JP7074879B2 - Temporary adhesive compositions, kits and laminates - Google Patents

Description

The present invention relates to a composition for temporary adhesion. The present invention also relates to a kit containing the temporary adhesive composition and a laminate containing a temporary adhesive layer formed by using the temporary adhesive composition.

In recent years, for the purpose of miniaturizing IC (integrated circuit) chips and the like, in semiconductor device manufacturing, attempts have been made to reduce the thickness of a substrate to be processed such as a wafer to 200 μm or less.

When the substrate to be processed is thin as described above, it is stably handled independently without damage when the substrate to be processed is subjected to processing for manufacturing semiconductor devices or when the substrate to be processed is moved between processes. That is difficult. Therefore, in order to improve the handleability of the substrate to be processed, the substrate to be processed is temporarily bonded to a carrier substrate (glass substrate, film, etc.), subjected to necessary treatment, and then the unnecessary carrier substrate is attached to the substrate to be processed. The technique of peeling from the glass is known.

For example, in Patent Documents 1 and 2, a temporary adhesive composition (temporary adhesive) is applied to a carrier substrate and dried to form a temporary adhesive layer, and a semiconductor wafer is used as a carrier substrate via the temporary adhesive layer. It is described that temporary bonding is performed.

Conventionally, the method of applying the temporary bonding composition on the carrier substrate is mainly the spin coating method because a thin and uniform adhesive layer can be easily formed in a short time.

Japanese Patent No. 6034796 International Publication No. 2016/0523115 (A1)

In recent years, from the viewpoint of increasing the number of chips per substrate, it has been studied to make the substrate to be processed for manufacturing semiconductor devices rectangular, and along with this, the method of applying the composition has also been expanded to a rectangular range. A method that enables coating (hereinafter, also simply referred to as “rectangular coating method”) is attracting attention. Examples of such a rectangular coating method include a slit coating method, a bar coating method, and a roller coating method.

This time, when the temporary adhesive composition is applied onto the carrier substrate by using the rectangular coating method as described above, the conventional method sufficiently provides the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer. The problem was found that it can be difficult to secure.

The present invention has been made in view of the above problems, and provides a temporary adhesive composition capable of sufficiently ensuring the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer even when a rectangular coating method is used. With the goal.

Another object of the present invention is to provide a kit including the above-mentioned temporary bonding composition and a rectangular substrate.

Furthermore, an object of the present invention is to provide a laminate including a temporary adhesive layer and a rectangular substrate formed by using the temporary adhesive composition.

The above-mentioned problems are (a) the state of the solid-liquid interface of the composition when it comes into contact with the coater member, and (b) the state of the solid-liquid interface when it comes into contact with the outside air, by utilizing the internal behavior of the temporary bonding composition due to the interface fluctuation. The problem could be solved by dynamically adjusting the state of the gas-liquid interface of the composition before the coating film was dried. Specifically, the above problems were solved by the following means <1>, preferably <2> to <17>.

<1>
Contains elastomers, organic solvents and surfactants,
The organic solvent contains a low boiling point organic solvent having a boiling point of 120 ° C. or lower at a ratio of 50 to 95% by mass with respect to the whole organic solvent.
The surfactant contains a fluorine-based surfactant A and a silicone-based surfactant B.
Temporary adhesive composition satisfying the formula (1) for the surfactant A and the surfactant B;
_WA / _WB = 1.5-5 formula (1);
In the formula (1), WA represents the content of the surfactant _A with respect to the entire surfactant in terms of mass%, and WB represents the content of the surfactant _B with respect to the entire surfactant in terms of mass%. Represents a quantity.
<2>
_WA / _WB is 1.5 to 3.0,
The composition for temporary adhesion according to <1>.
<3>
The content of the surfactant B in the entire composition is 0.00005 to 1% by mass.
The composition for temporary adhesion according to <1> or <2>.
<4>
The content of the above-mentioned surfactant with respect to the entire composition is 0.00002 to 2% by mass.
The composition for temporary adhesion according to any one of <1> to <3>.
<5>
The content of the organic solvent in the entire composition is 60 to 95% by mass.
The composition for temporary adhesion according to any one of <1> to <4>.
<6>
The content of the low boiling point organic solvent is 50% by mass or more with respect to the whole organic solvent.
The composition for temporary adhesion according to any one of <1> to <5>.
<7>
The contact angle of the temporary bonding composition with respect to the stainless SUS304 in the liquid state is 50 degrees or less.
The composition for temporary adhesion according to any one of <1> to <6>.
<8>
Low boiling organic solvent contains aliphatic hydrocarbons,
The composition for temporary adhesion according to any one of <1> to <7>.
<9>
Organic solvents contain aromatic hydrocarbons,
The composition for temporary adhesion according to any one of <1> to <8>.
<10>
The above-mentioned surfactant contains an acetylene-based surfactant C.
The composition for temporary adhesion according to any one of <1> to <9>.
<11>
For the surfactant C and the surfactant B, the formula (2) is satisfied.
The temporary adhesive composition according to <10>;
_WC / _WB = 0.005-500 formula (2);
In the formula (2), WC represents the content of the surfactant _C with respect to the whole surfactant in terms of mass%.
<12>
The above-mentioned surfactant and organic solvent satisfy the formula (3).
The temporary adhesive composition according to any one of <1> to <11>;
W _ALL / _WS = 0.000002 to 0.006 equation (3);
In the formula (3), _WALL represents the content of the entire surfactant with respect to the entire composition in terms of mass%, and _WS represents the content of the entire organic solvent in terms of mass% with respect to the entire composition. ..
<13>
Elastomer contains hydrogenated material,
The composition for temporary adhesion according to any one of <1> to <12>.
<14>
Elastomers include polystyrene-based elastomer hydrogenators,
The composition for temporary adhesion according to <13>.
<15>
The content of the polystyrene-based elastomer hydrogenated material with respect to the entire elastomer is 10 to 100% by mass.
The composition for temporary adhesion according to <14>.
<16>
A kit containing a rectangular substrate and the composition according to any one of <1> to <15>.
<17>
A laminate containing a rectangular substrate and a temporary adhesive layer formed by using the composition according to any one of <1> to <15>.

With the temporary adhesive composition of the present invention, even if a rectangular coating method is used when forming the temporary adhesive layer, the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer can be sufficiently ensured. Then, according to the kit of the present invention, a temporary adhesive layer having good peelability can be efficiently formed on a rectangular substrate by using the rectangular coating method. Further, the laminate of the present invention makes it possible to efficiently temporarily bond the substrate to be processed to the carrier substrate by using a rectangular substrate having a temporary adhesive layer having good peelability in semiconductor device manufacturing.

It is a schematic sectional drawing which shows the slit coater. It is a schematic sectional drawing which shows the bar coater. It is a schematic diagram of the 1st Embodiment which shows the manufacturing method of the semiconductor device. It is the schematic of the 2nd Embodiment which shows the manufacturing method of the semiconductor device.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.

In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.

As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.

Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent. For example, when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). It means.

As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.

As used herein, the concentration of solids in a composition is expressed as a percentage of the total mass of the composition by the mass of the other components excluding the solvent. Further, the temperature shall indicate 23 ° C. unless otherwise specified.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. For the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Further, unless otherwise specified, it shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in GPC measurement.

In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.

<Composition for temporary adhesion>
The composition for temporary adhesion of the present invention contains an elastomer, an organic solvent, and a surfactant, and the organic solvent is a low boiling point having a boiling point of 120 ° C. or lower at a ratio of 50 to 95% by mass with respect to the entire organic solvent. It contains an organic solvent, the surfactant contains a fluorine-based surfactant A and a silicone-based surfactant B, and the surfactant A and the surfactant B satisfy the formula (1).

_WA / _WB = 1.5-5 formula (1)
In the formula (1), WA represents the content of the surfactant _A with respect to the entire surfactant in terms of mass%, and WB represents the content of the surfactant _B with respect to the entire surfactant in terms of mass%. Represents a quantity.

The composition for temporary adhesion of the present invention contains the above-mentioned low boiling point organic solvent and the surfactant A and the surfactant B satisfying the formula (1) in a predetermined amount when forming the temporary adhesive layer. Even if the rectangular coating method is used, the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer can be sufficiently ensured. Details are unknown, but this is presumed as follows.

For example, as shown in FIG. 1, in the slit coating method, the temporary adhesive composition L discharged from the gap 13 formed by the stainless steel blade 16 of the slit coater 1 moves relative to the blade 16. It is applied to the surface of the substrate S (either the substrate to be processed or the carrier substrate). In FIG. 1, the blade 16 is moving in the direction A with respect to the substrate S. As a result, the coating film 14 is formed in a rectangular range corresponding to the width of the blade 16 and the relative movement distance, and the temporary adhesive layer is formed by drying the coating film 14. Further, as shown in FIG. 2, even in the bar coat method, a rectangular shape is used by using a wire bar 25 (a shaft on which a stainless steel wire is precisely wound) and a bar coater 2 provided with a stainless steel coating liquid supply unit 26. The coating film 24 is formed in the area. In this bar coater 2, the temporary adhesive composition L is supplied from the gap 23 between the coating liquid supply unit 26 and the wire bar 25, the coating film is uniformly flattened by the wire bar 25, and the coating film 24 dries. As a result, a temporary adhesive layer is formed. Therefore, when the temporary adhesive composition is applied onto the substrate by using the rectangular coating method as described above, for example, the composition may be discharged from a coater member such as a blade or a wire bar, or the coating film may be applied. It is considered that the coatability of the temporary adhesive composition is improved by shortening the drying time of the composition.

Therefore, in the temporary adhesive composition of the present invention, the viscosity of the above composition was adjusted by using a solvent having a large amount of a low boiling point organic solvent that easily volatilizes. It is considered that this facilitates the discharge of the composition from the coater member and shortens the drying time of the solvent. The temporary adhesive composition of the present invention further promotes the discharge of the composition from the coater member by containing the silicone-based surfactant B having high wettability (affinity) with respect to the metal material. Conceivable.

Further, since the composition for temporary adhesion of the present invention contains a fluorine-based surfactant A that tends to be unevenly distributed on the surface of the layered composition, the surface activity on the surface of the composition after the composition is discharged from the coater member. The concentration of agent A increases. This is a state in which the surfactant B is likely to appear on the surface of the composition due to the wettability of the surfactant B to the metal material when the composition is in contact with the coater member. It is considered that when the substance is discharged from the coater member and comes into contact with the outside air, the surfactant A tends to appear on the surface of the composition due to the uneven distribution of the surfactant A. When the coating film dries to form a temporary adhesive layer, the presence of the surfactant A unevenly distributed near the surface of the temporary adhesive layer suppresses the adhesive force of the temporary adhesive layer and ensures appropriate peelability. To.

