JP6606033B2 - LAMINATE AND METHOD FOR PRODUCING LAMINATE - Google Patents

Description

  The present invention relates to a laminate and a method for producing the laminate.

2. Description of the Related Art Conventionally, when bonding substrates, the adhesive is formed on one of the two substrates, and an adhesive layer is formed using a spin coating method to bond them.
Specifically, Patent Document 1 discloses a film forming method for forming a liquid film on a surface of an object having an outer peripheral edge, the object being rotated around a central axis of the surface, and a liquid material on the surface. And flowing the liquid material so as to cover at least the annular surface region along the outer peripheral edge of the object, preparing a rotating body having a rotating surface, and the surface of the object Contacting a part of the area with the rotating surface of the rotating body, rotating the object about the central axis, and simultaneously rotating the rotating body about its own rotating axis; A coating comprising: transferring a portion of the liquid material from the surface region to the rotating surface; and removing the liquid material transferred to the rotating surface from the rotating surface at a location away from the surface region. How to form There has been disclosed.

Patent Document 2 discloses a step of forming a film to be processed on a main surface of a semiconductor substrate and a process for processing the film to cover the film to be processed. Forming a first resist film to be a mask material, forming a second resist film for patterning the first resist film as the mask material so as to cover the first resist film, The second resist film is subjected to a predetermined photolithography process and a developing process to form a predetermined resist pattern, and the mask material is etched by etching the first resist film using the resist pattern as a mask. Forming the first resist film using the mask material as a mask, and forming the first resist film is suitable for processing the film to be processed. Applying a predetermined resist material having etching resistance onto the surface of the film to be processed to form a resist material film, and spraying an organic solvent on the outer periphery of the semiconductor substrate while rotating the semiconductor substrate Thereby removing the resist material film portion located on the outer peripheral portion, drying the semiconductor substrate from which the resist material portion located on the outer peripheral portion has been removed, and rotating the semiconductor substrate. And spraying at least one of a predetermined liquid and gas for crushing the resist material film onto the outer periphery of the resist material film left on the semiconductor substrate, and the resist material film A method for manufacturing a semiconductor device is disclosed that includes a step of performing a heat treatment.
Further, in Patent Document 3, an adhesive material attaching step for attaching an adhesive material to the entire adhesive surface of the first base portion, and a part of the adhesive material attached to the first base portion in the adhesive material attaching step are removed and opened. Forming an opening, and a substrate bonding step for bonding the second base to the bonding surface of the first base via the adhesive in which the opening is formed in the opening forming step. A convex portion where the surface of the adhesive is raised is formed, the opening forming step provides an opening that partially overlaps the convex portion, and the substrate bonding step is an adhesion in which the second base is bonded to the convex portion. A method for manufacturing a substrate is disclosed.

JP 2014-124626 A JP 2012-156454 A Japanese Patent Application Laid-Open No. 2015-0665354

Here, when an adhesive layer containing a thermoplastic resin is applied on the substrate by a coating method such as a spin coat method to form an adhesive layer containing a thermoplastic resin, the adhesive layer containing the thermoplastic resin is formed at the end of the adhesive layer. A raised part (edge bead) is formed. Furthermore, it has been found that when a substrate is applied on an adhesive layer having a raised portion and the two substrates are bonded (bonded) with an adhesive, the bonding ability may be inferior. That is, it has been found that there are cases in which thickness unevenness occurs in a laminate composed of two substrates and an adhesive layer between them, and voids (voids) occur in the bonded interface. Further, it has been found that when such a raised portion occurs, chipping is likely to occur on the processed substrate when processing such as back grinding is performed on one of the two substrates. Moreover, although the method of removing the bulging part is described in the said patent document, the process was complicated and it was not a method suitable for the contact bonding layer containing a thermoplastic resin.
The present invention has been made to solve the above-mentioned problems, and a laminated body in which thickness unevenness does not occur when chipping two substrates with an adhesive, and chipping is unlikely to occur during processing, and the above-described laminated body It aims at providing the manufacturing method of a body.

As a result of intensive studies by the inventor under the above-mentioned problems, it is possible to suppress unevenness in the thickness of the laminate by causing the raised portion at the end of the adhesive layer to have two or more peaks. It was found that chipping can be made difficult to occur.
Specifically, the above problem has been solved by the following <1>, preferably by <2> to <9>.
<1> A laminate having a substrate and an adhesive layer containing a thermoplastic resin having a raised portion at the end, and the raised portion at the end of the adhesive layer has two or more peaks.
<2> The laminate according to <1>, wherein the substrate has a disk shape.
<3> and the height H _n of the peak from the end of the n-th counted toward the center of the substrate, the height H _{n + 1} of the (n + 1) th peak, average thickness t of the adhesive layer is, t <H The laminated body according to <2>, wherein _{n + 1} <H _n <t + 40 / n is satisfied; provided that the average film thickness unit is μm, and the peak height unit is μm.
<4> and an end portion of the substrate, the shortest distance R _n between the position on the substrate corresponding to n-th peak counted toward the center from the edge of the substrate, the average thickness t of the adhesive layer N · t / 40 <R _n <n · t / 8 satisfying the laminate according to <2> or <3>; provided that the average film thickness unit is μm, and the shortest distance unit is mm.
<5> The laminate according to any one of <1> to <4>, wherein the raised portion has two peaks.
The laminated body as described in any one of <1>-<5> in which the contact bonding layer containing the <6> above-mentioned thermoplastic resin contains a polystyrene-type elastomer.
<7> The laminate according to any one of <1> to <6>, wherein the adhesive layer containing the thermoplastic resin includes a polyether-modified silicone.
<8> The laminate according to <7, wherein the polyether-modified silicone has a ratio represented by the formula (A) of 80% or more;
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is the mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mole percent of alkylene oxide contained in the polyether structure in the polyether-modified silicone.
<9> A step of applying an adhesive containing a solvent on the substrate by spin coating to form an adhesive layer, and adjusting so that the rising portion at the end of the adhesive layer has two or more peaks. The manufacturing method of the laminated body as described in any one of <1>-<8> including the process to do.

  According to the present invention, it is possible to provide a laminated body in which thickness unevenness does not occur and chipping hardly occurs during processing when the two substrates are bonded to each other with an adhesive, and a method for manufacturing the laminated body.

It is the schematic which shows an example of the mode of the edge part of a board | substrate and an adhesive agent (or adhesive layer) at the time of apply | coating an adhesive agent on a board | substrate with a spin coat method, and manufacturing an adhesive layer. It is the schematic which shows an example of the swelling part of the contact bonding layer in this invention. It is the schematic of 1st embodiment which shows the manufacturing method of a semiconductor element. It is the schematic of 2nd embodiment which shows the manufacturing method of a semiconductor element. The profile of the contact bonding layer of Example 1 and Comparative Example 1 is shown.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 this specification, “exposure” includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents “acryloyl” and “methacryloyl”. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value according to a gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, inner diameter) as a column. (ID) 6.0 mm × 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as an eluent.
In the embodiments described below, members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings to simplify or omit the description.

The laminate of the present invention has a substrate and an adhesive layer containing a thermoplastic resin having a raised portion at the end, and the raised portion at the end of the adhesive layer has two or more peaks. . By setting it as such a structure, the thickness nonuniformity of a laminated body can be suppressed and it can become difficult to generate | occur | produce chipping at the time of a process. This point will be described with reference to FIG.
FIG. 1 is a diagram showing an example of a state of a cross section of an end portion of a substrate and an adhesive (or adhesive layer) when an adhesive layer is manufactured by applying an adhesive onto the substrate by a spin coat method. is there. In FIG. 1, 1 is a substrate, 2 is an adhesive or adhesive layer, 3 is a second substrate, 4 is a void, and 5 is a peak of a raised portion. In the embodiments of (1) to (4) in FIG. 1, the adhesive after the second substrate is further bonded onto the adhesive in the drying initial stage, the middle drying stage, the drying end stage, and the adhesive, respectively, from the left. Or the change of the shape of the cross section of the adhesive layer) is shown. In addition, the embodiment (1) is an example in which the adhesive is baked at a relatively low temperature (for example, 60 to 100 ° C.), evacuated and dried using a conventional hot plate. In the embodiment of (2), the adhesive is baked at a relatively low temperature, the solvent contained in the adhesive is filled in the hot plate, and the leveling functions relatively slowly and more effectively. It is the example manufactured by making it dry and is an example of the embodiment of the present invention. The embodiment (3) is an example in which the adhesive is baked at a relatively high temperature (for example, 110 to 150 ° C.), and exhausted and dried using a conventional hot plate. The embodiment of (4) was manufactured by baking the adhesive at a relatively high temperature, filling the hot plate with the solvent contained in the adhesive, and adjusting and drying so that the leveling functions more effectively. It is an example.
In the initial stage of drying, a swelled portion is formed at the end of the adhesive layer 2 in any of the embodiments (1) to (4). In the embodiment of (1), the raised portion is leveled to some extent in the middle of drying, but drying is completed without being completely leveled, and when the second substrate is bonded, the adhesive layer 2 and the second substrate A part of the gap is generated between the three. As a result of studies by the present inventor, it has been found that this gap causes unevenness in thickness or causes chipping during processing. On the other hand, in the embodiments of (3) and (4), the degree to which the swelled part is leveled is low from the middle of drying to the end of drying. For this reason, when the second substrate 3 is provided on the adhesive (adhesive layer), a void 4 is formed between the adhesive layer 2 and the second substrate 3.
On the other hand, in the present invention, as shown in the embodiment (2), the rising portion at the end of the adhesive layer is adjusted to have two or more peaks 5 in the middle of drying. As a result, it is possible to provide a laminate that suppresses uneven thickness during bonding and is less likely to cause chipping during processing.
The substrate, the adhesive layer, and the second substrate are usually provided in the above order so as to be adjacent to each other. However, the adhesive layer and the second substrate are provided between the substrate and the adhesive layer without departing from the gist of the present invention. You may have another layer between.

Next, the peak of the rising portion in the present invention will be described with reference to FIG. However, it goes without saying that the configuration of the present invention is not limited to the configuration shown in FIG. FIG. 2 shows a laminated body in which an adhesive layer 2 is provided on the surface of a disk-shaped substrate 1, and the laminated body is cut in a direction perpendicular to the substrate surface and passing through the center of the disk-shaped substrate. A cross-sectional view is shown. The diameter direction is a direction parallel to the substrate surface, and the Z direction is a direction perpendicular to the substrate surface.
In the present invention, the end portion of the adhesive layer refers to a portion relatively outside the center of the substrate. For example, when the substrate is disk-shaped, the distance between the center of the circle of the disk and the circumference (the radius of the circle) is within 1/4, preferably within 1/8, more preferably 1 / Refers to 10 or less sites. The disc shape here does not have to be a circle in a mathematical sense, but includes a meaning that is understood by those skilled in the art of the present invention as a disc shape. For example, a commercially available general circular semiconductor substrate can be said to be a disk-shaped substrate.
The raised part in the present invention refers to a part having a height of 1.1 times or more the average film thickness of the adhesive layer. For example, the edge bead corresponds to a raised portion in the present invention.
The average film thickness t (unit: μm) of the adhesive layer in the present invention can be appropriately determined according to the application and the like, but is preferably 0.1 to 200 μm, and more preferably 1 to 100 μm. The average film thickness t of the adhesive layer is measured according to the method described in Examples described later.

