JP2023145379A - Method for manufacturing semiconductor device - Google Patents

Abstract

To provide a method for manufacturing a semiconductor device capable of reducing a residue after high-temperature processing and easily peeling the semiconductor device from a temporary fixing material even when high-temperature processing is performed at 300°C or higher with the semiconductor device temporarily fixed to the temporary fixing material.SOLUTION: A method for manufacturing a semiconductor device includes a temporary fixing step (1) of temporarily fixing a temporary fixing material to the semiconductor device, a heat treatment step (2) of subjecting the semiconductor device to heat treatment, and a peeling step (3) of peeling the semiconductor device after heat treatment from the temporary fixing material in this order, and peels the semiconductor device after heat treatment from the temporary fixing material under the condition that the following expressions (F1) and (F2) met in the peeling step (3). E'(T1)≤3×107 (F1) 0.080<L(T1)<2.0 (F2) In the expression (F1), T1 represents a temperature (°C) of the semiconductor device with which the temporary fixing material is in contact in the peeling step (3). E'(t) represents a storage elastic modulus (Pa) of the temporary fixing material at a temperature t in the peeling step (3). E'(T1) represents a value when the temperature t of E'(t) is T1. In the expression (F2), T1 represents a temperature (°C) of the semiconductor device with which the temporary fixing material is in contact in the peeling step (3). L(t) represents a tensile elongation rate of the temporary fixing material at a temperature t in the peeling step (3). L(T1) represents a value when the temperature t of L(t) is T1.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a semiconductor device.

When processing semiconductor devices such as semiconductor wafers and semiconductor chips, in order to make the semiconductor devices easier to handle and prevent them from being damaged, the semiconductor devices may be fixed to a support plate via an adhesive composition, or Semiconductor devices are often protected by attaching adhesive tape to them. For example, when a thick film wafer cut from high purity silicon single crystal etc. is ground to a predetermined thickness to make a thin film wafer, it is possible to bond the thick film wafer to a support plate via an adhesive composition. It will be done.

In this way, adhesive compositions and adhesive tapes used for semiconductor devices are required to have high adhesive properties that can firmly fix the semiconductor device during the processing process, and also to be able to be peeled off after the process is completed without damaging the semiconductor device. (Hereinafter, also referred to as "high adhesion and easy peeling.")
As a means of realizing high adhesion and easy peeling, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of a polymer. has been done. Utilizing the fact that the polymer is cured by ultraviolet irradiation due to the presence of a radiation-polymerizable functional group, the adhesive strength is reduced by irradiating ultraviolet rays during peeling, and the adhesive can be peeled off without leaving any adhesive residue.

Japanese Patent Application Publication No. 5-32946

2. Description of the Related Art As the performance of semiconductor devices has improved in recent years, various processes have been performed on semiconductor devices. For example, in the process of forming a metal thin film on the surface of a semiconductor device by sputtering, a metal thin film with better conductivity can be formed by processing at a high temperature of about 300 to 350°C.
However, when semiconductor devices protected using conventional adhesive compositions or adhesive tapes are subjected to high-temperature processing at temperatures of 300°C or higher, adhesion may be enhanced and the adhesive force may not be sufficiently reduced during peeling, or the adhesive may Remains may occur. In addition, semiconductor devices manufactured through high-temperature processing at 300°C or higher are becoming thinner, and if normal mechanical peeling methods are used, semiconductor devices may be damaged when the adhesive composition or adhesive tape is peeled off. Sometimes.

The present invention enables the semiconductor device to be removed from the temporary fixing material while suppressing the residue after the high temperature processing even when performing high temperature processing at 300°C or higher with the semiconductor device temporarily fixed to the temporary fixing material. An object of the present invention is to provide a method for manufacturing a semiconductor device that can be easily peeled off.