As described above, in the temporary bonding composition of the present invention, (a) the state of the solid-liquid interface of the composition when in contact with the coater member, and (b) the gas-liquid interface of the composition when in contact with the outside air. The state is dynamically adjusted before the coating film dries. In particular, in the temporary adhesive composition of the present invention, the ratio of the contents of the surfactant A and the surfactant B is set so as to satisfy the formula (1), and the uneven distribution and the interface of the surfactant A are set. It is considered that the above-mentioned interfacial behavior occurs when the wettability of the activator B with respect to the metal material is maintained in an appropriate balance.

From the above, it is presumed that even if the rectangular coating method is used, the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer can be sufficiently ensured.

<< Contact angle with stainless steel >>
The temporary bonding composition of the present invention (usually a liquid at 23 ° C.) preferably has a contact angle with respect to stainless steel (SUS304) of 50 degrees or less, more preferably 45 degrees or less, and more preferably 40 degrees. It is more preferably less than or equal to, and particularly preferably 35 degrees or less. As a result, the wettability of the device for carrying out the rectangular coating method with respect to the coater member is improved, and the discharge of the composition from the coater member is promoted.

Hereinafter, each component of the composition for temporary adhesion of the present invention will be described.

<< Elastomer >>
The composition of the present invention contains an elastomer. By containing the elastomer, it is possible to form a film such as a sheet having excellent adhesiveness by following fine irregularities of a carrier substrate or a device wafer and having an appropriate anchoring effect. Further, when the carrier substrate is peeled from the device wafer, the carrier substrate can be easily peeled from the device wafer without applying stress to the device wafer or the like, and damage or peeling of the device or the like on the device wafer can be prevented.

In addition, in this specification, an elastomer represents a polymer compound which shows elastic deformation. That is, it is defined as a polymer compound having a property of instantly deforming in response to an external force when an external force is applied and recovering its original shape in a short time when the external force is removed.

In the present invention, the elastomer can be deformed to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and 130% in a short time when the external force is removed. It is preferable to have the property of returning to the following.

In the present invention, the elastomer has a 5% heat mass reduction temperature raised from 25 ° C. to 20 ° C./min at 375 ° C. or higher, preferably 380 ° C. or higher, more preferably 390 ° C. or higher, and 400 ° C. or higher. Most preferred. The upper limit is not particularly limited, but is preferably 1000 ° C. or lower, more preferably 800 ° C. or lower, for example. According to this aspect, it is easy to form a film such as a sheet having excellent heat resistance. The mass reduction temperature is a value measured by a thermogravimetric measuring device (TGA) under a nitrogen stream under the above-mentioned temperature rising conditions. When the composition of the present invention contains two or more types of elastomers, it means a value in a mixture of two or more types of elastomers.

In the present invention, the glass transition temperature of the elastomer (hereinafter, also referred to as “Tg”) is preferably −50 to 300 ° C., more preferably 0 to 200 ° C. When Tg is within the above range, it has good followability to the surface of the device wafer at the time of bonding, and a film such as a sheet without voids can be formed. When the elastomer has two or more points of Tg, the value of Tg means the lower glass transition temperature.

In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and particularly preferably 50,000 to 100,000. Within this range, even when the carrier substrate is peeled from the device wafer and the residue derived from the elastomer remaining on the device wafer and / or the carrier substrate is removed, the solubility in the solvent is excellent, so that the device wafer and the carrier There are advantages such as no residue remaining on the substrate.

In the present invention, the elastomer includes an elastomer containing a repeating unit derived from styrene (polystyrene-based elastomer), a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacrylic elastomer, a silicone-based elastomer, and a polyimide-based elastomer. Etc. can be used. One or more selected from polystyrene-based elastomers, polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic elastomers, silicone-based elastomers, and polyimide-based elastomers is preferable, and from the viewpoint of solubility, heat resistance, and the like. Polystyrene elastomers are particularly preferred.

Further, the elastomer is preferably a hydrogenated product. In particular, a polystyrene-based elastomer hydrogenated product is preferable. When the elastomer is hydrogenated, it is easy to form a film such as a sheet having excellent heat resistance. Furthermore, it is easy to form a film such as a sheet having excellent peelability and cleaning / removing property after peeling. The above effect is remarkable when a polystyrene-based elastomer hydrogenated product is used. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.

The elastomer preferably contains the following polystyrene-based elastomer in an amount of 10 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass. % Is more preferably contained, and it is particularly preferable that the content is substantially composed of only a polystyrene-based elastomer. Further, among them, it is more preferable that the polystyrene-based elastomer hydrogenated product is contained in the above ratio.

<<< Polystyrene Elastomer >>>
In the present invention, the polystyrene-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene. Examples thereof include a copolymer (SBBS) and a hydrogenated product thereof, a styrene-ethylene-propylene-styrene block copolymer (SEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer and the like.

The content of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably 40% by mass or more, preferably 45% by mass or more, and more preferably 46% by mass or more. The upper limit can be, for example, 90% by mass or less, or 85% by mass or less.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer having a styrene block at one end or both ends, and a styrene block at both ends. It is particularly preferable that it is a block copolymer. If both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), the heat resistance is further improved. This is because the repeating unit derived from styrene, which has high heat resistance, is present at the end. In particular, since the styrene block is a reactive polystyrene-based hard block, it tends to be more excellent in heat resistance and chemical resistance, which is preferable. Further, it is considered that the phase separation between the hard block and the soft block is performed at 200 ° C. or higher by using an elastomer which is a block copolymer. The shape of the phase separation is considered to contribute to suppressing the occurrence of unevenness on the substrate surface of the device wafer. In addition, such elastomers are more preferred from the standpoint of solubility in solvents and resistance to resist solvents.

Further, when the polystyrene-based elastomer is hydrogenated, the stability against heat is improved, and deterioration such as decomposition and polymerization is unlikely to occur. Further, it is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.

In the present specification, the “styrene-derived repeating unit” is a styrene-derived structural unit contained in the polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene 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 1 to 5 carbon atoms, an acetoxy group, a carboxyl group and the like.

Commercially available products of polystyrene-based elastomers include, for example, Toughprene A, Toughprene 125, Toughprene 126S, Asaplen T, Asaplen T-411, Asaplen T-432, Asaplen T-437, Asaplen T-438, Asaplen T-439, and Toughtech H1272. , Tough Tech P1500, Tough Tech P5051, Tough Tech H1052, Tough Tech H1062, Tough Tech M1943, Tough Tech M1911, Tough Tech H1041, Tough Tech MP10, Tough Tech M1913, Tough Tech H1051, Tough Tech H1053, Tough Tech P2000, Tough Tech H1043 AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer 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 (Aron Kasei), 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 4271, Clayton D 4433, Clayton D 1170, Clayton D 1171, Clayton D 1173, Flex IR0307, Califrec SIR 0310, 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 D1191 , Clayton 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 G164 G1651, Clayton G1652, Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609, Clayton G4610 (manufactured by Kraton) TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5555, Dynaron 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8630P, Dynaron 8630P, Dynaron 8630P, Dynaron 8630P , Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P (manufactured by JSR Co., Ltd.), Denka STR series (manufactured by Denka 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 (manufactured by Mitsubishi Chemical Co., Ltd.), Septon S1001, Septon S8004, Septon S4033, Septon S2104, Septon S8007, Septon S2007, Septon S2004, Septon S2063, Septon HG252, Septon S8076, Septon S2002, Septon S1020, Septon S8104, Septon S2005, Septon S2006, Septon S4055, Septon S4044, Septon S4077, Septon S4099, Septon S8006, Septon V9461, Hybler 7311, Hybler 7125, Hybler 5127, Hybler 5127. These include Kuraray), Sumiflex (Sumitomo Bakelite Co., Ltd.), Leostomer, Actimer (RIKEN Vinyl Industry Co., Ltd.) and the like.

<<< Polyester Elastomer >>>
The polyester-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof can be mentioned.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids and adipines in which the hydrogen atom of these aromatic rings is substituted with a methyl group, an ethyl group, a phenyl group, or the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acids, sebacic acids and dodecanedicarboxylic acids, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acids. 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 benzene. Represents a direct bond (single bond) between rings. 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 polyester-based elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These may be used alone or in combination of two or more.

Further, as the polyester-based elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) moiety as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) moiety as a soft segment component shall be used. You can also. Examples of the multi-block copolymer include those of various grades depending on the type, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by Toray Dupont Co., Ltd.), Perplen (manufactured by Toyo Spinning Co., Ltd.), Primaloy (manufactured by Mitsubishi Chemical Corporation), Nouvellean (manufactured by Teijin Chemicals Ltd.), Esper 1612, 1620 (Hitachi Kasei Kogyo Co., Ltd.). Primaloy CP300 (manufactured by Mitsubishi Chemical Corporation) and the like.

<<< Polyolefin-based elastomer >>>
The polyolefin-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. 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. For example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like can be mentioned. Further, examples thereof include a copolymer of α-olefin and a non-conjugated diene having 4 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, etylidenenorbornene, butadiene and isoprene. Further, a carboxy-modified nitrile rubber obtained by copolymerizing a butadiene-acrylonitrile copolymer with methacrylic acid can be 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 Mirastomer (manufactured by Mitsui Chemicals, Inc.), Thermolan (manufactured by Mitsubishi Chemical Corporation), EXACT (manufactured by Exon Chemicals), ENGAGE (manufactured by Dow Chemicals), Esporex (manufactured by Sumitomo Chemicals), Sarlink (manufactured by Toyobo). (Manufactured by), Newcon (manufactured by Japan Polypropylene), EXCELINK (manufactured by JSR), etc.

<<< Polyurethane Elastomer >>>
The polyurethane-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an elastomer containing a structural unit of a hard segment composed of a small molecule glycol and a diisocyanate and a soft segment composed of a high molecular weight (long chain) diol and a diisocyanate can be mentioned.

Polymer (long chain) diols include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, and poly (1,6-he). 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 small molecule 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.
Commercially available polyurethane elastomers include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), Miractran (manufactured by Nippon Miractran), Elastolan (manufactured by BASF), Resamine (manufactured by Dainichiseika Kogyo), and Peresen (manufactured by Dainichiseika Kogyo). Dow Chemical), Iron Rubber (NOK), Mobilon (Nisshinbo Chemical), etc.

<<< Polyamide-based elastomer >>>
The polyamide-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an elastomer using a polyamide such as polyamide-6, 11 or 12 for a hard segment and a polyether such as polyoxyethylene, polyoxypropylene or polytetramethylene glycol and / or a polyester for a soft segment can be mentioned. 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 Elastoma, UBESTA XPA (manufactured by Ube Kosan Co., Ltd.), Daiamide (manufactured by Daiselhurus Co., Ltd.), PEBAX (manufactured by Toray Co., Ltd.), Grillon ELY (manufactured by Ms Japan Co., Ltd.), Novamid (manufactured by Mitsubishi Chemical Co., Ltd.), Grelak (manufactured by DIC Co., Ltd.), polyether ester amide PA-200, PA-201, TPAE-12, TPAE-32, polyesteramide TPAE-617, TPAE-617C ( (Made by T & K TOKA Co., Ltd.) and the like.