The peak of the raised portion in the present invention refers to a convex portion in the raised portion. 2 in FIG. 2 is a peak. In the present invention, two or more peaks may be used, but 2 to 5 are preferable, 2 to 4 are more preferable, 2 or 3 are further preferable, and 2 is more preferable. When the substrate is disk-shaped, the peaks usually exist concentrically when viewed from above the substrate surface.
The height of the peak is defined as H _n (unit: μm), which is the height of the n-th peak counted from the edge of the substrate toward the center. Then, as shown in FIG. 2, the height of the peak closest to the edge of the substrate is H ₁ , the height of the peak next to the edge is H _2, and the height of the peak closest to the edge is third. Is H ₃ . H ₄ or later is also similar. In the present invention, when there are peaks concentrically, the peak height in one circle is usually the same at any point, but if there is an error, the highest point is the peak height H. To do.
In the present invention, the height H _n of the n th peak counted toward the center from the edge of the substrate, the height H _{n + 1} of the (n + 1) th peak, average thickness t of the adhesive layer is, t <H n + ₁ <it is preferable to satisfy _{H n <t + 40 / n} , and more preferably satisfies the _{t + 5 <H n + 1} <H n <t + 40 / n-5.

In the present invention, the shortest distance R _n (unit: mm) between the edge of the substrate and the position on the substrate corresponding to the n-th peak counted from the edge of the substrate toward the center, and the average film thickness of the adhesive layer t preferably satisfies n · t / 40 <R _n <n · t / 8, and more preferably satisfies n · t / 30 <R _n <n · t / 12.
The position on the substrate corresponding to the nth peak counted from the edge of the substrate toward the center is the point that contacts the substrate when a perpendicular is drawn to the substrate from the highest point of the peak. Say. FIG. 2 shows the distances R ₁ , R ₂ , R ₃ between the edge of the substrate and the positions on the substrate corresponding to the first, second, and third peaks counted from the edge of the substrate toward the center. An example is shown.
The value of R _n is measured according to the method described in the examples below.

As described above, when two substrates are bonded using an adhesive, when the adhesive is applied by a spin coat method, a raised portion is formed at the end of the adhesive layer. The raised portion causes unevenness in the thickness of the laminate obtained by bonding the substrates, resulting in poor flatness (TTV (Total Thickness Variation)). Under such circumstances, in the present invention, it is preferable that the rising portion has two or more peaks and satisfies t <H _{n + 1} <H _n <t + 40 / n. By adopting such a configuration, the peak at the extreme end becomes a thin and long peak and is effectively crushed when the substrates are bonded. Further, by satisfying n · t / 40 <R _n <n · t / 8, the peak close to the center becomes a wide and low peak, and the peak is more easily flattened.
Further, the end of the substrate is likely to be deformed due to the inherent warpage of the substrate or the stress of the adhesive during processing, but in the present invention, the outer periphery of the substrate is the end most at the peak near the center. At this peak, the end face of the substrate can be held, and the subsequent processing stability can be improved.

In the laminate of the present invention, a step of spin-coating an adhesive containing a solvent on a substrate to form a layer, and a raised portion at the end of the layered adhesive have two or more peaks. It can manufacture by the manufacturing method including the process to adjust. However, it goes without saying that it may be a laminate obtained by a method other than the above.
In the present invention, the following method is exemplified as a method for adjusting the rising portion of the adhesive layer to have two or more peaks.
1) In a state where the adhesive containing the solvent is layered, at a temperature of room temperature or higher (for example, 20 to 40 ° C.), while exhausting so as not to cause condensation while the solvent is sufficiently filled, Leveling 2) With the adhesive containing the solvent layered on the substrate, the liquid or gas (preferably solvent) is brought into contact with the raised portion of the surface of the layered adhesive while rotating the substrate. (EBR processing, etc.)
3) Mechanically removing a part of the raised portion of the layered adhesive in a state where the solvent-containing adhesive is layered (jig processing, etc.)
Any of the above methods is preferably performed in a step of laminating an adhesive containing a solvent and drying the solvent. More specifically, the vapor pressure of the solvent in the hot plate maintains a state close to the saturated vapor pressure of the solvent to be used, and the solvent condenses on the side of the hot plate and the temperature in the hot plate decreases, In order to prevent condensation from falling on the adhesive, it is preferable that the air is exhausted with an appropriate air volume from the exhaust holes uniformly disposed in the apparatus. It is more preferable that the heater of the hot plate is provided above and below the substrate because the temperature distribution in the apparatus can be suppressed to a small level, and as a result, the adhesive can be leveled more uniformly.
Furthermore, in the present invention, after the adhesive layer is formed on the substrate by spin coating using an adhesive, at least one of the states after the second substrate is adhered on the adhesive layer It is preferable to clean the back surface and the bevel portion of the substrate using a back rinse. By adopting such a means, there is an advantage that the transport arm of the apparatus can be prevented from being contaminated and more stable peeling can be performed.
It should be noted that the layered adhesive and the adhesive layer are not clearly distinguished from each other in the process from application of the adhesive in layers to formation of the adhesive layer. Therefore, it is needless to say that the method for producing a laminate according to the present invention also includes a case where two or more peaks are formed in the raised portion of the adhesive layer after the adhesive layer is formed.

The board | substrate used by this invention can be suitably determined according to a use. The substrate in the present invention includes a support. The shape of the substrate is preferably a disc shape. By making it into a disk shape, it is possible to make it difficult to generate cracks when processed. Further, when a temporary adhesive is used as the adhesive, it is preferable to use a substrate to be processed and a carrier substrate. In this case, the temporary adhesive may be provided on the substrate to be processed, may be provided on the carrier substrate side, or may be provided on both.
The substrate is a semiconductor substrate selected from a silicon (Si) substrate, a germanium (Ge) substrate, a gallium nitride (GaN) substrate, a gallium arsenide (GaAs) substrate, an indium phosphide (InP) substrate, and a silicon carbide (SiC) substrate. Illustratively, a silicon substrate is preferred. In addition to the above, inorganic substrates such as glass substrates, quartz substrates and ceramic substrates, and organic substrates such as mold resins and epoxy resins are also preferably used as the substrates.

The adhesive layer in the present invention is formed using an adhesive containing a thermoplastic resin. The adhesive used in the present invention is usually an adhesive containing a solvent. In the case where the adhesive contains a solvent, it is applied by a coating method such as a spin coating method to form a layer, so that a raised portion is easily formed at the end. The adhesive used in the present invention preferably contains a resin and a solvent.
As described above, the adhesive may be a temporary adhesive that temporarily fixes the substrate and the substrate, or may be a permanent adhesive that fixes the substrate and the substrate semi-permanently. The present invention is particularly suitable when a temporary adhesive is used.
Hereinafter, the adhesive that can be used in the present invention will be described.

<Temporary adhesive>
<< Thermoplastic resin >>
The temporary adhesive used in the present invention contains at least one thermoplastic resin (hereinafter sometimes simply referred to as “resin”).
Examples of the resin include a block copolymer, a random copolymer, and a graft copolymer, and a block copolymer is preferable. Since the block copolymer can suppress the flow of the temporary adhesive during the heating process, the adhesion can be maintained even during the heating process, and the effect that the peelability does not change even after the heating process can be expected.

In the temporary adhesive used in the present invention, the resin is preferably an elastomer. By using an elastomer as the resin, it is possible to follow a fine unevenness of a substrate (a substrate to be processed such as a carrier substrate or a device wafer) and to form a temporary adhesive having excellent adhesiveness by an appropriate anchor effect. One or more types of elastomers can be used in combination.
In addition, in this specification, an elastomer represents the high molecular compound which shows elastic deformation. That is, when an external force is applied, it is defined as a polymer compound having a property of instantly deforming according to the external force and recovering the original shape in a short time when the external force is removed.

<<< Elastomer >>>>
In the present invention, the weight average molecular weight of the elastomer is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, and even more preferably from 50,000 to 100,000. An elastomer having a weight average molecular weight in this range is excellent in solubility in a solvent. Therefore, after peeling the carrier substrate from the substrate to be processed, the solvent is used to derive from the elastomer remaining on the substrate to be processed or the carrier substrate. When removing the residue, the residue is easily dissolved in the solvent and removed. For this reason, there exists an advantage that a residue does not remain in a to-be-processed substrate, a carrier substrate, etc.

  In the present invention, the elastomer is not particularly limited, and an elastomer (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacryl elastomer, a silicone elastomer Elastomers, polyimide elastomers, etc. can be used. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and a polystyrene-based elastomer is more preferable from the viewpoint of heat resistance and peelability.

  In the present invention, the elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene-based elastomer is preferable. When the elastomer is a hydrogenated product, thermal stability and storage stability are improved. Furthermore, the releasability and the removability of the temporary adhesive after peeling are improved. When a hydrogenated product of polystyrene elastomer is used, the above effect is remarkable. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.

In the present invention, the elastomer preferably has a 5% thermal mass reduction temperature of 250 ° C. or higher when the temperature is increased from 25 ° C. at a temperature increase rate of 20 ° C./min, more preferably 300 ° C. or higher. Preferably, it is 350 degreeC or more, More preferably, it is 400 degreeC or more. Moreover, although an upper limit does not have limitation in particular, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, a temporary adhesive having excellent heat resistance can be obtained.
The elastomer in the present invention can be deformed to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and 130% or less in a short time when the external force is removed. It is preferable to have the property of returning to

<<<<< Polystyrene Elastomer >>>>
There is no restriction | limiting in particular as a polystyrene-type elastomer, According to the objective, it can select suitably. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly (ethylene-propylene) diblock copolymer (SEP), polystyrene-poly (ethylene -Propylene) -polystyrene triblock copolymer (SEPS), polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer (SEBS), polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer. It is preferably at least one selected from the group consisting of (SEEPS).

  The proportion of the repeating unit derived from styrene in the polystyrene elastomer is preferably 90% by mass or less, more preferably 55% by mass or less, further preferably 48% by mass or less, still more preferably 35% by mass or less, and more preferably 33% by mass or less. Even more preferred. The lower limit of the ratio of the repeating unit derived from styrene may be 0% by mass, but may be 10% by mass or more. By setting it as such a range, the curvature of the laminated body which bonds substrates together with a temporary adhesive can be suppressed more effectively.