The present disclosure 1 includes a temporary fixing step (1) of temporarily fixing a temporary fixing material to a semiconductor device, a heat treatment step (2) of heat treating the semiconductor device, and peeling off the semiconductor device after the heat treatment from the temporary fixing material. and a peeling step (3) in this order, and in the peeling step (3), the heat-treated semiconductor device is peeled from the temporary fixing material under conditions that satisfy the following formulas (F1) and (F2). This is a method for manufacturing a semiconductor device.
E'(T1)≦3×10 ⁷ (F1)
0.080<L(T1)<2.0 (F2)
In formula (F1), T1 represents the temperature (°C) of the semiconductor device that the temporary fixing material contacts in the peeling step (3), and E'(t) represents the temperature t in the peeling step (3). represents the storage elastic modulus (Pa) of the temporarily fixed material, and E'(T1) represents the value of E'(t) when the temperature t=T1. In formula (F2), T1 represents the temperature (°C) of the semiconductor device with which the temporary fixing material comes into contact in the peeling step (3), and L(t) represents the temperature (°C) at the temperature t in the peeling step (3). It represents the tensile elongation rate of the temporary fixing material, and L(T1) represents the value of L(t) when the temperature t=T1.
The present disclosure 2 is the method for manufacturing the semiconductor device of the present disclosure 1, wherein the temporary fixing material has a weight reduction rate of 20% or less after being heated at 280° C. for 1 hour.
In the present disclosure 3, in the temporary fixing step (1), after applying a temporary fixing material precursor to the semiconductor device, the temporary fixing material precursor is cured by heating, so that the temporary fixing material is fixed on the semiconductor device. 1 is a method for manufacturing a semiconductor device according to the first or second disclosure of the present disclosure, in which a material is formed;
The present disclosure 4 is the present disclosure 3, wherein the temporary fixing material precursor is a silicone resin fluid or a polyimide resin fluid having an unreacted group of an acid dianhydride and an unreacted group of a diamine compound. This is a method for manufacturing a semiconductor device.
The present disclosure 5 is the method for manufacturing a semiconductor device according to the present disclosure 1 or 2, in which the temporary fixing material is bonded to the semiconductor device in the temporary fixing step (1).
The present disclosure 6 provides that the temporary fixing material has an adhesive layer containing a curable adhesive, and the curable adhesive includes a resin (1) having an imide skeleton as a repeating unit of the main chain, and a molecule. The semiconductor according to Present Disclosure 5, which contains a polyfunctional monomer or polyfunctional oligomer (2) having two or more functional groups containing carbon-carbon double bonds having energy ray reactivity and a molecular weight of 5000 or less. This is a method for manufacturing the device.
The present disclosure 7 provides a resin (1) having the imide skeleton as a repeating unit of the main chain, and having two or more functional groups containing a carbon-carbon double bond having energy ray reactivity in the molecule, At least one selected from the group consisting of polyfunctional monomers or polyfunctional oligomers (2) having a molecular weight of 5000 or less has an aliphatic group derived from dimer diamine, the method for manufacturing a semiconductor device according to present disclosure 6. .
The present disclosure 8 is the method for manufacturing the semiconductor device of the present disclosure 1, 2, 3, 4, 5, 6, or 7, wherein the T1 is 25° C. or more and 120° C. or less in the peeling step (3).
Present disclosure 9 is the semiconductor of present disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein in the peeling step (3), the peeling angle of the temporary fixing material is 90° or more and 180° or less. This is a method for manufacturing the device.
The present disclosure 10 provides the present disclosure 1, 2, 3, 4, 5, 6, and 7, wherein the peeling force of the temporary fixing material against the silicon wafer at the temperature T1 in the peeling step (3) is 1 N/inch or less. , 8 or 9.
The present invention will be explained in detail below.