<<< Polyimide-based elastomer >>>
The polyimide-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a block polymer consisting of engineering plastics such as aromatic polyimide and rubber components such as polyethers, polyesters, and polyolefins, which are soft segments and have a molecular weight of several hundred to 1,000, is polycondensed with hard segments and soft segments alternately. It can be preferably used. Specific examples of commercially available products include UBESTA XPA9040F1 (manufactured by Ube Kosan Co., Ltd.).

<<< Polyacrylic Elastomer >>>
The polyacrylic elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those containing acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate as main components, and
Acrylic acid esters, glycidyl methacrylate, allyl glycidyl ether and the like can be mentioned. Further, those obtained by copolymerizing with a cross-linking point monomer such as acrylonitrile or ethylene can be mentioned. Specific examples thereof include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

<<< Silicone Elastomer >>>
The silicone-based elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the main component is organopolysiloxane, and examples thereof include polydimethylsiloxane-based, polymethylphenylsiloxane-based, and polydiphenylsiloxane. Specific examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (all manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

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

The composition of the present invention preferably contains an elastomer in a proportion of 25% by mass or more, more preferably 28% by mass or more, still more preferably 30% by mass or more. Since the composition of the present invention has good solubility of the elastomer, the concentration of the elastomer can be increased. By increasing the elastomer concentration of the composition, a film such as a thick sheet can be formed.

Further, it is preferable that 80% by mass or more of the total solid content of the composition of the present invention is an elastomer, and more preferably 85% by mass or more.

The elastomer may contain a plurality of the types listed above.

<< Organic Solvent >>
The composition for temporary adhesion of the present invention contains an organic solvent. The organic solvent contains a low boiling point organic solvent having a boiling point of 120 ° C. or lower at a ratio of 50 to 95% by mass with respect to the entire organic solvent. The content of the organic solvent is preferably 60 to 95% by mass with respect to the entire composition. The upper limit is more preferably 90% by mass or less, still more preferably 85% by mass or less. The lower limit is more preferably 65% by mass or more, still more preferably 70% by mass or more.

<<< Low boiling organic solvent with a boiling point of 120 ° C or less >>>
The boiling point (1 atm) of this low boiling point organic solvent is 120 ° C. or lower, preferably 110 ° C. or lower, and more preferably 105 ° C. or lower. The lower limit is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and even more preferably 70 ° C. or higher. Within this range, the drying property of the composition is good, and the drying time of the composition can be easily shortened. Furthermore, it is easy to form a good planar film in which uneven drying and uneven thickness are suppressed.

The SP value of the low boiling point organic solvent is preferably 19 (MPa) ^1/2 or less, and preferably 18.5 (MPa) ^1/2 or less. The lower limit is preferably, for example, 16.5 (MPa) ^1/2 or more. When the SP value of the solvent (C) is 19 (MPa) ^1/2 or less, the solubility of the elastomer can be further enhanced.

The low boiling point organic solvent preferably contains one or more selected from aliphatic hydrocarbons, ketones, esters, alcohols, aromatic hydrocarbons and cyclic ethers. Further, the low boiling point organic solvent preferably contains at least one of an aliphatic hydrocarbon and an aromatic hydrocarbon, and particularly preferably contains at least one of an alicyclic hydrocarbon and an aromatic hydrocarbon.

Examples of the alicyclic hydrocarbon include cyclohexane (boiling point 81 ° C.) and methylcyclohexane (boiling point 101 ° C.).

Examples of the aliphatic hydrocarbon other than the alicyclic hydrocarbon include hexane (boiling point 69 ° C.), heptane (boiling point 98 ° C.), and 2-methylpentane (boiling point 60 ° C.).

Examples of the ketone include methyl ethyl ketone (boiling point 80 ° C.) and methyl isobutyl ketone (boiling point 116 ° C.).

Examples of the ester include methyl acetate (boiling point 58 ° C.).

Examples of the alcohol include isopropyl alcohol (boiling point 83 ° C.), ethanol (boiling point 78 ° C.), methanol (boiling point 65 ° C.) and the like.

Examples of aromatic hydrocarbons include toluene (boiling point 111 ° C.) and benzene (boiling point 80 ° C.).

Examples of the cyclic ether include tetrahydrofuran (boiling point 66 ° C.) and the like.

The content of the low boiling point organic solvent is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, based on the total amount of the organic solvent. The content of the low boiling point organic solvent is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less with respect to the entire organic solvent. When the content of the low boiling point organic solvent is in the above range, the solubility and drying property of the elastomer are improved. The low boiling point organic solvent may contain one or more of those exemplified above, and when two or more of them are contained, the total amount thereof is preferably within the above range.

The composition of the present invention preferably contains a low boiling point organic solvent in the composition in a proportion of 5 to 65% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 60% by mass. When the content of the low boiling point organic solvent is within the above range, the solubility and drying property of the elastomer are good.

Further, it is more preferable that the composition for temporary adhesion of the present invention contains an aromatic compound as a low boiling point organic solvent or as an organic solvent other than the low boiling point organic solvent.

The aromatic compound is preferably, for example, an aromatic hydrocarbon having an alkyl group, and more preferably a compound having a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms.

The alkyl group constituting the aromatic hydrocarbon solvent having an alkyl group used in the present invention is a linear, branched or cyclic alkyl group, and a linear or branched alkyl group is preferable. The number of carbon atoms constituting the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

The aromatic hydrocarbon solvent having an alkyl group used in the present invention is preferably a solvent having a benzene ring and 1 to 3 alkyl groups having 1 to 10 carbon atoms, and is represented by the following formula (X). It is more preferable that it is a solvent.
Equation (X)

In the above formula (X), R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.

R is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group or a tert-butyl group. Further, the total number of carbon atoms constituting R is preferably an integer of 2 to 5, and more preferably 3 or 4.

The boiling point of the aromatic hydrocarbon solvent having an alkyl group used in the present invention is preferably 50 to 250 ° C, more preferably 80 to 200 ° C, still more preferably 120 to 170 ° C. The compound having a boiling point of 120 ° C. or lower can also be used as the low boiling point organic solvent of the present invention.

Specific examples of the aromatic hydrocarbon-based solvent having an alkyl group used in the present invention include toluene, xylene, and trimethylbenzene (preferably 1,3,5-trimethylbenzene (mesitylene)), 1,2,4-trimethylbenzene. (Pseudocumen)), ethylbenzene, propylbenzene, 1-methylethylbenzene, butylbenzene (preferably n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, more preferably tert-butylbenzene), amyl Benzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2- Ethyltoluene, 1,2-diethylbenzene, o-simene (2-isopropyltoluene), 3-ethyltoluene, m-simene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-simene, 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-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and the like can be mentioned.

The aromatic hydrocarbon solvent having an alkyl group is preferably at least one of toluene, xylene, trimethylbenzene (preferably mesitylene), butylbenzene (preferably tert-butylbenzene) and diethylbenzene, and more preferably. Is xylene and at least one of trimethylbenzene and butylbenzene.

The content of the aromatic hydrocarbon solvent is preferably 5 to 100% by mass, more preferably 10 to 90% by mass, still more preferably 20 to 80% by mass, based on the total amount of the organic solvent. When the content of the aromatic hydrocarbon solvent is in the above range, the solubility, tackiness, and drying property of the elastomer are further improved.

In particular, the aromatic hydrocarbon solvent is preferably a solvent having a boiling point of 160 ° C. or higher among the above. Aromatic hydrocarbon solvents having a boiling point of 160 ° C. or higher include, for example, mesitylene (boiling point 165 ° C.), p-diisopropylbenzene (boiling point 210 ° C.), p-diisopropylbenzene (boiling point 181 ° C.), m-diethylbenzene (boiling point 182 ° C.). ), 1,3,5-triethylbenzene (boiling point 218 ° C.) and the like.

The content of the aromatic hydrocarbon solvent having a boiling point of 160 ° C. or higher is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and 40 to 70% by mass with respect to the entire organic solvent. Is more preferable. This makes it easy to adjust the dryness. In addition, the aspect of drying property is expanded as a whole solvent, and the range of preparation of the composition for temporary adhesion is also expanded.

The aromatic hydrocarbon solvent may contain one or more of those exemplified above, and when two or more of them are contained, the total amount thereof is preferably within the above range.

<< Surfactant >>
The composition for temporary adhesion of the present invention contains a fluorine-based surfactant A and a silicone-based surfactant B. Then, the composition of the present invention satisfies the formula (1) for the surfactant A and the surfactant B.

_WA / _WB = 1.5-5 formula (1);
In the formula (1), WA represents the content of the surfactant _A with respect to the entire surfactant in terms of mass%, and WB represents the content of the surfactant _B with respect to the entire surfactant in terms of mass%. Represents a quantity. The upper limit of the numerical range of _WA / _WB is preferably 4.5 or less, more preferably 4.3 or less, still more preferably 4.0 or less, and even more preferably 3.5. It is less than or equal to, and particularly preferably 3.0 or less. The lower limit is preferably 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more, still more preferably 1.9 or more, and particularly preferably 2.0. That is all.

In the present invention, the composition contains both the surfactant A and the surfactant B in a predetermined ratio, so that the coater member can be used to apply the composition (particularly in the coater member). (Fluidity after discharging from the coater member, etc.) is improved. As a result, the uniformity of the coating film and the film after drying and the liquid saving property are further improved.

Further, it is more preferable that the composition for temporary adhesion of the present invention satisfies the formula (3) with respect to the surfactant and the organic solvent.

W _ALL / _WS = 0.000002 to 0.006 equation (3);
In the formula (3), _WALL represents the content of the entire surfactant with respect to the entire composition in terms of mass%, and _WS represents the content of the entire organic solvent in terms of mass% with respect to the entire composition. .. The upper limit of the numerical range of W _ALL / _WS is preferably 0.005 or less, more preferably 0.002 or less, still more preferably 0.001 or less, still more preferably 0.0005. It is less than or equal to, and particularly preferably 0.0002 or less. The lower limit is preferably 0.000005 or more, more preferably 0.000007 or more, further preferably 0.00001 or more, still more preferably 0.00002 or more, and particularly preferably 0.00005 or more. That is all.

The content of the surfactant with respect to the entire composition (that is, WALL) is preferably _0.00002 to 2% by mass. The upper limit is more preferably 0.1% by mass or less, further preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less. The lower limit is more preferably 0.001% by mass or more, further preferably 0.005% by mass or more, and particularly preferably 0.007% by mass or more.