As an embodiment of the polystyrene-based elastomer in the present invention, an elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 55% by mass or less in all repeating units, and a repeating unit derived from styrene in all repeating units. And an elastomer B contained in a proportion of more than 55% by mass and 95% by mass or less. By using the elastomer A and the elastomer B in combination, the occurrence of warpage can be effectively suppressed. It can be presumed that the mechanism for obtaining such an effect is as follows. That is, since the elastomer A is a relatively soft material, it is easy to form a layered temporary adhesive (temporary adhesive layer) having elasticity. For this reason, even when a laminated body of a substrate and a carrier substrate is manufactured using a temporary adhesive and the substrate is polished to form a thin film, the temporary adhesive (temporary bonding) Layer) is elastically deformed and easily returns to its original shape. As a result, excellent flat polishing properties can be obtained. In addition, even if the laminate of the carrier substrate, workpiece substrate, and temporary adhesive after polishing is heat-treated and then cooled, the internal stress generated during cooling can be alleviated by the temporary adhesive (temporary adhesive layer). The occurrence of warpage can be effectively suppressed.
Moreover, since the said elastomer B is a comparatively hard material, it can be set as the temporary adhesive excellent in peelability by including the elastomer B.

  The mass ratio when blending the elastomer A and the elastomer B is preferably Elastomer A: Elastomer B = 1: 99 to 99: 1, more preferably 3:97 to 97: 3, and 5:95 to 95: 5. Is more preferable, and 10:90 to 90:10 is more preferable. If it is the said range, the effect mentioned above will be acquired more effectively.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer in which one end or both ends are styrene blocks, and both ends are styrene blocks. It is particularly preferred. When both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), the heat resistance tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance is present at the terminal. 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. In addition, such an elastomer is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
In addition, when the polystyrene elastomer 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 a solvent and resistance to a resist solvent.
The unsaturated double bond amount of the polystyrene elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and less than 0.5 mmol per 1 g of the polystyrene elastomer from the viewpoint of peelability. Further preferred. In addition, the amount of unsaturated double bonds here does not include the unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by NMR (nuclear magnetic resonance) measurement.

  In the present specification, “a 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 styrene derivative include α-methyl styrene, 3-methyl styrene, 4-propyl styrene, 4-cyclohexyl styrene, and the like. 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 2 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

  Examples of commercially available polystyrene elastomers include Tufprene A, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, and Tuftec H1272. , Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftech M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (above, Asahi Kasei Chemicals AR) 850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elasto -AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060 Elastomer AR-1040 (manufactured by Aron Kasei Co., Ltd.), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163, Clayton D1164, Clayton D1165 Clayton D1183, Clayton D1193, Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4270, Clayton D 4433, Clayton D 1170, Clayton D 1171, Clayton D 1173, Califlex IR0307 Flex IR 031 0, Califlex IR 0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152, Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1189, Clayton D1192 DX405, Clayton DX408, Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645, Clayton G 633, Clayton G1650, Clayton G1651, Clayton G1652 (G1652MU-1000), Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609 and Clayton G4610 TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, manufactured by Kraton Polymer Japan Co., Ltd. Dynalon 6200P, Dynalon 4630P, Dynalon 8601P, Dynalon 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 6201B, Dynalon 1321P, Dynalon 1320P, Dynalon 2324P (manufactured by JSR Corporation), Denka STR series (Electrochemical Industry) Co., Ltd.), Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon Series (Mitsubishi Chemical Corporation), Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2 07, septon 2063, septon 2104, septon 4033, septon 4044, septon 4055, septon 4077, septon 4099, septon HG252, septon 8004, septon 8006, septon 8007, septon 8076, septon 8104, septon V9461, septon V9475, septon V9827, Examples include Hibler 7311, Hibler 7125, Hibler 5127, Hibler 5125 (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (manufactured by Riken Technos Co., Ltd.), and the like.

<<<<< Polyester elastomer >>>>
There is no restriction | limiting in particular as a polyester-type elastomer, According to the objective, it can select suitably. Examples thereof include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, and the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.
Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. Examples thereof include alicyclic diols and divalent phenols represented by the following structural formulas.

In the above formula, Y ^DO represents any of an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO ₂ —, or a single bond. To express. R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1.

Specific examples of the divalent phenol include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These may be used alone or in combination of two or more.
Also, as the polyester elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component should be used. You can also. Examples of the multi-block copolymer include various grades depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by Toray DuPont Co., Ltd.), Perprene (manufactured by Toyobo Co., Ltd.), Primalloy (manufactured by Mitsubishi Chemical Corporation), Nouvelan (manufactured by Teijin Limited), Espel 1612 and 1620 (and above). And Hitachi Chemical Co., Ltd.).

<<<<< Polyolefin Elastomer >>>>
There is no restriction | limiting in particular as a polyolefin-type elastomer, According to the objective, it can select suitably. Examples thereof include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Moreover, the copolymer of a C2-C20 nonconjugated diene, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene and isoprene, and an α-olefin are exemplified. Moreover, the carboxy modified nitrile rubber which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer is mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer Examples include rubber.
Commercially available products include Miralastomer (Mitsui Chemicals), Thermoran (Mitsubishi Chemical) EXACT (ExxonMobil), ENGAGE (Dow Chemical Japan), Espolex (Sumitomo Chemical) ), Sarlink (manufactured by Toyobo Co., Ltd.), Newcon (manufactured by Nippon Polypro Co., Ltd.), EXCELLINK (manufactured by JSR Corporation), and the like.

<<<<< Polyurethane Elastomer >>>>
There is no restriction | limiting in particular as a polyurethane-type elastomer, According to the objective, it can select suitably. For example, an elastomer containing structural units of a hard segment composed of a low molecular weight glycol and diisocyanate and a soft segment composed of a polymer (long chain) diol and diisocyanate can be used.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
As the low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number average molecular weight of the short chain diol is preferably 48 to 500.
Examples of commercially available polyurethane-based elastomers include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), milactolan (manufactured by Japan Miractoran Corporation), elastollan (manufactured by BASF Japan Ltd.), resamine ( Dainichi Seika Kogyo Co., Ltd.), Peresen (Dow Chemical Japan Co., Ltd.), Iron Rubber (NOK Co., Ltd.), Mobilon (Nisshinbo Chemical Co., Ltd.), and the like.

<<<<< Polyamide elastomer >>>>
There is no restriction | limiting in particular as a polyamide-type elastomer, According to the objective, it can select suitably. For example, an elastomer using a polyamide such as polyamide 6, 11, or 12 as a hard segment and a polyether or polyester such as polyoxyethylene, polyoxypropylene, or polytetramethylene glycol as a soft segment. It is done. This elastomer is roughly classified into two types, a polyether block amide type and a polyether ester block amide type.
Commercially available products include UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), Grilon ELX (manufactured by Emschemy Japan Co., Ltd.), Nopamid ( (Mitsubishi Chemical Co., Ltd.), Relax (Toyobo), polyether ester amide PA-200, PA-201, TPAE-12, TPAE-32, polyesteramide TPAE-617, TPAE-617C (above, Inc.) T & K TOKA).

<<<<< Polyacrylic elastomer >>>>
There is no restriction | limiting in particular as a polyacrylic-type elastomer, According to the objective, it can select suitably. For example, copolymers containing acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, etc. as the main component of the monomer material, or copolymers of acrylic acid esters with glycidyl methacrylate, allyl glycidyl ether, etc. Is mentioned. Furthermore, the thing etc. which copolymerize acrylic acid ester and crosslinking point monomers, such as acrylonitrile and ethylene, etc. are mentioned. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

<<<<< Other elastomers >>>>
In the present invention, a rubber-modified epoxy resin (epoxy elastomer) can be used as the elastomer. Epoxy elastomers include, for example, bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, salicylaldehyde-type epoxy resins, phenol novolac-type epoxy resins or cresol novolac-type epoxy resins with a part or all of the epoxy groups at both terminal carboxylic acids. It can be obtained by modification with modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.

<<< other polymer compounds >>>
In the present invention, as the thermoplastic resin, other polymer compounds (also referred to as other polymer compounds) other than the above-described thermoplastic resins can be used. Other polymer compounds can be used alone or in combination of two or more.
Specific examples of other polymer compounds include, for example, hydrocarbon resins, novolac resins, phenol resins, unsaturated polyester resins, thermoplastic polyimide resins, polyvinyl chloride resins, polyvinyl acetate resins, polyacetal resins, polycarbonate resins, polyphenylenes. Examples include ether resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyarylate resins, and siloxane copolymers. Among these, hydrocarbon resins, thermoplastic polyimide resins, and polycarbonate resins are preferable, and hydrocarbon resins are more preferable.
In the present invention, a resin containing a fluorine atom, which will be described later, can be used as the resin, but a resin containing a fluorine atom (hereinafter also referred to as a fluororesin) is preferably substantially not contained. “Substantially free of fluororesin” means that the content of fluororesin is, for example, 0.1% by mass or less, preferably 0.05% by mass or less, and not contained at all with respect to the total mass of the resin. It is more preferable.

In the present invention, any hydrocarbon resin can be used.
The hydrocarbon resin basically means a resin composed of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, to a hydrocarbon resin consisting of only carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention, and in this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the total repeating unit of the resin. Is preferred.
Examples of the hydrocarbon resin meeting the above conditions include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, and polymerized rosin. , Polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, polystyrene -Polyolefin copolymers, olefin polymers (for example, methylpentene copolymers), and cycloolefin polymers (for example, norbornene copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers), etc. .

The acrylic resin in the present invention is a resin obtained by polymerizing a (meth) acrylate monomer.
(Meth) acrylate monomers include 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n- Octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-nonyl (meth) acrylate, isoamyl (meth) Acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenylmeta Acrylate), Benjirumeta (acrylate), and 2-methylbutyl (meth) acrylate.
Further, other monomers may be copolymerized without departing from the spirit of the present invention. When other monomers are copolymerized, the amount of the other monomers is preferably 10 mol% or less of the total monomers.
In addition to the above, Mitsubishi Rayon Co., Ltd., Acripet MF 001, 3M Japan Co., Ltd., LC-5320 F1035 and the like are exemplified.

In the present invention, an acrylic resin having an organopolysiloxane in the side chain is also preferable. Examples of the acrylic resin having an organopolysiloxane in the side chain include acrylic resins represented by the following formula (3).
Formula (3)
In the formula (3), when there are a plurality of R ^{1 s} , they may be the same or different, and —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ or —CH ₃ (CH ₂ ) ₃ is substituted. Show. When there are a plurality of R ^{2 s} , they may be the same or different and each represents —H, —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ or —CH ₃ (CH ₂ ) ₃ . When there are a plurality of R ^{3 s} , they may be the same or different and represent —H or —CH ₃ . When there are a plurality of R ^{4 s} , they may be the same or different, and —H, —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ , —CH ₃ (CH ₂ ) ₃ , or an epoxy group, An alkyl group having 1 to 6 carbon atoms substituted with at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, a vinyl group, a silanol group and an isocyanate group is shown. a is 50 to 150, b is 50 to 150, and c is 80 to 600. Moreover, m is 1-10.
Specific examples of the acrylic resin having an organopolysiloxane in the side chain include silicone graft acrylic resins manufactured by Shin-Etsu Chemical Co., Ltd., trade names: X-24-798A, X-22-8004 (R ⁴ : C ₂ H ₄ OH, the functional group equivalent: 3250 (g / mol)) , X-22-8009 (R 4: Si (OCH 3) 3 containing an alkyl group, the functional group equivalent: 6200 (g / mol)) , X-22- 8053 (R ⁴ : H, functional group equivalent: 900 (g / mol)), X-22-8084, X-22-8084EM, X-22-8195 (R ⁴ : H, functional group equivalent: 2700 (g / mol)), Toagosei Co., Ltd. Cymac series (US-270, US-350, US-352, US-380, US-413, US-450, etc.), Reseta GS-1000 series ( S-1015, GS-1302, etc.) and the like.