Curable adhesives that have excellent heat resistance and can be cured by heating or irradiation with energy rays are being considered as processing materials that can be applied to high-temperature processing at temperatures of 300° C. or higher. However, such curable adhesives with excellent heat resistance generally tend to be hard and difficult to stretch, so the peeling force increases when peeling, resulting in damage to the semiconductor device or damage to some of the curable adhesives. It may break off and leave a residue. In particular, the higher the bumps (protruding electrodes) formed on the surface of the semiconductor device, the more likely the semiconductor device will be damaged and the more likely a residue of the curable adhesive will be generated.
The present inventors have proposed a method for manufacturing a semiconductor device in which a semiconductor device is temporarily fixed to a temporary fixing material, and then the semiconductor device is subjected to heat treatment, and then the heat-treated semiconductor device is peeled from the temporary fixing material. We considered adjusting the temperature, storage modulus, and tensile elongation of the fixing material to satisfy a specific relational expression. The present inventors have discovered that according to such a method for manufacturing a semiconductor device, even when performing high-temperature processing at 300°C or higher with the semiconductor device temporarily fixed to the temporary fixing material, it is possible to Later, they discovered that the semiconductor device could be easily peeled off from the temporary fixing material while suppressing the residue, and the present invention was completed.

In the method for manufacturing a semiconductor device of the present invention, first, a temporary fixing step (1) is performed in which a semiconductor device is temporarily fixed to a temporary fixing material.

The method of temporarily fixing the semiconductor device to the temporary fixing material is not particularly limited, and may be appropriately selected depending on the form of the temporary fixing material. That is, when the temporary fixing material is a temporary fixing material such as a liquid or a paste, for example, a method of applying the temporary fixing material to the semiconductor device may be mentioned; In the case of the temporary fixing material, for example, there is a method of bonding the temporary fixing material to the semiconductor device. Another method may include forming the temporary fixing material on the semiconductor device by applying a temporary fixing material precursor to the semiconductor device and then curing the temporary fixing material precursor by heating.
The method of applying the temporary fixing material or the temporary fixing material precursor to the semiconductor device is not particularly limited, and examples thereof include spray coating, spin coating, and the like. The method of bonding the temporary fixing material to the semiconductor device is not particularly limited, and examples include heating lamination using a thermal laminator at about 50 to 100°C, and using a vacuum laminator at a pressure of 40 to 100 Pa. Examples include a method of laminating at about 70°C.

In the method for manufacturing a semiconductor device of the present invention, when the temporary fixing material is a hardening type, the temporary fixing material is further added after the temporary fixing step (1) and before the heat treatment step (2) described later. It is preferable to perform a curing step (4) of curing the material.

The method for curing the temporary fixing material is not particularly limited, and examples include a method of heating the temporary fixing material, a method of irradiating the temporary fixing material with energy rays, and the like. More specifically, for example, a method of heating the temporary fixing material in an oven at 170° C. for 10 minutes, a method of irradiating the temporary fixing material with ultraviolet rays of 405 nm and an irradiation intensity of 70 mW/cm ² at 1000 mJ/cm ² , etc. Can be mentioned.

In the method for manufacturing a semiconductor device of the present invention, next, a heat treatment step (2) is performed in which the semiconductor device is heat treated.

The type of heat treatment is not particularly limited, and examples thereof include heat treatments such as molding, sputtering, and thermocompression bonding for the semiconductor device. The heat treatment may be a high temperature processing treatment at 300° C. or higher.

In the method for manufacturing a semiconductor device of the present invention, a peeling step (3) is further performed in which the heat-treated semiconductor device is peeled off from the temporary fixing material.

In the peeling step (3), the heat-treated semiconductor device is peeled from the temporary fixing material under conditions that satisfy the following formulas (F1) and (F2). The temperature of the semiconductor device in contact with the temporary fixing material at the time of peeling (hereinafter also referred to as "temporary fixing material temperature"), the storage modulus of the temporary fixing material, and the tensile elongation rate satisfy such a relational expression. By adjusting this, even if high-temperature processing at 300°C or higher is performed with the semiconductor device temporarily fixed to the temporary fixing material, residue can be suppressed and removed from the temporary fixing material after the high-temperature processing. The semiconductor device can be easily peeled off. In the method for manufacturing a semiconductor device of the present invention, the temperature, storage modulus, and tensile elongation of the temporary fixing material at the time of peeling are studied in advance, and the following formulas (F1) and (F2) are satisfied. The conditions for the above peeling step (3) are determined.