<<< Fluorine Surfactant A >>>
The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass. Here, the fluorine content is the ratio of the mass of all fluorine atoms to the molecular weight. Regarding the fluorine content, the upper limit is more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The lower limit is more preferably 5% by mass or more, and particularly preferably 7% by mass or more. The surfactant A having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving property, and also has good peelability of the temporary adhesive layer.

The fluorine-based surfactant A is not particularly limited, but a fluorine-based surfactant that does not contain perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS) is preferable. Examples of the fluorine-based surfactant A that can be used in the present invention include commercially available products, Megafuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. , F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Co., Ltd.), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, AG7000, AG950, AG7600, Surfron S-112, S-113, S-131, S-141, S-145, S-381, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, same SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF301, EF303, EF351, EF352, EF801, EF802 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surfactant 250 (manufactured by Neos Co., Ltd.) Can be mentioned. In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like can be mentioned.

The content of the fluorine-based surfactant in the temporary bonding composition used in the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0, based on the entire composition. It is .003% by mass or more, and particularly preferably 0.004% by mass or more. The upper limit of this content is preferably 0.5% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably 0.008% by mass or less. be. The content of the fluorine-based surfactant is preferably 0.001 to 1.0% by mass with respect to the total solid content of the temporary bonding composition. The lower limit of this content 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 even more preferably 0.009% by mass or more. The upper limit of this content is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, further preferably 0.3% by mass or less, further preferably 0.15% by mass or less, and 0.09. Mass% or less is even more preferable. The content of the fluorine-based surfactant is preferably 0.01 to 99.99% by mass with respect to the total amount of the surfactant. The lower limit of the content is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more. The upper limit of this content is more preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 70% by mass or less.

When two or more types are used in combination, the total content is preferably within the above range.

<<< Silicone Surfactant B >>>
The composition for temporary adhesion used in the present invention contains a silicone-based surfactant. The silicone-based surfactant acts as a mold release agent, and the temporary adhesive layer can be easily removed from the substrate to be processed.

Examples of the silicone-based surfactant include compounds containing Si—O bonds, such as silicone oil, silane coupling agent, silicone resin, silicone rubber, and cyclic siloxane, and silicone oil is preferable.

Further, it is preferable that the silicone-based surfactant does not contain a reactive group such as a polymerizable group.

The silicone-based surfactant is preferably a polyether-modified silicone.

The ratio of the polyether-modified silicone used in the present invention is 80% or more represented by the formula (A).

Equation (A) {(MO + EO) / AO} x 100
In the above formula (A), MO is the mol% of the methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of the ethylene oxide contained in the polyether structure in the polyether-modified silicone. AO refers to the mol% of the 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, still more preferably 99% or more. , 100% is even more preferable.

The weight average molecular weight of the polyether-modified silicone is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 40,000.

In the present invention, the polyether-modified silicone heats the polyether-modified silicone from 20 ° C. to 280 ° C. at a heating rate of 20 ° C./min under a nitrogen stream of 60 mL / min, and heats the polyether-modified silicone at a temperature of 280 ° C. for 30 minutes. It is preferable that the mass reduction rate when held is 50% by mass or less. By using such a compound, the surface texture after processing of the substrate accompanied by heating is 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, still more preferably 30% by mass or less. The lower limit of the mass reduction rate of the above-mentioned polyether-modified silicone may be 0% by mass, but 15% by mass or more, further 20% by mass or more is sufficiently a practical level.

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 specified, but even if it is 1.400 or more, it is a sufficiently practical level.

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).

Equation (101)

In the above formula (101), R ¹¹ and R ¹⁶ are independently substituents, R ¹² and R ¹⁴ are independently divalent linking groups, 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 independently numbers of 0 to 20, and x1 and y1 are independently numbers of 2 to 100, respectively.
Equation (102)

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are independent substituents, R ²² is a divalent linking group, and R ²³ is a hydrogen atom or 1 to 5 carbon atoms. M2 and n2 are each independently a number of 0 to 20, and x2 is a number of 2 to 100.

Equation (103)

In the above formula (103), R ³¹ and R ³⁶ are independently substituents, R ³² and R ³⁴ are independently divalent linking groups, 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 independently numbers of 0 to 20, and x3 is a number of 2 to 100.

Equation (104)

In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are independent substituents, 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 independently numbers of 0 to 20, and x4 and y4 are independently numbers of 2 to 100, respectively.

In the above formula (101), R ¹¹ and R ¹⁶ are independent substituents, and an alkyl group or a phenyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable.

In the above formula (101), R ¹² and R ¹⁴ are independently divalent linking groups, and are a carbonyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, and 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 the formula (101), R ¹³ and R ¹⁵ are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. Alkyl groups are more preferred.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are independent substituents and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferred range is also the same.

In the above formula (102), R ²² is a divalent linking group, which is synonymous with R ¹² in the formula (101), and the preferable 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, which 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 independent substituents and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferable range is also the same.

In the above formula (103), R ³² and R ³⁴ are independently divalent linking groups and have the same meaning as R ¹² in the formula (101), and the preferable range is also the same.

In the above formula (103), R ³³ and R ³⁵ are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, which are synonymous with R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are independent substituents and are synonymous with R ¹¹ and R ¹⁶ in the formula (101). The preferred range is similar.

In the above formula (104), R ⁴⁷ is a divalent linking group, which is synonymous with R ¹² in the formula (101), and the preferable 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, which is synonymous with R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

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

The content of the polyoxyalkylene group in the molecule of the polyether-modified silicone used in the present invention is not particularly limited, but it is desirable that the content of the polyoxyalkylene group exceeds 1% by mass in the total molecular weight.

The content of the polyoxyalkylene group is defined by "{(formula amount of polyoxyalkylene group in one molecule) / molecular weight of one molecule} x 100".

Examples of the silane coupling agent include a fluorine atom-containing silane coupling agent, and triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane is preferable.

Further, examples of the silane coupling agent include JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and JP-A. 63-034540, 07-230165, 08-062834, 09-054432, 09-005988, 2001-330953, respectively. Surfactants are also mentioned and these descriptions are incorporated herein.

As the silicone-based surfactant used in the present invention, a commercially available product can also be used.

For example, "ADVALON FA33", "FLUID L03", "FLUID L033", "FLUID L051", "FLUID L053", "FLUID L060", "FLUID L066", "IM22", "WACKER-Belsil DMC 6038" (or more). , Asahi Kasei Wacker Silicone Co., Ltd.), "KF-352A", "KF-353", "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-22-4952 "(all manufactured by Shin-Etsu Chemical Co., Ltd.), "8526 ADDITION", "FZ-2203", "FZ-5609", "L-7001", "SF 8410", "2501 COSMETIC WAX", "5200 FORMURATION AID", "57 ADDITION", "8019 ADDITION", "8029 ADDITION", "8054 ADDITIVE", "BY16-066", "BY16-201", "ES-5612 FORMULATION AID", "FZ-2104", "FZ-2108", "FZ-2123", "FZ" -1622", "FZ-2164", "FZ-2191", "FZ-2207", "FZ-2208", "FZ-2222", "FZ-7001", "FZ-77", "L-7002" , "L-7604", "SF8427", "SF8428", "SH 28 PAINR ADDITION", "SH3749", "SH3773M", "SH8400", "SH8700" (all manufactured by Toray Dow Corning Co., Ltd.) , "BYK-37 8 ”,“ BYK-302 ”,“ BYK-307 ”,“ BYK-331 ”,“ BYK-345 ”,“ BYK-B ”,“ BYK-347 ”,“ BYK-348 ”,“ BYK-349 ” , "BYK-377" (all manufactured by Big Chemie Japan Co., Ltd.), "Silwet L-7001", "Silwet L-7002", "Silwet L-720", "Silwet L-7200", "Silwet L- 7210 "," Silwet L-7220 "," Silwet L-7230 "," Silwet L-7605 "," TSF4445 "," 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-7607", "Silwet L-7607" L-7608 ”,“ Silwet L-7622 ”,“ Silwet L-7650 ”,“ Silwet L-7657 ”,“ Silwet L-77 ”,“ Silwet L-8500 ”,“ Silwet L-8610 ”,“ TSF4440 ” , "TSF4441", "TSF4450", "TSF4460" (all manufactured by Momentive Performance Materials Japan GK) are exemplified.

The silicone-based surfactants include the trade names "BYK-300", "BYK-306", "BYK-310", "BYK-315", "BYK-313", "BYK-320", and "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" Made by Co., Ltd.), Product names "AC FS 180", "AC FS 360", "AC S 20" (all manufactured by Algin Chemie), Product names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow" KL-401 "," Polyflow KL-402 "," Polyflow KL-403 "," Polyflow KL-404 "," Polyflow KL-700 "(all manufactured by Kyoeisha Chemical Co., Ltd.), trade name" 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-651 ”,“ KP-390 ”,“ KP-391 ” , "KP-392" (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade names "LP-7001", "LP-7002", "8032 ADDITIVE", "FZ-2110", "FZ-2105", " 67 ADDITIVE ”,“ 8618 ADDITIVE ”,“ 3 ADDITIVE ”,“ 56 ADDITIVE ”(above, manufactured by Toray Dow Corning Co., Ltd.),“ TEGO WET 270 ”(manufactured by Evonik Degussa Japan Co., Ltd.),“ NBX -15 "(manufactured by Neos Co., Ltd.) and the like can also be used.

The content of the silicone-based surfactant in the temporary adhesive composition used in the present invention is preferably 0.00005% by mass or more, more preferably 0.0001% by mass or more, still more preferably 0, based on the entire composition. It is 0005% by mass or more, and particularly preferably 0.001% by mass or more. The upper limit of this content is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably 0. It is 005% by mass or less. The content of the silicone-based surfactant is preferably 0.001 to 1.0% by mass with respect to the total solid content of the temporary adhesive composition. The lower limit of this content 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 even more preferably 0.009% by mass or more. The upper limit of this content is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, further preferably 0.3% by mass or less, further preferably 0.15% by mass or less, and 0.09. Mass% or less is even more preferable. The content of the silicone-based surfactant is preferably 0.01 to 99.99% by mass with respect to the total amount of the surfactant. The lower limit of the content is more preferably 0.015% by mass or more, further preferably 0.02% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit of this content is more preferably 90% by mass or less, further preferably 80% by mass or less, particularly preferably 50% by mass or less, and most preferably 40% by mass or less.

The composition for temporary adhesion used in the present invention may contain only one type of silicone-based surfactant, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

<<< Acetylene-based surfactant C >>>
The composition for temporary adhesion of the present invention may contain an acetylene-based surfactant C (surfactant containing an acetylene group). Since the composition for temporary adhesion contains an acetylene-based surfactant, it has the effects of defoaming, defoaming and defoaming. It is considered that this is because the hydrophobic acetylene-based surfactant spreads on the surface of the foam and destabilizes the foam.