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

In formula, m represents the integer of 0-4. R ^{1 to} R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ^{1 to} X ³ and Y ^{1 to} Y ³ are respectively a hydrogen atom and 1 to 10 carbon atoms. hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen ^{_{atom, - (CH 2) n COOR}} 11, - (CH 2) n OCOR 12, - (CH 2) n NCO, - _{(CH 2) n NO 2,} - (CH 2) n CN, - (CH 2) n CONR 13 R 14, - (CH 2) n NR 15 R 16, - (CH 2) n OZ, - (CH 2 ) _N W, or (—CO) ₂ O, (—CO) ₂ NR ¹⁷ composed of X ¹ and Y ¹ , X ² and Y ² , or X ³ and Y ³ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), Z is a carbon Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR ¹⁸ or —OR ¹⁸ , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.

  The norbornene-based polymer is disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1, WO2004 / 070463A1, and the like. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization. The norbornene-based polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, such as APL8008T (Tg 70 ° C.), APL 6013T (Tg 125 ° C.) or APL 6015T (Tg 145 ° C.) having a different glass transition temperature (Tg). There is a grade. Pellets such as TOPAS 8007, 5013, 6013, 6015, etc. are available from Polyplastics. Further, Appear 3000 is sold by Ferrania.

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

  As the siloxane polymer, a siloxane polymer having a repeating unit represented by the following formula (1) is preferable.

In formula (1), R < ¹ > -R < ⁴ > shows monovalent hydrocarbon groups, such as a C1-C8 alkyl group which may be same or different. m is an integer of 1 to 100, B is a positive integer, and A is 0 or a positive integer. X is a divalent organic group represented by the following formula (2).
In formula (2), Z is a divalent organic group selected from any of the following structural units, and n is 0 or 1. R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, and may be the same or different from each other. k is independently 0, 1, or 2, respectively.

In the formula (1), specific examples of R ^{1 to} R ⁴ include a methyl group, an ethyl group, a phenyl group, and the like, and m is preferably an integer of 3 to 60, more preferably 8 to 40. Moreover, B / A is 0-20, especially 0.5-5.

  Details of the siloxane polymer can be referred to the descriptions in paragraph numbers 0038 to 0044 of JP2013-243350A, the contents of which are incorporated herein.

A thermoplastic siloxane polymer can be used as the siloxane polymer.
The thermoplastic siloxane polymer is an R ²¹ R ²² R ²³ SiO _1/2 unit (R ²¹ , R ²² and R ²³ are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group. And an organopolysiloxane containing a SiO _4/2 unit, wherein the R ²¹ R ²² R ²³ SiO _1/2 unit / SiO _4/2 unit molar ratio is 0.6 to 1.7, and The organopolysiloxane represented by (4) is partially dehydrated and condensed, and the ratio of the organopolysiloxane to be dehydrated and condensed to the organopolysiloxane is 99: 1 to 50:50, The weight average molecular weight is preferably 200,000 to 1,500,000.
Formula (4)
(In formula (4), R ¹¹ and R ¹² each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and n is 5000 to 10,000.)

In the above formula (4), R ¹¹ and R ¹² are specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, and cyclopentyl group. , Hydrocarbon groups such as alkyl groups such as n-hexyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, and some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms Group, more preferably a methyl group and a phenyl group.

The weight average molecular weight of the thermoplastic organopolysiloxane is preferably 200,000 or more, more preferably 350,000 or more, and preferably 1,500,000 or less, more preferably 1,000,000 or less. Further, the content of low molecular weight components having a molecular weight of 740 or less is preferably 0.5% by mass or less, more preferably 0.1% by mass or less.
As a commercial item, SILRES 604 (Asahi Kasei Wacker silicone company make) is illustrated.

As the thermoplastic polyimide resin, one obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method can be used.
Known methods include, for example, a method of dehydrating and ring-closing polyamic acid obtained by mixing tetracarboxylic dianhydride and diamine in an organic solvent in an approximately equimolar amount and reacting at a reaction temperature of 80 ° C. or lower. It is done. Here, “substantially equimolar” means that the molar ratio of tetracarboxylic dianhydride to diamine is close to 1: 1. If necessary, the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the thermoplastic polyimide resin can be adjusted.

  The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, Screw 3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2, 3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2, 6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride Anhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane Dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4 - Carboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, bis (oxabicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene- 2, 3, , 6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenyl) phenyl] propane Dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2′-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane Anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3 -Bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl -3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4 ',-oxydiphthalic dianhydride, 1,2- (ethylene ) Bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride) ), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9 -(Nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecame) Tylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride) and the like. One species can be used alone, or two or more species can be used in combination. Among these, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride is preferred, and 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride is more preferred.

There is no restriction | limiting in particular as diamine, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3 , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3′- Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, 3,3'-diaminodiph Nyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2 , 2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis ( 1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2 -Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoethoxy) phenyl) sulfide Bis (4- (4-aminoethoxy) phenyl) sulfide, bis (4- (3-aminoethoxy) phenyl) sulfone, bis (4- (4- Minoethoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, polyoxypropylenediamine, 4,9-dioxadodecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, 1,2-diaminoethane 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminosi Examples include chlorohexane and 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
Among these diamines, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, polyoxypropylene diamine, 2 , 2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadodecane-1,12-diamine, 1,6-diaminohexane, and 4,9,14-trioxaheptadecane-1,17- One or more selected from the group consisting of diamines are preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.

Examples of the solvent used in the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.
The reaction temperature between the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C. The imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 450 ° C.

  The weight average molecular weight (Mw) of the thermoplastic polyimide resin is preferably 10,000 to 1,000,000, and more preferably 20,000 to 100,000.

In the present invention, the thermoplastic polyimide resin is at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea. A thermoplastic polyimide resin having a solubility at 25 ° C. of 10% by mass or more is preferable.
Examples of the thermoplastic polyimide resin having such solubility include 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl. Examples thereof include thermoplastic polyimide resins obtained by reacting with -5-aminoindane. This thermoplastic polyimide resin is particularly excellent in heat resistance.

  A commercially available product may be used as the thermoplastic polyimide resin. For example, Durimide (registered trademark) 200, 208A, 284 (manufactured by FUJIFILM Corporation), GPT-LT (manufactured by Gunei Chemical Industry Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR -C (Nippon Advanced Paper Industries Co., Ltd.), EXTEM VH1003, VH1003F, VH1003M, XH1015 (above, SABIC Japan GK) are included.

  In the present invention, the polycarbonate resin preferably has a repeating unit represented by the formula (11).

Formula (11)
In Formula (11), Ar ¹ and Ar ² each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Ar ¹ and Ar ² in formula (11) each independently represent an aromatic group. Aromatic groups include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring , Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring , Isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene , Chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. Of these, a benzene ring is preferred.
These aromatic groups may have a substituent, but preferably do not have a substituent.
Examples of the substituent that the aromatic group may have include a halogen atom, an alkyl group, an alkoxy group, and an aryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As an alkyl group, a C1-C30 alkyl group is mentioned. 1-20 are more preferable and, as for carbon number of an alkyl group, 1-10 are more preferable. The alkyl group may be linear or branched. In addition, some or all of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As an alkoxy group, a C1-C30 alkoxy group is preferable. 1-20 are more preferable and, as for carbon number of an alkoxy group, 1-10 are more preferable. The alkoxy group may be linear, branched or cyclic.
As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable.

  The weight average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 1,000,000, and more preferably 10,000 to 80,000. If it is the said range, the solubility to a solvent and heat resistance are favorable.

  Examples of commercially available polycarbonate resins include PCZ-200, PCZ-300, PCZ-500, PCZ-800 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), APEC 9379 (manufactured by Bayer), Panlite L-1225LM (Teijin). Etc.).

<<< Tension modulus E of thermoplastic resin >>>
The resin preferably has a tensile elastic modulus E of 1 MPa or more and 4000 MPa or less, more preferably 1 MPa or more and 100 MPa or less, more preferably 1 MPa or more, at 25 ° C., in accordance with JIS (Japanese Industrial Standard) K 7161: 1994. More preferably, it is 60 MPa or less, more preferably 1 MPa or more and 35 MPa or less, still more preferably 1 MPa or more and 20 MPa or less, still more preferably 1 MPa or more and 15 MPa or less, and 3 MPa or more and 10 MPa or less. It is even more preferable. By setting it as such a range, it becomes possible to suppress curvature more effectively.

<<< Amount of thermoplastic resin blended >>>
The temporary adhesive used in the present invention preferably contains a thermoplastic resin in a total solid content of the temporary adhesive (all components excluding the solvent) at a ratio of 50.00 to 99.99% by mass. 00 to 99.99 mass% is more preferable, and 88.00 to 99.99 mass% is particularly preferable. If content of a thermoplastic resin is the said range, it will be excellent in adhesiveness and peelability.
When using an elastomer as the thermoplastic resin, the elastomer is preferably included in the total solid content of the temporary adhesive in a proportion of 50.00 to 99.99% by mass, more preferably 70.00 to 99.99% by mass. 88.00 to 99.99% by mass is particularly preferable. If the content of the elastomer is in the above range, the adhesiveness and peelability are excellent. When two or more types of elastomer are used, the total is preferably in the above range.
Moreover, when using an elastomer as resin, 50-100 mass% is preferable, as for content of the elastomer in resin total mass, 70-100 mass% is more preferable, 80-100 mass% is more preferable, 90-100 mass% Is more preferable. Further, the resin may be substantially only an elastomer. In addition, when resin is substantially only an elastomer, 99 mass% or more is preferable, as for content of the elastomer in resin total mass, 99.9 mass% or more is more preferable, and it is still more preferable to consist only of an elastomer.

<< Releasing agent >>
The temporary adhesive used in the present invention preferably contains a release agent. Examples of the release agent include a compound containing a fluorine atom and a compound containing a silicon atom, a compound containing a silicon atom is preferable, and a silicone compound is more preferable.
The silicone compound is a compound containing a Si—O bond, and examples thereof include low molecular weight silicones such as polyether-modified silicone, silane coupling agent, silicone resin, silicone rubber, and cyclic siloxane, and may be polyether-modified silicone. preferable.
The refractive index of the silicone compound is preferably 1.350 to 1.480, more preferably 1.390 to 1.440, and still more preferably 1.400 to 1.430.
The weight reduction rate when the silicone compound is heated at 280 ° C. for 30 minutes under a N ₂ stream is preferably 0 to 70%, more preferably 5 to 50%, and even more preferably 10 to 30%.