E'(T1)≦3×10 ⁷ (F1)
0.080<L(T1)<2.0 (F2)

In formula (F1), T1 represents the temperature (°C) of the temporary fixing material in the peeling step (3), and E'(t) represents the temperature (°C) of the temporary fixing material at the temperature t in the peeling step (3). represents the storage modulus (Pa) of E'(t), and E'(T1) represents the value of E'(t) at temperature t=T1. In formula (F2), T1 represents the temperature (°C) of the temporary fixing material in the peeling step (3), and L(t) represents the temperature (°C) of the temporary fixing material at the temperature t in the peeling step (3). It represents the tensile elongation rate, and L(T1) represents the value of L(t) when the temperature t=T1.

The above T1 is not particularly limited as long as it is adjusted to satisfy the above formulas (F1) and (F2), but the preferable lower limit is 25°C, the preferable upper limit is 120°C, and the more preferable lower limit is 40°C, more preferably A preferable upper limit is 100°C.

By setting the above E'(T1) (i.e., the storage elastic modulus (Pa) of the temporary fixing material at the temperature (°C) of the temporary fixing material in the peeling step (3)) to 3×10 ⁷ Pa or less After undergoing high-temperature processing, the semiconductor device can be easily peeled off from the temporary fixing material. From the viewpoint of further improving the releasability, the preferable upper limit of E'(T1) is 1×10 ⁷ Pa, and the more preferable upper limit is 8×10 ⁶ Pa.
The lower limit of E'(T1) is not particularly limited, but from the viewpoint of preventing the temporary fixing material from becoming too soft and remaining on the semiconductor device, the lower limit is preferably 1×10 ⁵ Pa, more preferably The lower limit is 5×10 ⁵ Pa.
In addition, the storage elastic modulus of the temporary fixing material at a specific temperature can be measured by the following method.
A test piece of 5 mm x 35 mm x 0.05 mm in thickness is prepared for the temporary fixing material. When the temporary fixing material is a hardening type, the obtained test piece is hardened under the conditions for performing the hardening step (4). The cured sample is heat treated under the conditions for the heat treatment step (2). The heat-treated sample was immersed in liquid nitrogen to cool to -50°C, and then measured using a viscoelastic spectrometer (e.g., DVA-200, manufactured by IT Kansei Control Co., Ltd.) in constant-rate heating tensile mode. The temperature is raised to 300°C at a heating rate of 10°C/min and a frequency of 10Hz, and the storage modulus at temperature T1 is measured.

Further, the storage modulus of the temporary fixing material at room temperature is not particularly limited, but from the viewpoint of adjusting the E'(T1) within the above range, the preferable lower limit of the storage modulus of the temporary fixing material at 25°C is 1×10 ⁵ Pa, a preferable upper limit is 1×10 ¹⁰ Pa, a more preferable lower limit is 5×10 ⁵ Pa, and a more preferable upper limit is 5×10 ⁹ Pa. In addition, the storage elastic modulus here means that when the temporary fixing material is a hardening type, it is heated for 10 minutes in an oven at 170°C or exposed to 1000 mJ/cm of ultraviolet rays at a wavelength of 405 nm and an irradiation intensity of 70 mW/ ^cm2 . cm ² means the storage elastic modulus of the temporary fixing material after irradiation.

The method for adjusting E'(T1) within the above range is not particularly limited, and includes, for example, a method of adjusting the composition of the temporary fixing material, and a method of adjusting the temperature of the temporary fixing material in the peeling step (3). etc. Furthermore, when the temporary fixing material is composed of multiple layers including a base material, a method of adjusting the above E'(T1) by selecting the type and thickness of the base material can be mentioned.