The acetylene-based surfactant may contain an acetylene group in the molecule. The number of acetylene groups in the molecule is not particularly limited, but 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 1 to 2 is further preferable. The molecular weight of the acetylene-based surfactant is preferably relatively small, preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. There is no particular lower limit, but it is practical that it is 200 or more.

The acetylene-based surfactant is preferably a compound represented by the following formula (9).

In the formula, R ⁹¹ and R ⁹² are independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. .. The aromatic heterocyclic group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.

R ⁹¹ and R ⁹² may each independently have a substituent, and examples of the substituent include the above-mentioned substituent T.

The compound of the formula (9) is preferably represented by the following formula (91).

R ⁹³ to R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. It is an integer, m10 is an integer twice n10, and l9 and l10 are independently numbers of 0 or more and 12 or less. R ⁹³ to R ⁹⁶ are hydrocarbon groups, and among them, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkenyl group (2 to 12 carbon atoms are preferable). Preferably, 2 to 6 are more preferable, 2 to 3 are more preferable), an alkynyl group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, 2 to 3 are more preferable), and an aryl group (6 to 6 carbon atoms is more preferable). 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable). .. The alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched. R ⁹³ to R ⁹⁶ may have a substituent T as long as the effect of the present invention is exhibited. Further, R ⁹³ to R ⁹⁶ may be bonded to each other or form a ring via a linking group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L to form a ring.

R ⁹³ and R ⁹⁴ are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). Of these, the methyl group is preferable.

R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms). Of these, − (C _n11 R ⁹⁸ _m11 ) -R ⁹⁷ is preferable. Here, R ⁹⁷ and R ⁹⁸ are each independently preferably a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). n11 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m11 is twice the number of n11.

R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.

n9 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m9 is an integer that is twice n9.

n10 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m10 is an integer that is twice n10.

l9 and l10 are independently numbers from 0 to 12. However, l9 + l10 is preferably a number of 0 to 12, more preferably a number of 0 to 8, further preferably a number of 0 to 6, further preferably a number of more than 0 and less than 6, and more than 0 and 3 or less. The number of is even more preferable. Regarding l9 and l10, the compound of the formula (91) may be a mixture of compounds different in the number, in which case the number of l9 and l10, or l9 + l10 is the number including the decimal point. You may.

The surfactant represented by the formula (91) is preferably the surfactant represented by the following formula (92).

R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less. Among them, R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). 2, 6 is more preferable, 2 to 3 is more preferable), an alkynyl group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, 2 to 3 is more preferable), and an aryl group (6 to 22 carbon atoms is more preferable). Is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable). The alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may have a substituent T as long as the effects of the present invention are exhibited. Further, R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or form a ring via a linking group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L to form a ring.

It is preferable that R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are each independently an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). Of these, the methyl group is preferable.

l11 + l12 is preferably a number of 0 to 12, more preferably a number of 0 to 8, even more preferably a number of 0 to 6, even more preferably a number of more than 0 and less than 6, and a number of more than 0 and 5 or less. Is even more preferable, and a number of more than 0 and 4 or less is even more preferable, and a number of more than 0 and 3 or less may be used, or a number of more than 0 and 1 or less may be used. In addition, in l11 and l12, the compound of the formula (92) may be a mixture of compounds different in the number, in which case the number of l11 and l12, or l11 + l12 is the number including the decimal point. May be good.

As acetylene-based surfactants, the following Surfynol 104 series (trade name, Nisshin Kagaku Kogyo Co., Ltd.), the following Acetyrenol E00, E40, E13T, 60 (all trade names) , Kawaken Fine Chemicals Co., Ltd.), among which Surfinol 104 series, acetylenol E00, E40 and E13T are preferable, and acetylenol E40 and E13T are more preferable. The Surfinol 104 series and acetylenol E00 are surfactants having the same structure.

In the composition for temporary adhesion, the content of the surfactant containing an acetylene group is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, still more preferably 0. It is 001% by mass or more, and particularly preferably 0.002% by mass or more. The upper limit of this content is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably 0.005% by mass or less. be. The content of the surfactant containing an acetylene group is preferably 0.005% by mass or more, more preferably 0.007% by mass or more, still more preferably 0.01, based on the total solid content of the composition for temporary adhesion. It is mass% or more. The upper limit of this content is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. The content of the acetylene-based surfactant is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on the total amount of the surfactant. The upper limit of this content is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, and particularly preferably 40% by mass or less. As the acetylene-based surfactant, one type or a plurality of acetylene-based surfactants may be used. When a plurality of items are used, it is preferable that the total amount thereof is within the above range.

When two or more types are used in combination, the total content is preferably within the above range.

Further, the temporary adhesive composition preferably satisfies the formula (2) with respect to the acetylene-based surfactant C and the silicone-based surfactant B.

_WC / _WB = 0.005 to 500 formula (2)
In the formula (2), WC represents the content of the acetylene-based surfactant _C with respect to the entire surfactant in terms of mass%. The upper limit of the numerical range of _WC / _WB is preferably 100 or less, more preferably 50 or less, still more preferably 10 or less, and particularly preferably 5 or less. The lower limit is preferably 0.006 or more, more preferably 0.01 or more, and further preferably 0.05 or more.

When the temporary adhesive composition satisfies the above formula (2), there is an effect that coating defects caused by bubbles generated during coating are reduced.

<<< Other Surfactants >>>
The composition for temporary adhesion of the present invention may further contain a surfactant other than the surfactants A to C as the surfactant. Such surfactants include, for example, various surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants.

Further, the composition for temporary adhesion of the present invention may have a structure that does not substantially contain a surfactant other than the surfactants A to C. Here, "substantially free" means that the content of the surfactant other than the surfactants A to C is 1% by mass or less with respect to the total amount of the surfactant.

<< Other additives >>
Further, in order to improve the physical properties of the temporary adhesive layer, the composition for temporary adhesion of the present invention is, for example, an antioxidant, a plasticizer, a filler, an adhesion accelerator, an ultraviolet absorber, and a dispersant, if necessary. It may contain a known additive such as.

<<< Antioxidant >>>
The composition for temporary adhesion of 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 phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035 (all manufactured by BASF Japan Ltd.), Sumilizer MDP-. Examples thereof include S and Sumilizer GA-80 (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, Sumilizer TPL-R, Sumilizer TPM, Sumilizer TPS, Sumilizer MB, Sumitomo Chemical Co., Ltd., etc. Can be mentioned.

Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol). Phenylphosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, Irgafos168, Irgafos38 (above, manufactured by BASF Japan Co., Ltd.), Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned. ..

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

Examples of the amine-based antioxidant include dimethylaniline and phenothiazine.

As the antioxidant, Irganox1010, Irganox1330, 3,3'-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox1010 and Irganox1330 are more preferable, and Irganox1010 is particularly preferable.

Further, among the above-mentioned antioxidants, it is preferable to use a phenol-based antioxidant in combination with a sulfur-based antioxidant or a phosphorus-based antioxidant, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. Is most preferable. 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 making such a combination, it can be expected that the deterioration of the temporary adhesive composition due to the oxidation reaction can be efficiently suppressed. When a phenol-based antioxidant and a sulfur-based antioxidant are used in combination, the mass ratio of the phenol-based antioxidant and the sulfur-based antioxidant is the phenol-based antioxidant: sulfur-based 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, Sumilizer GA-80 and Sumilizer TP-D are preferable, and Irganox 1010 and Sumilizer TP-D, Irganox 1010 and Sumilizer TP-D, Ir. More preferred, Irganox 1010 and Sumilizer TP-D are particularly preferred.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

When the composition for temporary adhesion contains an antioxidant, the content of the antioxidant may be contained in a ratio of 0.001 to 20.0% by mass with respect to the total solid content of the composition for temporary adhesion. It is preferably contained in a proportion of 0.005 to 10.0% by mass, more preferably.

Only one type of antioxidant may be used, or two or more types may be used. When there are two or more kinds of antioxidants, it is preferable that the total is in the above range.

<<< Plasticizer >>>
The temporary adhesive composition used in the present invention may contain a plasticizer, if necessary. By blending a plasticizer, a temporary adhesive layer satisfying the above-mentioned various performances can be obtained.

As the plasticizer, phthalates, fatty acid esters, aromatic polyvalent carboxylic acid esters, polyesters and the like can be used.

Examples of phthalates include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical Industry Co., Ltd.), PL-200, DOIP (above, manufactured by CGG Ester Co., Ltd.). ), Sun Associate DUP (manufactured by Shin Nihon 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 (all manufactured by NOF CORPORATION), and DBA. , DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (all manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

As aromatic polyvalent carboxylic acid esters, TOTM (manufactured by Daihachi Chemical Industry Co., Ltd.), Monosizer W-705 (manufactured by Daihachi Chemical Industry Co., Ltd.), UL-80, UL-100 (manufactured by ADEKA Corporation) Made) and so on.

Examples of the polyester include Polysizer TD-1720, Polysizer S-2002, Polysizer S-2010 (all manufactured by DIC Corporation), BAA-15 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

Among the above-mentioned plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL, and Polysizer 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 temperature at which the weight of the plasticizer decreases by 1% by mass when the weight change is measured under a nitrogen flow and a constant rate of temperature increase of 20 ° C./min. The temperature 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 specified, but may be, for example, 500 ° C. or lower.

The amount of the plasticizer added is preferably 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 2.% of the total solid content of the temporary adhesive composition. It is 0% by mass.

<Preparation of composition>
The composition for temporary adhesion of the present invention can be prepared by mixing each of the above-mentioned components. Mixing of each component is usually carried out in the range of 0 ° C to 100 ° C. Further, it is preferable to mix each component and then filter, for example, with a filter. Filtration may be performed in multiple stages or may be repeated many times. It is also possible to refilter the filtered liquid.

The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. Examples thereof include a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon 6, nylon 6 and 6, and a polyolefin resin such as polyethylene and polypropylene (PP). Among these materials, polypropylene and nylon are preferable.

The pore diameter of the filter is suitable, for example, about 0.003 to 5.0 μm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the composition 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 twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent filters are the same or smaller than the pore diameter of the first filtering. Further, a plurality of first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As the commercially available filter, for example, it can be selected from various filters provided by Nippon Paul Co., Ltd., Advantech Toyo Co., Ltd., Entegris Japan Co., Ltd., KITZ Micro Filter Co., Ltd., and the like.

<Formation of temporary adhesive layer>
The temporary adhesive layer is preferably formed by a method of applying the temporary adhesive composition onto a rectangular substrate by, for example, a rectangular coating method such as a slit coating method or a bar coating method. In particular, since the composition for temporary adhesion of the present invention is excellent in wettability to stainless steel and tackiness of the composition, it can be efficiently applied to a rectangular area without causing unnecessary dripping.