The polyether-modified silicone used in the present invention preferably has a ratio represented by the formula (A) of 80% or more.
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is the mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mole percent of alkylene oxide contained in the polyether structure in the polyether-modified silicone.
The ratio represented by the above formula (A) is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and further preferably 99% or more. 100% is even more preferable.

  500-100000 are preferable, as for the weight average molecular weight of polyether modified silicone, 1000-50000 are more preferable, and 2000-40000 are further more preferable.

  In the present invention, the polyether-modified silicone is heated at a temperature increase rate of 20 ° C./min from 20 ° C. to 280 ° C. under a nitrogen stream of 60 mL / min for 30 minutes at a temperature of 280 ° C. It is preferable that the mass reduction rate when held is 50% by mass or less. By using such a compound, the surface shape of the substrate after heating tends to be further improved. The mass reduction rate of the polyether-modified silicone is preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether-modified silicone may be 0% by mass, but 15% by mass or more, and even 20% by mass or more is sufficiently practical.

  In the present invention, the refractive index of light of the polyether-modified silicone is preferably 1.440 or less. The lower limit is not particularly defined, but even if it is 1.400 or more, it is sufficiently practical.

The polyether-modified silicone used in the present invention is preferably a polyether-modified silicone represented by any of the following formulas (101) to (104).
Formula (101)
In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, and R ¹³ and R ¹⁵ are hydrogen It is an atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1 and p1 are each independently a number from 0 to 20, and x1 and y1 are each independently a number from 2 to 100.
Formula (102)
In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, and R ²³ is a hydrogen atom or a carbon number of 1 to 5 M2 and n2 are each independently a number of 0 to 20, and x2 is a number of 2 to 100.
Formula (103)
In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, and R ³³ and R ³⁵ are hydrogen. It is an atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number from 0 to 20, and x3 is a number from 2 to 100.
Formula (104)
In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent, R ⁴⁷ is a divalent linking group, and R ⁴⁸ is , A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m4 and n4 are each independently a number from 0 to 20, and x4 and y4 are each independently a number from 2 to 100.

In the formula ^{(101), R 11} and ^{R 16} are each independently a substituent, preferably an alkyl group or a phenyl group having 1 to 5 carbon atoms, more preferably a methyl group.
In the above formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and are a carbonyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group having 6 to 16 carbon atoms. , An alkenylene group having 2 to 8 carbon atoms, an alkynylene group having 2 to 5 carbon atoms, and an arylene group having 6 to 10 carbon atoms are preferable, and an oxygen atom is more preferable.
In formula (101), R ¹³ and R ¹⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An alkyl group is more preferred.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, which has the same meaning as R ¹¹ and R ¹⁶ in formula (101), and the preferred range is also the same.
In the above formula (102), R ²² is a divalent linking group, has the same meaning as R ¹² in formula (101), and the preferred range is also the same.
In the above formula (102), R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is synonymous with R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, which has the same meaning as R ¹¹ and R ¹⁶ in formula (101), and the preferred range is also the same.
In the formula (103), R ³² and R ³⁴ are each independently a divalent linking group, and have the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (103), R ³³ and R ³⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are synonymous with R ¹³ and R ¹⁵ in the formula (101), and their preferred ranges are also the same.

In the formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent, and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), The preferable range is also the same.
In the above formula (104), R ⁴⁷ is a divalent linking group and has the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (104), R ⁴⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and has the same meaning as R ¹³ and R ¹⁵ in formula (101), and the preferred range is also the same.

  Of formula (101) to formula (104), formula (103) or formula (104) is preferable, and formula (104) is more preferable.

In the polyether-modified silicone used in the present invention, the content of polyoxyalkylene groups in the molecule is not particularly limited, but it is desirable that the content of polyoxyalkylene groups exceeds 1% by mass in the total molecular weight.
The content of the polyoxyalkylene group is defined by “{(formula weight of polyoxyalkylene group in one molecule) / molecular weight of one molecule} × 100”.

Examples of silane coupling agents include fluorine atom-containing silane coupling agents, such as chlorodimethyl [3- (2,3,4,5,6-pentafluorophenyl) propyl] silane, pentafluorophenyldimethylchlorosilane, Pentafluorophenylethoxydimethylsilane, pentafluorophenylethoxydimethylsilane, trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane , Trimethoxy (3,3,3-trifluoropropyl) silane, triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane, trimethoxy (1H , 1H, H, 2H-heptadecafluorodecyl) silane, trimethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, trichloro [3- (pentafluorophenyl) propyl] silane, trimethoxy (11-pentafluorophenoxyundecyl) Silane, triethoxy [5,5,6,6,7,7,7-heptafluoro-4,4-bis (trifluoromethyl) heptyl] silane, trimethoxy (pentafluorophenyl) silane, triethoxy (1H, 1H, 2H , 2H-nonafluorohexyl) silane is preferred.
Furthermore, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, The surfactants described in Kaihei 8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are also exemplified as those usable in the present invention.

A commercial item can also be used for the silicone compound used by this invention.
For example, ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, WACKER-Belsil DMC 6038 (above, manufactured by Asahi Kasei Silicone Co., Ltd.), KF-352A, KF-352A, KF-352A KF-615A, KP-112, KP-341, X-22-4515, KF-354L, KF-355A, KF-6004, KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6020, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048, KF-6123, KF-6204, KF-640 KF-642, KF-643, KF-644, KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, X-22-4492 (above , Manufactured by Shin-Etsu Chemical Co., Ltd.), 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WAX, 5200 FORMULATION AID, 57 ADDITIVE, 8019 ADDITIVE, 8029 ADDITIVE, 8029 036, BY16-201, ES-5612 FORMULATION AID, FZ-2104, FZ-2108, FZ-2123, FZ-2162, FZ-2164, FZ-2191, FZ-2207, Z-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH 28 PAINR ADDITION, SH3749, SH3773M, SH8400, SH8700 (above, Toray Dow Corning Co., Ltd.) Manufactured by), BYK-378, BYK-302, BYK-307, BYK-331, BYK-345, BYK-B, BYK-347, BYK-348, BYK-349, BYK-377 (above, BYK Chemie Japan, Inc. )), Silwet L-7001, Silwet L-7002, Silwet L-720, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230, Silwet L-7605, TSF44 45, TSF4446, TSF4452, Silwet Hydrostable 68, Silwet L-722, Silwet L-7280, Silwet L-7500, Silwet L-7550, Silwet L-7600, Silwet L-7602, Silwet L-7604, Silwet L-7604, Silwet L-7608, Silwet L-7622, Silwet L-7650, Silwet L-7657, Silwet L-77, Silwet L-8500, Silwet L-8610, TSF4440, TSF4441, TSF4450, TSF4460 The product is manufactured by
Commercially available products are also trade names “BYK-300”, “BYK-306”, “BYK-310”, “BYK-315”, “BYK-313”, “BYK-320”, “BYK-322”. , “BYK-323”, “BYK-325”, “BYK-330”, “BYK-333”, “BYK-337”, “BYK-341”, “BYK-344”, “BYK-370”, “ “BYK-375”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “BYK-3550”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720” (above, manufactured by Big Chemie Japan Co., Ltd.) ), Trade names “AC FS 180”, “AC FS 360”, “AC S 20” (above, made by Algin Chemie), quotient Product names “Polyflow KL-400X”, “Polyflow KL-400HF”, “Polyflow KL-401”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-404”, “Polyflow KL-700” ( Kyoeisha Chemical Co., Ltd.), trade names “KP-301”, “KP-306”, “KP-109”, “KP-310”, “KP-310B”, “KP-323”, “KP” -326 "," KP-341 "," KP-104 "," KP-110 "," KP-112 "," KP-360A "," KP-361 "," KP-354 "," KP-357 ”,“ KP-358 ”,“ KP-359 ”,“ KP-362 ”,“ KP-365 ”,“ KP-366 ”,“ KP-368 ”,“ KP-330 ”,“ KP-650 ”, "KP- 51 ”,“ KP-390 ”,“ KP-391 ”,“ KP-392 ”(manufactured by Shin-Etsu Chemical Co., Ltd.), trade names“ LP-7001 ”,“ LP-7002 ”,“ 8032 ADDIIVE ” "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (manufactured by Toray Dow Corning Co., Ltd.), "TEGO WET 270" (Evonik Degussa Japan Co., Ltd.), “NBX-15” (Neos Co., Ltd.) and the like can also be used.

  Examples of the compound containing a fluorine atom include a fluorine-based liquid compound. As the fluorinated liquid compound, paragraph numbers 0025 to 0035 of International Publication No. WO2015 / 190477 can be referred to, the contents of which are incorporated herein. Examples of commercially available products include those corresponding to the fluorinated liquid compound, for example, MegaFuck F-557, among the MegaFac series manufactured by DIC Corporation.

When a temporary adhesive contains a mold release agent, the content has the preferable range of 0.001-1.0 mass% of the total solid of an adhesive agent. These other mold release agents may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
In particular, when the temporary adhesive used in the present invention contains a silicone compound, the content is preferably 0.001 to 1.0 mass% of the solid content of the temporary adhesive. The lower limit of the content of the silicone compound is more preferably 0.004% by mass or more, further preferably 0.006% by mass or more, further preferably 0.008% by mass or more, and further preferably 0.009% by mass or more. . The upper limit of the content of the silicone compound is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, and even more preferably 0.15% by mass or less. 0.09 mass% or less is still more preferable.
The temporary adhesive used in the present invention may contain only one kind of silicone compound or may contain two or more kinds. When 2 or more types are included, the total amount is preferably within the above range.

<< Plasticizer >>
The temporary adhesive used in the present invention may contain a plasticizer as necessary. By blending a plasticizer, a temporary adhesive layer that satisfies the above-mentioned various performances can be obtained.
As the plasticizer, phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.

Examples of the phthalate ester include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical Industry Co., Ltd.), PL-200, DOIP (above, manufactured by CG Esther Co., Ltd.) ), Sansosizer DUP (manufactured by Shin Nippon Rika Co., Ltd.) and the like.
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 (above, manufactured by Daihachi Chemical) and the like.
As aromatic polycarboxylic acid ester, TOTM (made by Daihachi Chemical Industry Co., Ltd.), Monosizer W-705 (made by Daihachi Chemical Industry Co., Ltd.), UL-80, UL-100 (ADEKA Corporation) Manufactured).
Examples of the polyester include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (manufactured by DIC Corporation), BAA-15 (Daihachi Chemical Industry Co., Ltd.), and the like.
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 plasticizer has a temperature at which the weight is reduced by 1% by mass under a nitrogen stream under a temperature rising condition at a constant rate of 20 ° C./min. It is preferably 250 ° C or higher, more preferably 270 ° C or higher, and particularly preferably 300 ° C or higher. The upper limit is not particularly defined, but can be, for example, 500 ° C. or less.