By setting the L (T1) (i.e., the tensile elongation rate of the temporary fixing material at the temperature (°C) of the temporary fixing material in the peeling step (3)) to be larger than 0.080 and smaller than 2.0. It is possible to prevent a portion of the temporary fixing material from being torn off or from remaining on the semiconductor device due to the temporary fixing material becoming too soft, and to suppress residues of the temporary fixing material. The above L(T1) is preferably 1.7 or less, more preferably 1.5 or less. The above L(T1) is preferably larger than 0.090, more preferably 0.10 or more, and even more preferably 0.15 or more.
The tensile elongation rate of the temporary fixing material at a specific temperature can be measured by setting two marked lines on the temporary fixing material and measuring the distance between the marked lines before and after peeling.
More specifically, after the temporary fixing step (1), two marked lines are provided on the temporary fixing material. At this time, the two marked lines are set to be perpendicular to the direction of peeling of the temporary fixing material. Thereafter, the heat treatment step (2), the peeling step (3), and, if necessary, the curing step (4) are performed. Regarding the distance between the gauge lines before and after the above peeling step (3), the distance between the gauge lines before peeling at temperature T1 is set as A (T1), the distance between the gauge lines after peeling at temperature T1 is set as B (T1), The tensile elongation rate L (T1) is calculated using the following formula.
L(T1)=(B(T1)-A(T1))/A(T1)

The method for adjusting the L(T1) within the above range is not particularly limited, and includes, for example, a method of adjusting the composition of the temporary fixing material, the temperature of the temporary fixing material in the peeling step (3), a peeling method, and a peeling method. Examples include methods of adjusting angle, peeling speed, etc. Furthermore, when the temporary fixing material is composed of multiple layers including a base material, a method of adjusting the above L(T1) by selecting the type and thickness of the base material, etc. may be mentioned.
The above-mentioned peeling method is not particularly limited, and includes, for example, a normal mechanical peeling method, a peel peeling method, and the like.
The peeling angle is the angle at which the temporary fixing material is pulled with respect to the semiconductor device. Generally, the larger the peeling angle, the higher the tensile elongation rate of the temporary fixing material. The following is preferable, and 100° or more and 160° or less are more preferable.
The peeling speed is the speed at which the temporary fixing material is pulled against the semiconductor device, and generally the faster the peeling speed, the lower the tensile elongation rate, and preferably 10 mm/sec or more and 100 mm/sec or less. , more preferably 30 mm/sec or more and 70 mm/sec or less.

The peeling force of the temporary fixing material against the silicon wafer at the temperature T1 (temperature of the temporary fixing material) in the peeling step (3) is not particularly limited, but a preferable upper limit is 1 N/inch. By setting the peeling force to the silicon wafer at 1 N/inch or less, the semiconductor device can be easily peeled off from the temporary fixing material after high-temperature processing. From the viewpoint of further improving the peelability, a more preferable upper limit of the peeling force to the silicon wafer is 0.8 N/inch.
The lower limit of the peeling force to the silicon wafer is not particularly limited, but from the viewpoint of suppressing unintended peeling in the heat treatment step (2), the lower limit is preferably 0.01 N/inch, and the more preferable lower limit is 0.05 N/inch. .
In addition, the peeling force of the temporary fixing material to the silicon wafer can be measured by the following method.
After cutting the temporary fixing material into a width of 1 inch, a silicon wafer (manufactured by Aites, 8 inch silicon dummy wafer: thickness 725 ± 25 μm, P type (Boron), crystal orientation (100), resistivity 1 to 100 Ω cm , mirror finish) using a 100° C. laminator (Leon 13DX, speed memory 5, manufactured by Lamy Corporation). When the temporary fixing material is a hardening type, the temporary fixing material is cured under the conditions for performing the above-mentioned curing step (4). The cured sample is heat treated under the conditions for the heat treatment step (2). A 180° peel test is performed on the heat-treated sample at 25° C. and a tensile speed of 300 mm/min to measure the peel force (N/inch).

The form of the temporary fixing material used in the method of manufacturing a semiconductor device of the present invention is not particularly limited, and may be in the form of a liquid, paste, etc., or in the form of a sheet, film, etc. There may be. Further, the temporary fixing material may be a single layer or a plurality of layers.
Further, the temporary fixing material may be formed on the semiconductor device by curing a temporary fixing material precursor by heating as described above. In such a case, the temporary fixing material precursor is not particularly limited, but may be a fluid of silicone resin or a fluid of polyimide resin having an unreacted group of an acid dianhydride and an unreacted group of a diamine compound. It is preferable that there be.
More specifically, examples of the silicone resin fluid include a polydimethylsiloxane solution in which a polydimethylsiloxane compound and a solvent are mixed. More specifically, examples of the fluid of the polyimide resin include a polyamic acid solution in which a polyamic acid compound of pyromellitic dianhydride and 9,10-diaminophenanthrene is mixed in a solvent.