<Laminate and kit>
The laminated body of the present invention is a laminated body including a rectangular substrate and a temporary adhesive layer formed by using the temporary adhesive composition of the present invention. Further, the kit of the present invention is a kit including a rectangular substrate and the composition for temporary adhesion of the present invention. In the present invention, the rectangular substrate is not particularly limited as long as it is a substrate within a range that can be generally handled as a rectangle. The rectangular substrate is, for example, a rectangular substrate in which each internal angle is within the range of 90 degrees ± 10 degrees, and the corners may be rounded.

The size of the rectangular substrate is preferably 100 to 4000 mm on a side, and the thickness is preferably 0.7 to 7 mm, for example. The material of the rectangular substrate is, for example, silicon, glass, compound semiconductors such as SiC, GaN, and GaAs, and mold resins. Further, the rectangular substrate may be a substrate to be processed such as a device wafer having a structure formed on the surface and the inside thereof, or may be a carrier substrate for supporting the substrate to be processed. As described above, since the temporary adhesive composition of the present invention is a composition suitable for the rectangular coating method, the temporary adhesive layer can be easily formed on the rectangular substrate.

The temporary bonding composition of the present invention may be used for methods other than the rectangular coating method, such as a spin coating method and a dipping method.

As described above, the temporary adhesive layer is formed on at least one surface of the substrate to be processed and the carrier substrate. That is, a temporary adhesive layer may be formed on only one of these and bonded to the other, or both of them may be provided with a temporary adhesive layer and bonded to each other.

Next, since the composition for temporary adhesion usually contains a solvent, it is heated to volatilize the solvent. The heating temperature is preferably higher than the boiling point of the solvent, more preferably 110 ° C. or higher, further preferably 130 ° C. to 200 ° C., and particularly preferably 160 ° C. to 190 ° C.

<Manufacturing method of laminates and semiconductor devices>
In the method for manufacturing a semiconductor device using the temporary adhesive composition of the present invention (also referred to as "temporary adhesive"), the temporary adhesive of the present invention is used as a cleaning agent (for example, an acid or a base and an organic solvent). Includes.) Is included. With such a configuration, the temporary adhesive layer can be effectively removed.

In the step of removing the temporary adhesive layer, in order to effectively remove the residue, it is preferable to wash with the following cleaning agent A and then with the following cleaning agent B. The cleaning agent A contains at least one organic acid whose acid group contains a sulfur atom or a phosphorus atom, and an organic solvent. With such a configuration, the residue derived from the silicon-containing compound can be effectively removed, and the peeling of the layer to be laminated thereafter can be effectively suppressed. Detergent B contains an organic carboxylic acid compound and at least one solvent consisting of water and a water-soluble solvent. With such a configuration, the residue derived from the organic acid in the detergent A can be effectively removed.

As a mode for removing the temporary adhesive, the temporary adhesive layer on the work substrate such as a device wafer is removed, and the excess temporary adhesive in the process of temporarily adhering the work substrate and the carrier substrate is removed. , And removing the temporary adhesive remaining on the carrier substrate for reuse of the carrier substrate is exemplified.

<< First Embodiment >>
Hereinafter, an embodiment of a method for manufacturing a semiconductor device will be described with reference to FIG. The present invention is not limited to the following embodiments.

3A to 3E are schematic cross-sectional views (FIGS. 3A and 3B) illustrating temporary adhesion between the rectangular carrier substrate and the device wafer, respectively, and are temporarily adhered to the carrier substrate. A state in which the device wafer is thinned (FIG. 3 (C)), a state in which the carrier substrate and the device wafer are peeled off (FIG. 3 (D)), and a state after the temporary adhesive layer is removed from the device wafer (FIG. 3 (E). )) Is a schematic cross-sectional view showing.

In this embodiment, as shown in FIG. 3A, first, an adhesive carrier substrate 100 in which the temporary adhesive layer 11 is provided on the carrier substrate 12 is prepared.

The temporary adhesive layer 11 is formed by using the temporary adhesive of the present invention. The device wafer 60 is provided with a plurality of device chips 62 on the surface 61a of the silicon substrate 61.

The thickness of the silicon substrate 61 is preferably 200 to 1200 μm, for example. The device chip 62 is preferably, for example, a metal structure, and the height is preferably 10 to 100 μm.

In the process of forming the temporary adhesive layer 11, the back surface and the end surface of the carrier substrate 12 and the device wafer 60 are cleaned with a cleaning agent A, a cleaning agent B, a stripping solution or an organic solvent (hereinafter, also referred to as “cleaning agent or the like”). A cleaning step may be provided. Specifically, by removing the residue of the temporary adhesive layer adhering to the end surface or the back surface of the carrier substrate or the device wafer with a cleaning agent or the like, contamination of the device can be prevented, and the TTV of the thin device wafer can be prevented. (Total Tickness Variation) can be reduced. Here, the stripping liquid is a composition for removing the temporary adhesive layer, and refers to, for example, a relatively weakly acidic composition in which an acid, a base, a surfactant, or the like is added to water or an organic solvent.

Next, as shown in FIG. 3B, the adhesive carrier substrate 100 and the device wafer 60 are crimped to temporarily bond the carrier substrate 12 and the device wafer 60.

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 fact that the temporary adhesive layer 11 completely covers the device chip 62 is effective when it is desired to further reduce the TTV of the thinning device wafer (that is, when it is desired to further improve the flatness of the thinning device wafer). ..

That is, when the device wafer is thinned, by protecting the plurality of device chips 62 with the temporary adhesive layer 11, 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 thinning device wafer is reduced, and as a result, the finally obtained thinness is reduced. The TTV of the 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 (for example, but not limited to, grinding, chemical mechanical polishing (CMP), or the like to reduce the thickness of the film. Treatment, treatment under high temperature and vacuum such as chemical vapor deposition (CVD) and physical vapor deposition (PVD), treatment with chemicals such as organic solvent, acidic treatment liquid and basic treatment liquid, plating treatment, activity. Irradiation of light, heat treatment, cooling treatment, etc.). In FIG. 3C, the thickness of the silicon substrate 61 is reduced (for example, the thickness is reduced to the above-mentioned thickness) to obtain a thin device wafer 60a.

Even if a step of cleaning the temporary adhesive layer protruding outside the area of the substrate surface of the device wafer with a cleaning agent or the like is provided at the stage after thinning the device wafer and before processing under high temperature and vacuum. good. Specifically, after thinning the device wafer, the temporary adhesive layer that protrudes is removed by using a cleaning agent or the like, so that the temporary adhesive layer is directly treated at high temperature and under vacuum. It is possible to prevent deformation and deterioration of the adhesive layer.

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 width of the substrate surface of the carrier substrate is C μm, the width of the substrate surface of the device wafer is D μm, and the width of the film surface of the temporary adhesive layer is T μm, (C-200) ≧ T ≧ D. It is more preferable to meet. Further, the width of the substrate surface of the carrier substrate is C μm, the width of the substrate surface of the device wafer is D μm, the width of the film surface on the side in contact with the carrier substrate of the temporary adhesive layer is _TC μm, and the device wafer of the temporary adhesive layer. When the width of the film surface on the contacting side is T _D μm, it is preferable to satisfy (C-200) ≧ _TC > T _D ≧ D. With such a configuration, it is possible to further suppress deformation and deterioration of the temporary adhesive layer due to the treatment under high temperature and vacuum directly applied to the temporary adhesive layer.

The area of the film surface of the temporary adhesive layer means the 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, the surface corresponding to the surface 61a in FIG. 3, and is the surface on the side where the device chip is provided. The width of the film surface of the temporary adhesive layer is also considered in the same manner.

The width T of the film surface of the temporary adhesive layer is _TC μm for the width of the film surface on the side in contact with the carrier substrate of the temporary adhesive layer, and the film surface on the side in contact with the device wafer of the temporary adhesive layer. When the width is T _D μm, T = ( _TC + T _D ) / 2. The width of the substrate surface of the carrier substrate and the width of the substrate surface of the device wafer refer to the width of the surface on the side in contact with the temporary adhesive layer. Further, in the above inequality, the corresponding widths are compared when they are pasted together.

Further, as a mechanical or chemical treatment, after the thinning treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thinning device wafer 60a, and a through silicon via is formed in the through hole. A process for forming (not shown) may be performed.

Further, after the carrier substrate 12 and the device wafer 60 are temporarily bonded, heat treatment may be performed before the carrier substrate 12 is peeled off. As an example of heat treatment, heating may be performed when performing mechanical or chemical treatment.

The maximum temperature reached in the heat treatment is preferably 80 to 400 ° C, more preferably 130 ° C to 400 ° C, still more preferably 180 ° C to 350 ° C. The maximum temperature reached in the heat treatment is preferably a temperature lower than the decomposition temperature of the temporary adhesive layer. The heat treatment is preferably heating at the maximum temperature reached for 30 seconds to 30 minutes, more preferably 1 minute to 10 minutes at the maximum temperature reached.

Next, as shown in FIG. 3D, the carrier substrate 12 is peeled off from the thinning device wafer 60a (device wafer that has been mechanically or chemically treated). The temperature at the time of peeling is preferably 40 ° C. or lower, and may be 30 ° C. or lower. The lower limit of the temperature at the time of peeling is, for example, 0 ° C. or higher, preferably 10 ° C. or higher.

The method of peeling is not particularly limited, but it is preferable that the thinning device wafer 60a is fixed and the carrier substrate 12 is pulled up from the end in the direction perpendicular to the thinning device wafer 60a and peeled. At this time, it is preferable that the peeling interface is peeled off at the interface between the carrier substrate 12 and the temporary adhesive layer 11. The pulling speed at the time of peeling is preferably 30 to 100 mm / min, more preferably 40 to 80 mm / min. In this case, it is preferable that the adhesion strength A at the interface between the carrier substrate 12 and the temporary adhesive layer 11 and the adhesion strength B between the device wafer surface 61a and the temporary adhesive layer 11 satisfy the following formulas.

A <B ... Equation (A1)
Further, the force for pulling up the end portion at the time of peeling is preferably 0.33 N / mm or less, and may 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.

Further, as will be described later, the peeling of the device wafer and the carrier substrate may be performed by laser peeling.

Then, as shown in FIG. 3E, the thinning device wafer can be obtained by removing the temporary adhesive layer 11 from the thinning device wafer 60a.

The method for removing the temporary adhesive layer 11 is, for example, a method of removing the temporary adhesive layer using a cleaning agent (a method of swelling the temporary adhesive layer with a cleaning agent and then peeling it off, or a method of spraying a cleaning agent onto the temporary adhesive layer to destroy and remove it. , A method of dissolving and removing the temporary adhesive layer by dissolving it in a cleaning agent, etc.), a method of decomposing and vaporizing the temporary adhesive layer by irradiation with active light, radiation or heat, and the like.

