd., fluorine compound)
A-9: KP541 (Shin-Etsu Chemical Co., Ltd., silicon compound)
A-10: Dionin THV (manufactured by 3M, fluorine compound)
A-11: 15-85 (mass ratio) mixture of RS-72-K and Die Free FB962 (manufactured by Daikin, fluorine-based compound).
Among the above, it is A-1 to A-4 and A-11 that the release layer constitutes the three-dimensional crosslinked body.
[solvent]
Perfluorohexane: (Wako Pure Chemical Industries, Ltd.)
PGMEA: propylene glycol 1-monomethyl ether 2-acetate CT-Solv180: mesitylene MEK manufactured by AGC: methyl ethyl ketone NEP: N-methyl-2-pyrrolidone

<Protective layer-device wafer formation (wafer 2 formation)>
On the side where the electrodes of a 4-inch Si wafer on which Cu electrodes with a height of 10 μm and a diameter of 50 μm are formed at intervals of 200 μm are present, the composition shown in the following table is adjusted so that the solid content concentration of mesitylene is 25% by mass. Each composition for forming a protective layer was applied with a spin coater (Opticaat MS-A100, manufactured by Mikasa, 1200 rpm, 30 seconds), and then baked on a hot plate at 80 ° C., 10 minutes, and 250 ° C. for 15 minutes to form a film.
Solvents are Examples 1-2, 6-9 are mesitylene only, Example 3 is a solvent in which mesitylene and decalin are mixed at a weight ratio of 95: 5, Example 4 is decalin, Example 5 is p-menthane and decalin. Were mixed at a weight ratio of 95: 5 (both mass ratios). In Comparative Examples 1 to 12, decalin was used.

Each SEPTON described in the table is manufactured by Kuraray, and each TOPAS is manufactured by Polyplastics.
A1 is a styrene / dicyclopentanyl methacrylate / stearyl methacrylate = 20/60/20 (mass ratio) copolymer synthesized by a known method with a composition having a weight average molecular weight of 10,000.
A2 is a copolymer of styrene / 1-adamantyl methacrylate / stearyl methacrylate = 20/60/20 (mass ratio) synthesized by a known method with a composition having a weight average molecular weight of 10,000.
HG252 is Kuraray's SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene terminal hydroxyl group modification.
B-2 is polystyrene (manufactured by ALDRICH, Mw = 100000).
Deomaster S-90 is made by Sekisui Plastics.
Irganox 1010 is a phenolic antioxidant manufactured by BASF.
Sumilizer TPD is a sulfur-based antioxidant manufactured by Sumitomo Chemical.

<Preparation of test piece>
Test pieces were prepared by thermocompression bonding of the wafer 1 and the wafer 2 in the combinations described in the following table.
[Crimping]
A 4-inch Si wafer or wafer 2 on which nothing was applied to the surface was divided into 20 mm × 30 mm sample pieces. Similarly, the sample pieces of the wafer 1 of 20 mm × 30 mm divided are overlapped so that the release layer is in contact with the protective layer of the wafer 2 or the wafer 2 on which nothing is applied on the surface, with a 20 mm × 20 mm square, Pressure bonding was performed at 200 ° C. and 0.11 MPa for 5 minutes.

<Measurement of Young's modulus (unit: GPa)>
Using a tensile tester (Tensilon) with a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm, according to JIS-K7127 in an environment of 25 ° C. and 65% RH in the longitudinal direction and width direction of the film. The Young's modulus value was measured. In the evaluation, Young's modulus in the longitudinal direction and the width direction was measured 5 times each, and an average value in the longitudinal direction and the width direction was used.

<Measurement of elongation at break (unit:%)>
Using a tensile tester (Tensilon) with a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm, in the longitudinal and width directions of the film in an environment of 25 ° C. and 65% RH, in accordance with JIS-K6251 The elongation at break was measured. In the evaluation, the breaking elongations in the longitudinal direction and the width direction were measured 5 times each, and the average value in the longitudinal direction and the width direction was used.

<Measurement of melt flow rate (MFR) (unit: g / 10 min)>
The measured value in the condition of 200 ° C. and 10 kg load based on JIS K7210 was used.

<Evaluation of surface unevenness of laminate test piece>
Irregularities on the surface of the silicon substrate of the laminate after pressure bonding were confirmed by an atomic force microscope (AFM). The smaller the unevenness, the better the surface uniformity.
A: Ra ≦ 0.5 μm
B: 0.5 μm <Ra <2 μm
C: Ra ≧ 2 μm

<Electrical characteristics of device after chemical vapor deposition (CVD) process at 220 ° C.>
A laminated body was prepared by pressurizing and compressing a Si wafer obtained by applying the protective layer to a 4-inch silicon substrate under the above conditions.
Thereafter, the wafer was thinned by grinding to 40 μm. Two hundred copper plugs were formed by using a through-silicon via (TSV). Specifically, Si was etched by a Bosch process to form a through hole. Thereafter, a tetraethoxysilane (TEOS) -SiO ₂ insulating film was formed on the side wall of the through hole. Thereafter, TEOS-SiO ₂ on the electrode was selectively etched to form a TiN barrier layer in order to prevent Cu diffusion. After forming the barrier layer, Cu plugs were formed by plating. Chemical mechanical polishing (CMP polishing) was performed to expose the surface of the Si substrate. Thereafter, plugging of Cu was performed by reactive ion etching (RIE). A SiO ₂ film was formed on the obtained laminate at 200 ° C. for 1 minute, and the SiO ₂ film was etched after photolithography. The formation time of the SiO ₂ film was 1 minute, 5 minutes, 30 minutes, and 60 minutes, and the heat resistance of the protective layer was confirmed.
The protective layer was mechanically peeled off and washed easily with mesitylene. Only Example 10 was simply washed with a solution of 5% by weight of decalin in mesitylene.
It was evaluated whether a current flows through each copper plug. The number of plugs whose current has been confirmed is shown below.