  The addition amount of the plasticizer is preferably 0.01% by mass to 5.0% by mass and more preferably 0.1% by mass to 2.0% by mass with respect to the total solid content of the temporary adhesive.

<< Solvent >>
The temporary adhesive used in the present invention contains a solvent. Any known solvent can be used without limitation, and an organic solvent is preferred.
Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyoxyacetate ( Examples: methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (Example: methyl 3-oxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) Etc.), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxy) Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate ( For example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Methyl, 2-oxobutanoic acid Le, esters such as 1-methoxy-2-propyl acetate;
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone;
Toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, t-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1 -Phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indane, 1 , 2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4- t Butyltoluene, 1,4-di-t-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-t-butyl-o-xylene, 1, 2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-t-butyl-m-xylene, 3,5-di-t-butyltoluene, 1,2, , 3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and other aromatic hydrocarbons;
Preferable examples include hydrocarbons such as limonene, p-menthane, nonane, decane, dodecane and decalin.
Among these, mesitylene, t-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate Diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferred.

  These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface. In this case, particularly preferably, mesitylene, t-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate It is a mixed solution comprised by the above.

The amount of the solvent of the temporary adhesive is preferably such that the total solid content concentration of the temporary adhesive is 5 to 80% by mass, more preferably 10 to 50% by mass, from the viewpoint of applicability, and 15 to 40% by mass. Is particularly preferred.
One type of solvent may be sufficient and 2 or more types may be sufficient as it. When two or more solvents are used, the total is preferably in the above range.
In addition, as for the content rate of the solvent in the temporary adhesive layer obtained by applying and drying a temporary adhesive in a layer form, 1 mass% or less is preferable, 0.1 mass% or less is more preferable, and it is especially preferable not to contain.

<< Antioxidant >>
The temporary adhesive used in the present invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, and the like can be used.
Examples of the phenol-based antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, Irganox 1330, Irganox 3114, Irganox 1035 (above, manufactured by BASF Japan Ltd.), Sumilizer MDP- S, Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, and Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of phosphorus antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol) phenyl. Examples thereof include phosphite, diphenylisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, Irgafos 168, Irgafos 38 (above, manufactured by BASF Japan Ltd.).
Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
As the antioxidant, Irganox 1010, Irganox 1330, 3,3′-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
Of the above antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. Most preferred. In particular, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it can be expected that the deterioration of the temporary adhesive due to the oxidation reaction can be efficiently suppressed. When a phenolic antioxidant and a sulfurous antioxidant are used in combination, the mass ratio of the phenolic antioxidant to the sulfurous antioxidant is: phenolic antioxidant: sulfurous antioxidant = 95: 5 5:95 is preferable, and 25:75 to 75:25 is more preferable.
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 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.

When the temporary adhesive contains an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass with respect to the total solid content of the temporary adhesive, and 0.005 to 10.0. The mass% is more preferable.
Only one type of antioxidant may be used, or two or more types may be used. When there are two or more antioxidants, the total is preferably in the above range.

<< Other additives >>
In the range which does not impair the effect of this invention, the temporary adhesive used by this invention is various additives, for example, a hardening | curing agent, a hardening catalyst, a filler, an adhesion promoter, as needed in addition to the additive mentioned above, An ultraviolet absorber, an aggregation inhibitor, etc. can be mix | blended. When these additives are blended, the total blending amount is preferably 3% by mass or less based on the total solid content of the temporary adhesive.

The temporary adhesive used in the present invention preferably does not contain impurities such as metals. The content of impurities is preferably 1 mass ppm (parts per million) or less, more preferably 100 mass ppt (parts per trigger) or less, still more preferably 10 mass ppt or less, and substantially free (of the measuring device) It is particularly preferred that it is below the detection limit.
Examples of a method for removing impurities such as metals from the temporary adhesive include filtration using a filter. The pore size of the filter is preferably a pore size of 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. The filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. You may use the filter previously wash | cleaned with the organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination. Moreover, various filter materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
Moreover, as a method of reducing impurities such as metals contained in the temporary adhesive, a raw material having a low metal content is selected as a raw material constituting the temporary adhesive, and filter filtration is performed on the raw material constituting the temporary adhesive. Examples thereof include a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). The preferable conditions for filter filtration performed on the raw materials constituting the temporary adhesive are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Permanent adhesive>
The permanent adhesive in the present invention is not for temporary fixing like a temporary adhesive, but for the purpose of semi-permanently fixing two substrates, such as incorporating two substrates in a bonded state in an element or the like. Say. When two substrates are bonded with a permanent adhesive, it can be preferably used for applications such as sensors, MEMS (Micro Electro Mechanical Systems), and decoding between chips having different functions.
Examples of permanent adhesives include hot melt adhesives described in JP-A-2015-212316, hot-melt adhesives described in JP-A-2013-227458, and hot-melt adhesives described in JP-A-8-92543. The description of paragraphs 0052 to 0055 of WO06 / 118033 can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the solvent described regarding the said temporary adhesive agent is used preferably as a solvent which may be mix | blended with a permanent adhesive. Further, the content of the solvent in the permanent adhesive is preferably the same as the content described for the temporary adhesive.

<Formation of adhesive layer>
As described above, the adhesive layer is formed by applying an adhesive on the substrate by spin coating, spraying, slit coating, roller coating, flow coating, doctor coating, dipping, or the like. can do.
As described above, the adhesive layer is formed on the surface of at least one of the two substrates to be bonded. An adhesive layer may be formed on only one of the substrates and bonded to the other substrate, or both may be bonded to each other by providing an adhesive layer.
Next, since the adhesive usually contains a solvent as described above, the adhesive is heated to volatilize the solvent (drying step). The heating temperature at this time is preferably higher than the boiling point of the solvent, more preferably 110 ° C. or more, further preferably 130 ° C. to 200 ° C., and particularly preferably 160 ° C. to 190 ° C.

<< Preparation of adhesive >>
The adhesive used in the present invention can be prepared by mixing the above-described components. Mixing of each component is normally performed in the range of 0 degreeC-100 degreeC. Moreover, after mixing each component, it is preferable to filter with a filter, for example. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can also be refiltered.
As a filter, if it is conventionally used for the filtration use etc., it can be used without being specifically limited. Examples thereof include a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon 6, nylon 6, 6, or the like, or a polyolefin resin such as polyethylene or polypropylene (PP). Among these materials, polypropylene and nylon are preferable.
The pore size of the filter is suitably about 0.003 to 5.0 μm, for example. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the adhesive while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or smaller than the first filtering hole diameter. A plurality of first filters having different pore diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. The commercially available filter can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd., or Kitz Micro Filter Co., Ltd., for example.

<Method for Manufacturing Semiconductor Device>
Hereinafter, an embodiment of a method for manufacturing a semiconductor element using a temporary adhesive will be described with reference to FIG. In addition, this invention is not limited to the following embodiment.
3A to 3E are schematic cross-sectional views (FIGS. 3A and 3B) for explaining the temporary bonding between the carrier substrate and the device wafer, and the device wafer temporarily bonded to the carrier substrate. The thinned state (FIG. 3C), the carrier substrate and the device wafer are peeled off (FIG. 3D), and the state after the temporary adhesive is removed from the device wafer (FIG. 3E). It is a schematic sectional drawing shown.

In this embodiment, as shown in FIG. 3A, first, an adhesive carrier substrate 100 in which a temporary adhesive layer 11 is provided on a carrier substrate 12 is prepared.
The temporary adhesive layer 11 is formed using a temporary adhesive, and it is preferable that the temporary adhesive layer 11 is substantially free of a solvent.
The device wafer 60 is formed by providing a plurality of device chips 62 on a surface 61 a of a silicon substrate 61.
The thickness of the silicon substrate 61 is preferably 200 to 1200 μm, for example. The device chip 62 is preferably a metal structure, for example, and the height is preferably 10 to 100 μm.
In the process of forming the temporary adhesive layer, a process of cleaning the back surface of the carrier substrate and the device wafer using a peeling solution may be provided. Specifically, by removing the residue of the temporary adhesive layer adhering to the end surface or back surface of the carrier substrate or the device wafer using a peeling solution, the contamination of the apparatus can be prevented, and the TTV ( (Total Thickness Variation) can be reduced.

Next, as shown in FIG. 3B, the adhesive carrier substrate 100 and the device wafer 60 are pressure-bonded, and the carrier substrate 12 and the device wafer 60 are temporarily bonded.
The temporary adhesive layer 11 preferably completely covers the device chip 62. Further, when the height of the device chip is X μm and the thickness of the temporary adhesive layer is Y μm, it is preferable to satisfy the relationship of “X + 100 ≧ Y> X”.
The provisional adhesive layer 11 completely covering the device chip 62 is effective when it is desired to further reduce the TTV of the thinned device wafer (that is, when the flatness of the thinned device wafer is to be further improved). .
That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the temporary adhesive layer 11, so that it is possible to almost eliminate the uneven shape on the contact surface with the carrier substrate 12. Therefore, even if the thickness is reduced in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the reduced thickness device wafer is reduced. The TTV of the integrated device wafer can be further reduced.

  Next, as shown in FIG. 3C, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (though not particularly limited, for example, thinning treatment such as grinding or chemical mechanical polishing (CMP)). , Chemical vapor deposition (CVD), physical vapor deposition (PVD) and other high-temperature and vacuum treatments, treatments using chemicals such as organic solvents, acidic treatment solutions and basic treatment solutions, plating treatments, actinic rays Irradiation, heat treatment, cooling treatment, etc.). In FIG. 3C, the silicon substrate 61 is thinned (for example, thinned so as to have the above-described thickness) to obtain a thinned device wafer 60a.