From the viewpoint of reducing the amount of solvent used, it is preferable to peel off the temporary adhesive layer 11 from the device wafer 60a in a film-like state. The method of peeling and removing the temporary adhesive layer in the form of a film means a method of peeling off the temporary adhesive layer in the form of a film without performing chemical treatment such as using a cleaning agent or the like. When the temporary adhesive layer is peeled off in a film-like state, manual peeling or mechanical peeling is preferable. In order to peel off and remove the temporary adhesive layer in a film-like 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 ・ ・ ・ ・ Equation (B1)

After the carrier substrate 12 is peeled off from the thinning device wafer 60a, various known treatments are applied to the thinning device wafer 60a to manufacture a semiconductor device having the thinning device wafer 60a.

<< Second Embodiment >>
A second embodiment of the semiconductor manufacturing method will be described with reference to FIG. The same parts as those in the first embodiment described above are designated by the same reference numerals, and the description thereof will be omitted.

4 (A) to 4 (E) are schematic cross-sectional views (FIGS. 4 (A) and 4 (B)) illustrating temporary bonding between the carrier substrate and the device wafer, respectively, and the device wafer temporarily bonded to the carrier substrate is shown. The thinned state (FIG. 4 (C)), the state where the carrier substrate and the device wafer are peeled off (FIG. 4 (D)), and the state after the temporary adhesive layer is removed from the device wafer (FIG. 4 (E)). It is a schematic cross-sectional view which shows.

In this embodiment, as shown in FIG. 4A, a temporary adhesive layer is formed on the surface 61a of the device wafer, which is different from the first embodiment.

When the temporary adhesive layer 11a is provided on the surface 61a of the device wafer 60, it is formed by applying (preferably applying) a temporary adhesive to the surface of the surface 61a of the device wafer 60 and then drying (baking) it. 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 crimped to temporarily bond the carrier substrate 12 and the device wafer 60. Next, as shown in FIG. 4C, the back surface 61b of the silicon substrate 61 is mechanically or chemically treated to reduce the thickness of the silicon substrate 61 as shown in FIG. 4C. Thinning is obtained to obtain a thinning device wafer 60a. Next, as shown in FIG. 4D, the carrier substrate 12 is peeled off from the thinning device wafer 60a. Then, as shown in FIG. 4E, the temporary adhesive layer 11a is removed from the thinning device wafer 60a.

The method for manufacturing a semiconductor device of the present invention is not limited to the above-described embodiment, and can be appropriately modified, improved, and the like.

Further, in the above-described embodiment, the silicon substrate is mentioned as the device wafer, but the present invention is not limited to this, and any subject that can be subjected to mechanical or chemical treatment in the method for manufacturing a semiconductor device. It may be a processing member.

Further, in the above-described embodiment, as the mechanical or chemical treatment for the device wafer (silicon substrate), the thinning treatment of the device wafer and the formation treatment of the through silicon via are mentioned, but the treatment is limited thereto. However, any processing required in the method for manufacturing a semiconductor device can be mentioned.

In addition, the shape, dimensions, number, arrangement location, and the like of the device chips in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited.

<< Third Embodiment >>
The composition for temporary adhesion of the present invention may be used alone as a temporary adhesive layer, or may be laminated with a laser peeling layer. The laser exfoliation layer is composed of a material that loses its strength or adhesiveness before being irradiated with light by being altered by absorption of light. Therefore, by using the laser release layer, the laminate can be broken by applying a slight external force (for example, lifting the carrier substrate), and the carrier substrate and the device wafer can be easily separated. Such a laser exfoliation layer preferably contains at least one of a polyimide resin, an aromatic polymer, carbon black and a pyrolytic compound. The "pyrolytic compound" refers to a compound having a 5% thermal mass reduction temperature of 300 ° C. or lower. The 5% thermal mass reduction temperature of the pyrolytic compound is preferably 250 ° C. to 150 ° C. The 5% heat mass reduction temperature can be measured by thermogravimetric analysis (TGA) at a heating rate of 10 ° C./min under a nitrogen atmosphere. The pyrolytic compounds are, for example, cycloolefin resins, fluorocarbon compounds, acrylic resins, terpene resins, petroleum resins, novolak resins and elastomers. Among these, as the thermally decomposable compound, a cycloolefin resin, a fluorocarbon compound, a terpene resin, a petroleum resin and an elastomer are preferable, and a cycloolefin resin and a fluorocarbon compound are particularly preferable.

The laser light used may be, for example, a YAG laser, a ruby laser, a glass laser, a _YVO4 laser, an LD laser, a solid laser such as a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that can be absorbed by the laser separation layer. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, a He-Ne laser, a semiconductor laser, a laser beam such as a free electron laser, or a non-laser laser may be appropriately used.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Preparation of composition for temporary adhesion>
As shown in Tables 1 to 4 below, each component of the temporary adhesive composition is mixed to form a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. , A composition for temporary adhesion was prepared. The component ratios in each table are expressed in% by mass. Further, in the table, the numerical values described in the columns of "whole elastomer", "whole organic solvent", "whole surfactant" and "whole antioxidant" represent the ratio to the whole composition. On the other hand, the numerical values described in the individual columns of each component represent the ratio to the entire group of compounds (any one of elastomer, organic solvent, surfactant and antioxidant) to which the component belongs.

Details of the compounds used are as follows.

<< Elastomer >>
PS-1: Septon 4033 (manufactured by Kuraray Co., Ltd., polystyrene-based elastomer)
PS-2: Septon 2104 (manufactured by Kuraray Co., Ltd., polystyrene-based elastomer)
P-1: Iupizeta FPC2136 (manufactured by Mitsubishi Gas Chemical Company, Inc., special polycarbonate)
P-2: Iupizeta FPC0330 (special polycarbonate manufactured by Mitsubishi Gas Chemical Company, Inc.)

<< Organic Solvent >>
LS-1: Cyclohexane (boiling point 80.8 ° C., corresponding to a low boiling point organic solvent)
LS-2: Toluene (boiling point 110.6 ° C, corresponding to low boiling point organic solvent)
S-1: Mesitylene (1,3,5-trimethylbenzene, boiling point 164.7 ° C, manufactured by Toyo Gosei Co., Ltd.)

<< Surfactant >>
SA-A: FC-540 (fluorine-based, made by DIC)
SA-B: TSF4445 (polyether-modified organopolysiloxane, manufactured by Momentive Performance Materials Japan GK)
SA-C: Acetyleneol E40 (acetylene-based, manufactured by Kawaken Fine Chemical Co., Ltd. SA-D: Pluronic PE10500 (propylene glycol, ethylene glycol copolymer, manufactured by BASF))

<< Antioxidant >>
OX-1: Irganox1010 (manufactured by BASF Japan Ltd.)
OX-2: Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.)

<Manufacturing of laminate for temporary bonding>
The laminated body for tensile peeling (Examples 1 to 20 and Comparative Examples 1 to 6) will be described. Under the following coating conditions, each of the temporary adhesive compositions shown in the above table was applied onto a 100 mm × 100 mm glass substrate using a slit coater to form a coating film. In the decompression chamber, the coating film is vacuum dried under the condition of ultimate vacuum degree 0.4 Torr (1 Torr = 133.322 Pa), the laminate is taken out from the decompression chamber, and then 190 for 3 minutes using a hot plate. By heating and drying at ° C., a temporary adhesive layer having a thickness of 20 μm was formed. This is a temporary adhesive laminate including a temporary adhesive layer and a glass substrate.

Next, a laminated body for laser peeling (Examples 21 to 25) will be described. First, a laser release layer was formed on a 100 mm × 100 mm glass substrate by the manufacturing method shown below. Then, a temporary adhesive layer was formed on each laser peeling layer under the same conditions as in Example 1. This is a temporary adhesive laminate including a temporary adhesive layer, a laser release layer, and a glass substrate.

<< Application conditions for temporary adhesive composition >>
-Substrate temperature: Room temperature (23 ° C)
・ Coating gap: 300 mm
・ Coating amount per unit time: 0.5 ml / s
・ Movement speed: 5 mm / sec

<< Method of forming a laser release layer >>
<<< LP-1 >>>
The laser peeling layer LP-1 is a peeling layer containing a polyimide resin. The laser release layer LP-1 was formed as follows. First, 27.7% by mass of polyimide (product name: Upia-AT1001, manufactured by Ube Kosan Co., Ltd.) and 72.3% by mass of N-methylpyrrolidone were mixed. Then, the mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a composition for a release layer. Then, using a spin coater (EVG101 manufactured by EV Group), the composition for the release layer was applied to the surface of the glass substrate, dried at 80 ° C. for 3 minutes, and then dried at 190 ° C. for 3 minutes to make the thickness. A 1 μm release layer was formed.

<<< LP-2 >>>
The laser release layer LP-2 is a release layer containing a cycloolefin resin. The laser exfoliation layer LP-2 was formed as follows. First, 80 parts of a cycloolefin polymer (trade name "ARTON RX4500", manufactured by JSR Co., Ltd.), 20 parts of a hydrogenated terpene resin (trade name "CLEARON P150", manufactured by Yasuhara Chemical Co., Ltd.), and 20 parts. 125 parts of liquid styrene-butadiene rubber (trade name "L-SBR-820", manufactured by Kuraray Co., Ltd.) and 3 parts of hindered phenolic antioxidant (trade name "IRGANOX1010", manufactured by BASF). Carbon black dispersion (trade name "MHI Black # 209", manufactured by Mikuni Color Co., Ltd., solid content 35% by mass) and 367 parts of mesitylene were mixed. Then, the mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a composition for a release layer. Then, using a spin coater (EVG101 manufactured by EV Group), the composition for the release layer was applied to the surface of the glass substrate, dried at 80 ° C. for 3 minutes, and then dried at 190 ° C. for 3 minutes to make the thickness. A 1 μm release layer was formed.

<<< LP-3 >>
The laser peeling layer LP-3 is a peeling layer containing a fluorocarbon compound. The laser release layer LP-3 was formed as follows. A fluorocarbon film was placed on the adhesive layer of the bare silicon wafer with an adhesive layer by a CVD method using _C4 F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film formation temperature of 240 ° C. A peeling layer having a thickness of 1 μm was formed.

<<< LP-4 >>>
The laser peeling layer LP-4 is a peeling layer containing an aromatic polymer. The laser release layer LP-4 was formed as follows. First, 100 parts of the polymer (A1) synthesized by the following method, 10 parts of 4,4'-bis (diethylamino) benzophenone, 315 parts of cyclohexanone, and 210 parts of methoxypropyl acetate were mixed. Then, the mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a composition for a release layer. Then, using a spin coater, the composition for a release layer was applied to the surface of the glass substrate and dried at 80 ° C. for 3 minutes and then at 190 ° C. for 3 minutes to form a release layer having a thickness of 1 μm.