A: 200 to 190 B: 189 to 170 C: 169 to 150 D: 149 to 130 E: 129 to 110 F: 109 to 90 G: 89 or less

  It shows that it is so stable that it cannot be disconnected for a long time.

  In the above examples, the release layer forming composition 1 was replaced with the release layer forming compositions 2 to 11 shown in Table 1. When the release layer forming composition 2, 3, 4 or 11 was used, the same effects as in the above examples and comparative examples were confirmed. When the release layer forming compositions 5 to 10 were used, the effects were slightly inferior to those when the release layer forming compositions 1 to 4 and 11 were used, but were sufficiently practical.

  Instead of the release layer, a reaction layer and a separation layer were provided in accordance with the description in International Publication WO2013 / 0665417, Paragraph No. 0133. Although Examples 1 to 9 of the present application were superior, it was confirmed that the uneven shape of the polished surface of the substrate of the device wafer hardly occurred and the electrical characteristics were excellent.

11, 21-30, 11 'Release layer 11A, 21A-30A High adhesion region 11B, 21B-30B Low adhesion region 12 Support substrate 60 Device wafer 60' Thin device wafer 61 Silicon substrate 61a Silicon substrate surface 61b Silicon substrate back surface 61b 'Back surface of thin device wafer 62 Device chip 63 Structure 71 Protective layer 80 Temporary bonding layer 100, 100' Adhesive support

Claims (21)

A composition for forming a protective layer for bonding a device wafer and a support substrate, comprising a resin having a melt flow rate at 200 ° C. under a load of 10 kg in accordance with JIS K-7210 and an organic solvent of 4 to 150 g / 10 min. And the Young's modulus based on JISK-7127 of the said composition for protective layer formation is 0.02 GPa or less, The composition for protective layer formation. The composition for forming a protective layer according to claim 1, wherein the resin contains a repeating unit derived from styrene, and the content of the repeating unit derived from styrene in the resin is 14 to 70% by mass. The composition for forming a protective layer according to claim 2, wherein the block copolymer is a hydrogenated product. The protective layer-forming composition according to claim 2 or 3, wherein both ends of the block copolymer are repeating units derived from styrene. The composition for protective layer formation according to any one of claims 2 to 4, wherein the block copolymer is a hydrogenated product of a block copolymer of styrene and a conjugated diene. Furthermore, the composition for protective layer formation of any one of Claims 1-5 containing 2 or more types of antioxidant. The composition for protective layer formation of Claim 6 containing a phenolic antioxidant and sulfur-type antioxidant as said 2 or more types of antioxidant. The protective layer according to claim 6 or 7, wherein at least one of the two or more kinds of antioxidants is an antioxidant having 2 to 6 groups represented by the following structure (A) in one molecule. Forming composition.
Structure (A)
The composition for forming a protective layer according to claim 6 or 7, wherein at least one of the two or more antioxidants is the following compound.
The composition for protective layer formation of any one of Claims 1-9 whose melt flow rate in 200 degreeC in the 10kg load based on JISK-7210 of the said resin is 20 g / 10min or more. The composition for protective layer formation of any one of Claims 1-10 whose breaking elongation based on JISK-6251 of the said resin is 1200% or less. The composition for protective layer formation of any one of Claims 1-11 whose breaking elongation based on JISK-6251 of the said resin is 400 to 600%. The composition for protective layer formation of any one of Claims 1-12 whose breaking elongation based on JISK-6251 of the said resin is 500% or less. The organic solvent contains at least one compound selected from the group consisting of esters, ethers, ketones, saturated aliphatic hydrocarbons, aromatic hydrocarbons, and condensed polycyclic hydrocarbons. 14. The protective layer-forming composition according to any one of 13 above. Device wafer, protective layer, support substrate in this order,
The laminated body which the said protective layer uses the composition for protective layer formation of any one of Claims 1-14. The laminated body of Claim 15 which has a peeling layer or a separation layer between the said protective layer and a support substrate. The laminated body of Claim 16 containing the peeling layer in which the said laminated body contains a fluorine atom and / or a silicon atom. The laminate according to claim 17, wherein the release layer is obtained by curing at least one of a bifunctional or higher functional radically polymerizable monomer or oligomer having a fluorine atom and an alkoxysilane compound having a fluorine atom. The laminated body according to any one of claims 15 to 18, wherein the support substrate is a silicon substrate, a glass substrate, a metal substrate, a sapphire substrate, a SiC substrate, or a GaN substrate. The kit containing the composition for protective layer formation of any one of Claims 1-14, and the composition for peeling layer formation containing the material containing a fluorine atom and / or a silicon atom. A kit comprising a composition for forming a protective layer according to any one of claims 1 to 14 and a liquid for swelling or dissolving a protective layer formed using the composition for forming a protective layer.