After the device wafer is thinned, it may be provided with a step of cleaning the temporary adhesive layer protruding outside the area of the substrate surface of the device wafer with a peeling solution before performing the processing under high temperature and vacuum. . Specifically, after thinning the device wafer, the temporary bonding layer that protrudes is removed using a stripping solution, whereby temporary bonding is performed by directly applying the treatment under high temperature and vacuum to the temporary bonding layer. Layer deformation and alteration can be prevented.
In the present invention, the area of the film surface of the temporary adhesive layer is preferably smaller than the area of the substrate surface of the carrier substrate. Further, in the present invention, when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the device wafer is D μm, and the diameter of the film surface of the temporary adhesive layer is T μm, (C−200) ≧ T ≧ D It is more preferable to satisfy. Furthermore, the diameter of the substrate surface of the carrier substrate is _C μm, the diameter of the substrate surface of the device wafer is _D μm, the diameter of the film surface of the temporary adhesive layer on the side in contact with the carrier substrate is _TC μm, and the device wafer of the temporary adhesive layer It is preferable that (C−200) ≧ T _C > T _D ≧ D is satisfied when the diameter of the film surface on the side in contact is T _D μm. By setting it as such a structure, the deformation | transformation and the quality change of the temporary adhesion layer by the process under high temperature and a vacuum being directly performed to a temporary adhesion layer can be suppressed more.
In addition, the area of the film surface of the temporary adhesive layer means an area when viewed from a direction perpendicular to the carrier substrate, and the unevenness of the film surface is not considered. The same applies to the substrate surface of the device wafer. That is, the substrate surface of the device wafer referred to here is, for example, a surface corresponding to the 61a surface in FIG. 3 and the surface on which the device chip is provided. The same applies to the diameter of the temporary adhesive layer such as the film surface.
The diameter T of the film surface of the temporary adhesive layer is the diameter of the film surface on the side of the temporary adhesive layer in contact with the carrier substrate, T _C μm, and the film surface on the side of the temporary adhesive layer in contact with the device wafer. When the diameter is T _D μm, T = (T _C + T _D ) / 2. The diameter of the substrate surface of the carrier substrate and the diameter of the substrate surface of the device wafer refer to the diameter of the surface in contact with the temporary adhesive layer.
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thinned device wafer 60a after the thinning process, and the silicon through electrode is formed in the through hole. You may perform the process which forms (not shown).
In addition, the heat treatment may be performed after the carrier substrate 12 and the device wafer 60 are temporarily bonded to each other before being peeled off. As an example of the heat treatment, heating is performed when performing a mechanical or chemical treatment.
80 to 400 degreeC is preferable, as for the highest reached temperature in heat processing, 130 to 400 degreeC is more preferable, and 180 to 350 degreeC is further more preferable. The highest temperature reached in the heat treatment is preferably lower than the decomposition temperature of the temporary adhesive layer. The heat treatment is preferably heating for 30 seconds to 30 minutes at the highest temperature, and more preferably heating for 1 minute to 10 minutes at the highest temperature.

Next, as shown in FIG. 3D, the carrier substrate 12 is peeled from the thinned device wafer 60a (device wafer subjected to mechanical or chemical treatment). The temperature at the time of peeling is preferably 40 ° C. or lower, and can also be 30 ° C. or lower. The lower limit of the temperature at the time of peeling is, for example, 0 ° C. or higher, and preferably 10 ° C. or higher. The peeling in the present invention is highly valuable in that it can be performed at a room temperature of about 15 to 35 ° C.
The peeling method is not particularly limited, but it is preferable that the thinned device wafer 60a is fixed and the carrier substrate 12 is pulled up from the end in the direction perpendicular to the thinned device wafer 60a for peeling. At this time, the peeling interface is preferably the interface between the carrier substrate 12 and the temporary adhesive layer 11. The pulling speed during peeling is preferably 30 to 100 mm / min, and more preferably 40 to 80 mm / min. In this case, the adhesive strength A at the interface between the carrier substrate 12 and the temporary adhesive layer 11 and the adhesive strength B between the device wafer surface 61a and the temporary adhesive layer 11 preferably satisfy the following formula (A1).
A <B Formula (A1)
The force for pulling up the edge during peeling is preferably 0.33 N / mm or less, and can also be 0.2 N / mm or less. The lower limit is preferably 0.07 N / mm or more. The force at this time can be measured using a force gauge.

Then, as shown in FIG. 3E, the thinned device wafer can be obtained by removing the temporary adhesive layer 11 from the thinned device wafer 60a.
The removal method of the temporary adhesive layer 11 is, for example, a method of removing using a peeling liquid (a method of peeling and removing the temporary adhesive layer after swelling with the peeling liquid, a method of destroying and removing the temporary adhesive layer by spraying the peeling liquid) And a method of dissolving and removing the temporary adhesive layer by dissolving it in a stripping solution), a method of decomposing or evaporating the temporary adhesive layer by irradiation with actinic rays, radiation or heat.
From the viewpoint of reducing the amount of solvent used, it is preferable to peel and remove (peel off) the temporary adhesive layer in a film state. The method of peeling and removing the temporary adhesive layer in a film state means that the temporary adhesive layer is peeled and removed by applying a physical force without performing chemical treatment such as using a peeling solution (peel off). ). When the temporary adhesive layer is peeled and removed in the film state, peeling by hand or mechanical peeling is preferable. In order to peel and remove the temporary adhesive layer in a film state, it is preferable that the adhesion strength B between the device wafer surface 61a and the temporary adhesive layer 11 satisfies the following formula (B1).
B ≦ 4N / cm ・ ・ ・ ・ Formula (B1)

  Moreover, as a peeling liquid, the organic solvent which melt | dissolves the temporary adhesion layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.), limonene, p-menthane, nonane, decane, dodecane, decalin, etc.), aromatic Hydrocarbons (toluene, xylene, anisole, mesitylene, pseudocumene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2- Dimethylpropyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o -Cymene Indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o -Xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyl Toluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene Zen, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.), 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 ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), others (triethyl phosphate, tricresyl phosphate, N-phenylethanol) Ruamine, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, etc.) Can be mentioned.

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.
Furthermore, 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.

  Examples of the acid include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid and boric acid, alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid and 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 setting the content of the surfactant within the above-described range, the peelability between the temporary adhesive layer 11 and the thinned device wafer 60a tends to be further improved.

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

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

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

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

  Further, if necessary, the stripping solution may contain additives such as an antifoaming agent and a water softening agent.

  After peeling the carrier substrate 12 from the thinned device wafer 60a, various known processes are performed on the thinned device wafer 60a to manufacture a semiconductor element having the thinned device wafer 60a.

When the temporary adhesive layer is attached to the carrier substrate, the carrier substrate can be regenerated by removing the temporary adhesive layer. As a method for removing the temporary adhesive layer, a method of physically removing the temporary adhesive layer by spraying with a brush, ultrasonic waves, ice particles or aerosol, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent, activity A chemical removal method such as a method of decomposing or vaporizing by irradiation with light, radiation, or heat can be mentioned, and conventionally known cleaning methods can be used depending on the carrier substrate.
For example, when a silicon substrate is used as the carrier substrate, a conventionally known silicon wafer cleaning method can be used. For example, as an aqueous solution or organic solvent that can be used for chemical removal, strong acid, strong base, strong The oxidizing agent or a mixture thereof is raised. Specifically, acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidation of hydrogen peroxide and the like Or a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride, etc. Can be mentioned.

  From the viewpoint of adhesiveness when the regenerated carrier substrate is used, it is preferable to use a carrier substrate cleaning solution. The carrier substrate cleaning liquid preferably contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid. From the viewpoint of detergency of the temporary adhesive layer on the carrier substrate, an inorganic acid is preferable, and sulfuric acid is most preferable.

  As hydrogen peroxide, 30% by mass hydrogen peroxide water can be preferably used, and the mixing ratio of the strong acid and 30% by mass hydrogen peroxide water is preferably 1: 100 to 100: 1 by mass ratio, and 1: 1. -10: 1 is more preferable, and 3: 1 to 5: 1 is most preferable.

A second embodiment of the semiconductor manufacturing method will be described with reference to FIG. The same parts as those of the first embodiment described above are denoted by the same reference numerals and the description thereof is omitted.
4A to 4E are schematic cross-sectional views (FIGS. 4A and 4B) for explaining the temporary bonding between the carrier substrate and the device wafer, and the device wafer temporarily bonded to the carrier substrate. The thinned state (FIG. 4C), the carrier substrate and the device wafer are peeled off (FIG. 4D), and the state after the temporary adhesive layer is removed from the device wafer (FIG. 4E). It is a schematic sectional drawing shown.
As shown in FIG. 4A, this embodiment is different from the first embodiment in that a temporary adhesive layer is formed on the surface 61a of the device wafer.
When the temporary adhesive layer 11a is provided on the surface 61a of the device wafer 60, the temporary adhesive is applied (preferably applied) to the surface 61a of the device wafer 60, and then dried (baked). be able to. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
Next, as shown in FIG. 4B, the carrier substrate 12 and the device wafer 60 are pressure-bonded, and the carrier substrate 12 and the device wafer 60 are temporarily bonded. Next, as shown in FIG. 4C, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment to reduce the thickness of the silicon substrate 61, thereby obtaining a thinned device wafer 60a. . Next, as shown in FIG. 4D, the carrier substrate 12 is peeled from the thinned device wafer 60a. Then, as shown in FIG. 4E, the temporary adhesive layer 11a is removed from the thinned device wafer 60a.

The method for manufacturing a semiconductor element of the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
In the above-described embodiments, the silicon substrate is used as the device wafer. However, the present invention is not limited to this, and any device that can be subjected to mechanical or chemical treatment in the method of manufacturing a semiconductor element is used. It may be a processing member.
In the above-described embodiment, the device wafer (silicon substrate) is mechanically or chemically treated as a device wafer thinning process and a through silicon via formation process, but is not limited thereto. It is not a thing, and any process required in the manufacturing method of a semiconductor element is mentioned.
In addition, the shape, dimension, 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.

  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.

<Preparation of adhesive>
As shown below, each component of the adhesive was mixed to make a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 5 μm to prepare an adhesive.

<< Adhesive composition >>
-Thermoplastic resins listed in Table 1: amounts listed in Table 1-Additives listed in Table 1: amounts listed in Table 1-Solvents listed in Table 1: amounts listed in Table 1 <<<< Ingredients blended in adhesive >>>
・ Irganox 1010 (manufactured by BASF Japan): 1 part by mass ・ Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 1 part by mass

The resins listed in Table 1 are as follows.
In Table 2 above, COP refers to a cycloolefin polymer.

The additives and solvents in Table 1 are as follows.
A-1: KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
A-2: Megafuck F-557 (manufactured by DIC Corporation)
S-1: Mesitylene (manufactured by Toyo Gosei Co., Ltd.)
S-2: 1,4-diethylbenzene (manufactured by Toray Industries, Inc.)

In Table 1 above, EBR (Edge Bead Removal) means edge bead processing, and is processing for adjusting the edge bead shape with respect to the adhesive layer after film formation.
The jig means jig processing. Polytetrafluoroethylene (PTFE) having a diameter of 5 mm with the tip rounded on the surface of the adhesive while rotating the substrate provided with the adhesive layer after film formation at a speed of 700 rpm. This was done by pressing a metal rod.