Method for synthesizing polymer (A1):
A reactor equipped with a condenser, a thermometer and a stirrer is charged with 100 parts of 2,6-dihydroxynaphthalene, 100 parts of propylene glycol monomethyl ether acetate, and 50 parts of paraformaldehyde (formaldehyde equivalent), and 2 parts of oxalic acid is added. , Heated at 120 ° C. for 5 hours while dehydrating. Then, water was added to the reaction solution and the mixture was stirred. After recovering the precipitate, it was washed with water and dried at 50 ° C. for 17 hours to obtain a 2,6-dihydroxynaphthalene / formaldehyde condensate (polymer (A1)). The Mw of the polymer (A1) was 1550.

<<< LP-5 >>>
The laser peeling layer LP-5 is a peeling layer containing carbon black. The laser release layer LP-5 was formed as follows. First, 2.5% by mass of carbon black (product name # 950, manufactured by Mitsubishi Chemical Co., Ltd.), 3.25% by mass of silica (product name: AEROSIL 200, manufactured by Nippon Aerosil), and 0.75% by mass of dispersion. An agent (product name: Disperbyk 168, manufactured by Big Chemie Japan), 3.5% by mass of acrylic resin (product name: Joncryl 690, manufactured by BASF Japan) and 90% by mass of propylene glycol monomethyl ether acetate were mixed. Then, the mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a composition for a release layer. Then, using a spin coater, the composition for a release layer was applied to the surface of the glass substrate and dried at 80 ° C. for 3 minutes and then at 190 ° C. for 3 minutes to form a release layer having a thickness of 1 μm.

<Evaluation>
For the present invention, the contact angle was measured by the method shown below. Further, regarding the present invention, the coatability of the temporary adhesive composition, the peelability of the temporary adhesive layer, the void defect at the time of adhesion, and the tackiness of the composition (difficulty of dripping) are obtained by the methods shown below. We evaluated each. The evaluation results are shown in Tables 1 to 4 above.

<< Measurement of contact angle >>
A droplet having a droplet size of 10 μL consisting of each composition is dropped on a smooth surface of stainless steel (SUS304) with a syringe, and the angle formed by the droplet is measured using a static contact angle meter (manufactured by Kyowa Surface Science Co., Ltd.). did. Then, each composition was measured three times, and the arithmetic mean value was adopted as the contact angle. Other conditions shall be in accordance with JIS R3257: 1999.

<< Applyability of Temporary Adhesive Composition >>
The applicability of the temporary adhesive composition was evaluated based on the evaluation value of the in-plane uniformity of the temporary adhesive layer in which the temporary adhesive composition became a film. For this evaluation value, the film thickness was measured at 115 points in the plane using an F-50 film thickness meter manufactured by FILMETRIX, the arithmetic mean value of these film thicknesses was M, and the standard deviation was σ. Calculated.
Evaluation value of in-plane uniformity = 3σ ÷ M × 100 [%]
Then, based on this evaluation value, evaluation was made according to the following criteria.
A: Evaluation value is less than 5% B: Evaluation value is 5% or more and less than 10% C: Evaluation value is 10% or more

<< Peelability of temporary adhesive layer >>
The peelability of the temporary adhesive layer was evaluated based on the magnitude of the peeling force required for peeling the film of the temporary adhesive layer from the carrier substrate. The magnitude of the peeling force was measured as follows.
A 100 mm × 100 mm glass substrate was used as the carrier substrate, and each temporary adhesive composition shown in the above table was applied to the surface thereof with a slit coater to form a coating film. In the decompression chamber, the coating film is vacuum-dried under the condition of the ultimate vacuum degree of 0.4 Torr, the laminate is taken out from the decompression chamber, and then heated and dried at 190 ° C. for 3 minutes using a hot plate. , A temporary adhesive film was formed on the surface of the glass substrate. The film thickness of the temporary adhesive film at this time was 20 μm. The temporary adhesive film obtained above is cut to a width of 30 mm, and the end of the film having a width of 30 mm is oriented perpendicular to the surface of the glass substrate under the conditions of a temperature of 25 ° C. and a pulling speed of 300 mm / min. The force (peeling force, unit: N / m) applied when pulling up and pulling up using a force gauge (manufactured by Imada Co., Ltd., DS2-20N) was measured.
Then, based on the magnitude of this peeling force, the evaluation was made according to the following criteria.
A: Peeling force is 30 N / m or more and 40 N / m or less B: Peeling force is 20 N / m or more and less than 30 N / m, or more than 40 N / m and 50 N / m or less C: Peeling force is less than 20 N / m or 50 N Over / m

<< Void defects during bonding >>
The number of voids when the carrier substrate was bonded to the semiconductor substrate via the temporary adhesive layer was measured as follows.
Each temporary bonding composition shown in the above table was applied onto a 100 mm × 100 mm glass substrate using a slit coater to form a coating film. In the decompression chamber, the coating film is vacuum-dried under the condition of the ultimate vacuum degree of 0.4 Torr, the laminate is taken out from the decompression chamber, and then heated and dried at 190 ° C. for 3 minutes using a hot plate. , A temporary adhesive film having a thickness of 20 μm was formed on the surface of the glass substrate. The device surface of the pseudo device wafer formed by cutting a glass wafer into 100 mm squares is bonded to the surface of the glass substrate on which the temporary adhesive film is formed, and under the conditions of a vacuum atmosphere, a substrate temperature of 200 ° C., and a pressure of 0.11 MPa. These were crimped for 3 minutes to prepare a test piece. Then, voids of 10 μm or more were counted from the glass substrate side using an optical microscope.

<< Tackiness of Temporary Adhesive Composition >>
The tackiness of the temporary adhesive composition was evaluated based on the degree of liquid dripping in the initial stage after application of the temporary adhesive composition. The degree of dripping is the observation result when a sample consisting of each composition is applied to a glass substrate, heated at 140 ° C. for 1 minute, and then the substrate is tilted vertically.

Then, based on the degree of this dripping, the evaluation was made according to the following criteria.
A: No dripping occurred B: Some dripping occurred.
C: Liquid dripping occurred on the entire surface.

As shown in Tables 1 to 4, in the examples of the present invention, the contact angle with respect to stainless steel was reduced and the action of the low boiling point organic solvent was excellent in the applicability of the temporary adhesive composition, and the surfactant was used. A temporary adhesive layer having excellent peelability was obtained by a dynamic action. Further, even when the temporary adhesive composition of the example of the present invention was applied by the spin coating method, a temporary adhesive layer having sufficient coatability and peelability could be formed. That is, according to the present invention, a temporary adhesive composition capable of sufficiently ensuring the coatability of the temporary adhesive composition and the peelability of the temporary adhesive layer can be obtained even by using the rectangular coating method.

In particular, when the contact angle was 50 degrees or less, the wettability with respect to the coater member was improved, and it was found that the coatability of the composition was further improved. It was also found that according to the present invention, it is possible to suppress the generation of voids that are likely to occur when the temporary adhesive layer is bonded. Further, the composition for temporary adhesion of the present invention is also excellent in tackiness and can suppress the spread of useless composition in the direction perpendicular to the coating direction, so that efficient coating is possible in the rectangular coating method. Will be.

It was also found that the temporary adhesive composition of the present invention can be used for a single temporary adhesive layer, and can also be used in combination with a laser peeling layer to ensure sufficient adhesiveness.

1 Slit coater 2 Bar coater 11, 11a Temporary adhesive layer 12 Carrier substrate 13, 23 Gap 14, 24 Coating film 16 Blade 25 Wire bar 26 Coating liquid supply unit 60 Work substrate (device wafer)
60a Thinning device wafer 61 Silicon substrate 61a Front surface 61b, 61b1: Back surface 62 Device chip 100 Adhesive carrier substrate L Temporary adhesive composition S substrate

Claims (17)

Contains elastomers, organic solvents and surfactants,
The organic solvent contains a low boiling point organic solvent having a boiling point of 120 ° C. or lower at a ratio of 50 to 95% by mass with respect to the whole organic solvent.
The surfactant contains a fluorine-based surfactant A and a silicone-based surfactant B.
Temporary adhesive composition satisfying the formula (1) with respect to the surfactant A and the surfactant B;
_WA / _WB = 1.5-5 formula (1);
In the formula (1), WA represents the content of the surfactant _A with respect to the entire surfactant in terms of mass%, and WB represents the total content of the surfactant _B in terms of mass%. Represents the content for. The _WA / _WB is 1.5 to 3.0.
The composition for temporary adhesion according to claim 1. The content of the surfactant B in the entire composition is 0.00005 to 1% by mass.
The composition for temporary adhesion according to claim 1 or 2. The content of the surfactant with respect to the entire composition is 0.00002 to 2% by mass.
The composition for temporary adhesion according to any one of claims 1 to 3. The content of the organic solvent in the entire composition is 60 to 95% by mass.
The composition for temporary adhesion according to any one of claims 1 to 4. The content of the low boiling point organic solvent is 50% by mass or more with respect to the entire organic solvent.
The composition for temporary adhesion according to any one of claims 1 to 5. The contact angle of the temporary bonding composition with respect to the stainless SUS304 in a liquid state is 50 degrees or less.
The composition for temporary adhesion according to any one of claims 1 to 6. The low boiling point organic solvent contains an aliphatic hydrocarbon,
The composition for temporary adhesion according to any one of claims 1 to 7. The organic solvent contains aromatic hydrocarbons,
The composition for temporary adhesion according to any one of claims 1 to 8. The surfactant contains an acetylene-based surfactant C.
The composition for temporary adhesion according to any one of claims 1 to 9. For the surfactant C and the surfactant B, the formula (2) is satisfied.
The composition for temporary adhesion according to claim 10;
_WC / _WB = 0.005-500 formula (2);
In the formula (2), WC represents the content of the surfactant _C with respect to the whole surfactant in terms of mass%. For the surfactant and the organic solvent, the formula (3) is satisfied.
The temporary adhesive composition according to any one of claims 1 to 11.
W _ALL / _WS = 0.000002 to 0.006 equation (3);
In the formula (3), _WALL represents the content of the entire surfactant with respect to the entire composition in terms of mass%, and _WS represents the content of the entire organic solvent in terms of mass% with respect to the entire composition. .. The elastomer comprises a hydrogenator,
The composition for temporary adhesion according to any one of claims 1 to 12. The elastomer comprises a polystyrene-based elastomer hydrogenator.
The composition for temporary adhesion according to claim 13. The content of the polystyrene-based elastomer hydrogenated material with respect to the entire elastomer is 10 to 100% by mass.
The composition for temporary adhesion according to claim 14. A kit comprising a rectangular substrate and the composition according to any one of claims 1 to 15. A laminate including a rectangular substrate and a temporary adhesive layer formed by using the composition according to any one of claims 1 to 15.

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