<Formation of laminate>
<< Formation of Laminate (Examples 1 to 3, 6, 8 to 16) >>
As a substrate, a disc-shaped silicon substrate having a diameter of 12 inches (1 inch is 2.54 cm) is used, and the adhesive is coated on the surface thereof using a coating apparatus (EVG 101, manufactured by Evi Group Japan Co., Ltd.). To form a film. Using a hot plate (EVG 105, manufactured by Evi Group Japan Co., Ltd.), heat at the baking temperature shown in Table 1 for 3 minutes, and further heat at 180 ° C. for 3 minutes to dry the solvent, and the silicon substrate An adhesive layer was formed on the surface. Let the obtained laminated body be the laminated body A. FIG.
In the above, the hot plate was modified from the rear exhaust to the top exhaust so that the exhaust can be efficiently performed by increasing the number of exhaust ports formed in the top plate. As a result, the solvent component that causes convection on the surface of the adhesive coating film can be efficiently discharged out of the system while heating and leveling the adhesive coating film, and the peak of the bulge at the end is 2 I made it.
The obtained laminate A is set in a coating apparatus (EVG 101, manufactured by Evi Group Japan Co., Ltd.) with the silicon substrate facing down, while increasing the rotational speed from 1250 rpm to 2000 rpm at an acceleration of 50 rpm / s. The adhesive layer attached to the bevel portion was removed by performing BSR (Back Side Rinse) treatment using mesitylene at a flow rate of 20 mL / min.

<< Formation of Laminate (Example 4) >>
While rotating the substrate provided with the adhesive layer to the layered product A at a speed of 700 rpm, the mesitylene was flowed at a flow rate of 20 mL / min on the adhesive layer at a position corresponding to a distance of 20 mm from the edge of the substrate for 15 seconds. A layered product A was formed in the same manner as in Example 1 except that EBR was performed by supplying the product.

<< Formation of Laminate (Example 5) >>
While rotating the substrate provided with the adhesive layer to the layered product A at a speed of 700 rpm, the diameter of the surface of the adhesive is rounded for 20 seconds at a position corresponding to a distance of 6 mm from the edge of the substrate. A laminate A was formed in the same manner as in Example 1 except that the jig treatment was performed by pressing a 5 mm polytetrafluoroethylene (PTFE) rod.

<< Formation of Laminate (Example 7) >>
While rotating the substrate provided with the adhesive layer to the layered product A at a speed of 700 rpm, the substrate is placed on the adhesive layer at a position corresponding to a distance of 20 mm from the edge of the substrate for 10 seconds and 10 mm from the edge of the substrate. A laminate A was formed in the same manner as in Example 4 except that EBR was performed by supplying mesitylene at a flow rate of 20 mL / min for 10 seconds to a position corresponding to the distance of.

<< Formation of Laminate (Example 17) >>
While rotating the substrate provided with the adhesive layer to the layered product A at a speed of 700 rpm, the substrate is placed on the adhesive layer at a position corresponding to a distance of 20 mm from the edge of the substrate for 10 seconds and 10 mm from the edge of the substrate. A laminate A was formed in the same manner as in Example 4 except that EBR was performed by supplying mesitylene at a flow rate of 20 mL / min for 30 seconds to a position corresponding to the distance.

<< Formation of Laminate (Example 18) >>
While rotating the substrate provided with the adhesive layer to the layered product A at a speed of 700 rpm, the diameter of the surface of the adhesive is rounded for 20 seconds at a position corresponding to a distance of 10 mm from the edge of the substrate A laminate A was formed in the same manner as in Example 1 except that the jig treatment was performed by pressing a 5 mm polytetrafluoroethylene (PTFE) rod.

<< Film thickness evaluation >>
The silicon substrate of the laminate A obtained above was measured with a film thickness sensor fixed to an XY stage. From the central part of the silicon substrate, the shape of the adhesive layer at a position corresponding to the end of the silicon substrate was measured. The shape of the raised portion (edge bead) at the end of the adhesive layer (cross-sectional shape perpendicular to the substrate surface of the raised portion) and the film thickness were measured. In the measurement, as shown in FIG. 2, the diameter direction of the substrate surface and the Z direction (direction perpendicular to the diameter direction of the substrate surface) are determined. The diameter direction of the substrate surface is every 0.1 mm, and the Z direction is every 1 mm. Measured.
The average film thickness t of the adhesive layer is an average value of the thickness of the adhesive layer (unit: μm).
The height (H _n ) of the peak in the diameter direction is indicated as H ₁ , H ₂ , H _{3 in} order from the end closer to the end of the adhesive layer (see FIG. 2, but there are also examples in which H ₃ does not exist is there). For H ₁ , H ₂ , and H ₃ , the height of the peak of each concentric circle is usually the same at any point, but if there is an error, the height of the highest point is set. and the _{H 1, H 2, H 3} .
The shortest distance (R _n ) between the end of the substrate in the diametric direction and the position on the substrate corresponding to the n-th peak counted from the end of the substrate toward the center is the end of the substrate (silicon substrate) R ₁ , R ₂ , and R ₃ are shown in order from the nearest (see FIG. 2, but there are examples in which R ₃ does not exist).
Furthermore, a value of n · t / 40 and a value of n · t / 8 were calculated from the value of R _n and the number of n.
In the measurement, ST-T80 manufactured by Keyence Corporation was used as a film thickness sensor.
The profiles of Example 1 and Comparative Example 1 are shown in FIG. In FIG. 5, the diameter direction (Radius) indicates the distance from the position of the adhesive layer corresponding to the center of the silicon substrate, and the unit is mm. The Z direction (FT) indicates the film thickness of the adhesive layer, and its unit is μm (in FIG. 5, it is expressed as um for convenience). FIG. 5 (1) is the profile of Example 1, and it was confirmed that two peaks were formed. FIG. 5B is the profile of Comparative Example 1, and it was confirmed that one peak was formed.

<< Bonding process >>
The laminated body A obtained above and the second silicon substrate having a diameter of 12 inches were subjected to a pressure of 1 Pa with a wafer bonding apparatus (EVG 540, manufactured by Evi Group Japan Co., Ltd.) so that the adhesive layer is on the inside. Then, a temperature of 200 ° C. and a pressure of 0.3 MPa were applied and thermocompression bonded for 1 minute to obtain a laminate B.

<< TTV evaluation >>
Using the laminate B obtained by the above bonding treatment with a film thickness sensor (manufactured by Otsuka Electronics Co., Ltd., SF-3 / BB) fixed to an XY stage, the thickness unevenness of the laminate (TTV) : Total Thickness Variation). In the measurement, following the evaluation of the film thickness, the diameter direction of the substrate surface and the Z direction (direction perpendicular to the diameter direction of the substrate surface) are determined. The diameter direction of the substrate surface is every 0.1 mm and the Z direction is 1 mm. Measured every other time.
Evaluation was based on the following criteria. Evaluation C or higher is a practical level.
A: TTV is less than 4 μm B: TTV is not less than 4 μm and less than 8 μm C: TTV is not less than 8 μm and less than 12 μm D: TTV is not less than 12 μm

<< Back grinding (thinning) processing >>
The back surface of the second silicon substrate of the laminate B (the surface that is not in contact with the adhesive layer) is polished to a thickness of 40 μm using a back grinder (manufactured by DISCO Corporation, DFG8540) to reduce the thickness. Body C was obtained.

<< Chipping evaluation >>
The end surface of the second silicon substrate, which is a thinned substrate, of the laminate C was observed with a light microscope (MX51, manufactured by Olympus Corporation) in the circumferential direction of the disk. The number of occurrences of chipping with a length of 1 mm or more (cracks on the end face of the second silicon substrate) was measured and evaluated based on the following criteria. Evaluation C or higher is a practical level.
A: The number of chipping is 0 B: The number of chipping is 1 or more and 5 or less C: The number of chipping is 6 or more and 10 or less D: The number of chipping is 11 or more

<< Peeling evaluation >>
The thinned second silicon substrate of the laminate C was placed on the lower side, and the lower second silicon substrate was fixed together with the dicing frame at the center of the dicing tape using a dicing tape mounter. Then, using a wafer debonder device (Synapse Z, manufactured by Tokyo Electron Ltd.), at 25 ° C., the upper silicon substrate is pulled up at a speed of 3 mm / min in a direction perpendicular to the lower silicon substrate. Then, it was confirmed whether the upper or lower silicon substrate could be peeled without cracking, and evaluation was performed according to the following criteria.
A: The substrate could be peeled without cracking.
B: Adhesive strength was weak and the periphery of the wafer was partially floating, but the substrate could be peeled off without being cracked, or the substrate was cracked at a lifting speed of 3 mm / min, but the substrate was It was possible to peel without cracking.
C: The substrate was cracked at a pulling speed of 2 mm / min, but was peelable without being cracked at a pulling speed of 1 mm / min.
D: Other than A, B and C above.

  As is clear from the above results, when the laminate of the present invention is used, it is possible to provide a laminate that can adhere two substrates with little thickness unevenness and can be thinned with little damage. (Examples 1-18). On the other hand, when there was one peak (Comparative Example 1), the thickness unevenness was large.

1: Substrate 2: Adhesive or adhesive layer 3: Second substrate 4: Void 5: Peak 11, 11a: Temporary adhesive layer 12: Carrier substrate 60: Device wafer 60a: Thinned device wafer 61: Silicon substrate 61a: Surface 61b, 61b1: back surface 62: device chip 100: adhesive carrier substrate

Claims (8)

A disk-shaped substrate and an adhesive layer including a thermoplastic resin having an end raised portion generated when an adhesive is applied, and the raised portion at the end of the adhesive layer has two or more peaks. A laminate comprising:
The height H _n of the n th peak counted toward the center from the edge of the substrate, the height H _{n + 1} of the (n + 1) th peak, average thickness t of the adhesive layer is, t <H n + ₁ <H _n satisfy _<t + 40 / n, the product Sotai; however, the unit of the average thickness is [mu] m, a unit of the peak height of [mu] m. A disk-shaped substrate and an adhesive layer including a thermoplastic resin having an end raised portion generated when an adhesive is applied, and the raised portion at the end of the adhesive layer has two or more peaks. A laminate comprising:
The shortest distance R _n between the edge of the substrate and the position on the substrate corresponding to the n-th peak counted from the edge of the substrate toward the center, and the average film thickness t of the adhesive layer are n · t / 40 _<satisfy R n <n · t / 8 , the product Sotai; however, the unit of the average thickness is [mu] m, a unit of the minimum distance is in mm. The laminate according to claim 1 or 2 , wherein the adhesive layer containing the thermoplastic resin contains polyether-modified silicone. A substrate and an adhesive layer including a thermoplastic resin having an end raised portion that occurs when an adhesive is applied, and the raised portion at the end of the adhesive layer has two or more peaks, A laminate,
The laminated body in which the contact bonding layer containing the said thermoplastic resin contains polyether modified silicone. The laminate according to claim 3 or 4, wherein the polyether-modified silicone has a ratio represented by the formula (A) of 80% or more;
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is the mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mole percent of alkylene oxide contained in the polyether structure in the polyether-modified silicone. The laminate according to any one of claims 1 to 5 , wherein the raised portion has two peaks. The laminated body of any one of Claims 1-6 in which the contact bonding layer containing the said thermoplastic resin contains a polystyrene-type elastomer as the said thermoplastic resin. A step of applying an adhesive containing a solvent on a substrate by a spin coating method to form an adhesive layer, and a step of adjusting so that the raised portion at the end of the adhesive layer has two or more peaks. The manufacturing method of the laminated body of any one of Claims 1-7 containing.