When the temporary fixing material is in the form of a sheet or film, the temporary fixing material may have an adhesive layer on one or both surfaces of the base material, and may have an adhesive layer on one or both surfaces of the base material. It may also have only an adhesive layer. When the above-mentioned base material is not included, there is no need to select a base material having both light transmittance and heat resistance, and the above-mentioned temporary fixing material has a cheaper and simpler structure.

Examples of the base material include sheets made of transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, and polyimide. Further, a sheet having a mesh structure, a sheet with holes, glass, etc. can also be used.

The thickness of the base material is not particularly limited, but from the viewpoint of increasing light transmittance and flexibility, a preferable lower limit is 5 μm, a preferable upper limit is 150 μm, a more preferable lower limit is 10 μm, and a more preferable upper limit is 100 μm. It is.

The temporary fixing material preferably contains a curable adhesive. When the temporary fixing material is in the form of a sheet or film, it is preferable that the temporary fixing material has an adhesive layer containing the curable adhesive.
The above-mentioned curable adhesive is not particularly limited as long as it is an adhesive that cures by heating or irradiation with energy rays, but it may contain a resin (1) having an imide skeleton as a repeating unit of the main chain. preferable.
The above-mentioned resin (1) having an imide skeleton as a repeating unit of the main chain has extremely excellent heat resistance due to the imide skeleton, and decomposition of the main chain is difficult to occur even when processing at a high temperature of 300°C or higher. . Therefore, by including the resin (1) having the above-mentioned imide skeleton as a repeating unit of the main chain, the above-mentioned curable adhesive can be used even when subjected to high-temperature processing at 300°C or higher. It can be easily peeled off afterwards.

The curable adhesive only needs to have reactivity as a whole, and the resin (1) itself having the imide skeleton as a repeating unit of the main chain may have reactivity. However, the resin (1) having the above-mentioned imide skeleton as a repeating unit of the main chain does not need to have reactivity itself.
In addition, when the resin (1) itself having the imide skeleton as a repeating unit of the main chain has no reactivity, the above-mentioned curable adhesive can be cured by further containing another component having a reactive functional group. The mold adhesive as a whole needs to be reactive.

The resin (1) having the above-mentioned imide skeleton as a repeating unit of the main chain is not particularly limited, but contains a carbon-carbon double bond (hereinafter also simply referred to as "carbon-carbon double bond") that has energy ray reactivity. A resin (1-I) which has a functional group and has an imide skeleton as a repeating unit of the main chain, or does not have a functional group containing a carbon-carbon double bond having energy ray reactivity, In addition, a resin (1-II) having an imide skeleton as a repeating unit of the main chain is preferable. These resins (1) having an imide skeleton as a repeating unit in the main chain may be used alone or in combination of two or more. Among them, resin (1-I) having a functional group containing the above carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain; It is more preferable to use the resin (1-II) in combination with no group and having an imide skeleton as a repeating unit of the main chain. By using these together, the curable adhesive has better curability, higher heat resistance, and less internal stress during reaction.

By containing the resin (1-I) which has a functional group containing a carbon-carbon double bond and an imide skeleton as a repeating unit of the main chain, the curable adhesive can be heated or energized. Curing progresses by irradiation with radiation, and the adhesive strength decreases significantly, so it can be easily peeled off even after high-temperature processing.
The above-mentioned functional group containing a carbon-carbon double bond is not particularly limited, and examples thereof include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acrylic group, and a group containing these. . These carbon-carbon double bond-containing functional groups may be substituted. Among these, maleimide groups, substituted maleimide groups, allyl groups, and substituted allyl groups are preferable because higher heat resistance can be obtained.

The resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is a functional group containing a carbon-carbon double bond. The equivalent weight (weight average molecular weight/number of functional groups containing carbon-carbon double bonds) is preferably 4,000 or less. When the functional group equivalent is 4000 or less, the curable adhesive can be more easily peeled off even after high-temperature processing. This is thought to be because the presence of a functional group containing the carbon-carbon double bond at a density above a certain level in the resin molecule shortens the distance between crosslinks, thereby further suppressing the promotion of adhesion. The functional group equivalent is more preferably 3,000 or less, and even more preferably 2,000 or less. Although the lower limit of the functional group equivalent is not particularly limited, the lower limit is substantially about 600.

The resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain has a weight average molecular weight (Mw) of 1000 or more and 30,000 or less. It is preferable that there be. When the weight average molecular weight (Mw) is within the above range, the curable adhesive has improved heat resistance, improved flexibility of the cured product, and can exhibit high conformability to the adherend. After high-temperature processing, it can be peeled off more easily. Further, if the weight average molecular weight (Mw) is within the above range, the resin (1-I ) can also be prevented from becoming too low in solubility in the solvent. The weight average molecular weight (Mw) is more preferably 1,500 or more and less than 20,000, and even more preferably 5,000 or more and less than 10,000.
In addition, the said weight average molecular weight is measured as a polystyrene equivalent molecular weight by gel permeation chromatography (GPC) method. More specifically, using an APC system (manufactured by Waters or equivalent), mobile phase THF, flow rate 1.0 mL/min, column temperature 40°C, sample concentration 0.2% by weight, RI/PDA detection. It can be measured under the conditions of the instrument. As the column, HR-MB-M 6.0×150 mm (product name, manufactured by Waters Co., Ltd., or an equivalent product thereof), etc. can be used.

The resin (1-I) having a functional group containing the carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain has the functional group containing the carbon-carbon double bond, It may be present either in the side chain or at the end. The resin (1-I) has a functional group containing the above carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain. In this case, the curable adhesive shortens the distance between crosslinks, thereby suppressing adhesion and making it easier to peel off. Furthermore, when the functional group containing the carbon-carbon double bond is located at the end, the reactivity of the functional group containing the carbon-carbon double bond becomes higher.

Specific examples of the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain include the following resins. That is, it has a structural unit represented by the following general formula (1a), a structural unit represented by the following general formula (1b), and a structural unit represented by the following general formula (1c) (provided that s> 0, t≧0, u≧0), and resins in which both ends are represented by X ¹ and X ² , respectively.

In general formulas (1a) to (1c), P ¹ , P ² and P ³ each independently represent an aromatic group, and Q ¹ is a substituted or unsubstituted linear, branched or cyclic group. represents an aliphatic group, Q ² represents a substituted or unsubstituted group having an aromatic structure, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. At least one selected from the group consisting of X ¹ , X ² and X ³ represents a functional group containing a carbon-carbon double bond having energy ray reactivity.

In the above general formulas (1a) to (1c), P ¹ , P ² and P ³ are preferably aromatic groups having 5 to 50 carbon atoms. Since P ¹ , P ² and P ³ are aromatic groups having 5 to 50 carbon atoms, the above-mentioned curable adhesive can exhibit higher heat resistance and can be subjected to high temperature processing at 300°C or higher. Even if it is, it can be easily peeled off after high-temperature processing.

In the above general formula (1a), Q ¹ is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. Since Q ¹ is a substituted or unsubstituted linear, branched, or cyclic aliphatic group having 2 to 100 carbon atoms, the above-mentioned curable adhesive has improved flexibility of the cured product and is easy to adhere to. It exhibits high conformability to the body, and can be peeled off more easily after high-temperature processing.
Further, Q ¹ is preferably an aliphatic group derived from a diamine compound as described below. Among these, from the viewpoint of increasing flexibility, solvents and other From the viewpoint of increasing compatibility with the components, Q ¹ is preferably an aliphatic group derived from dimer diamine.

More specifically, examples of the aliphatic group derived from the dimer diamine include a group represented by the following general formula (4-1), a group represented by the following general formula (4-2), and a group represented by the following general formula (4-2). At least one selected from the group consisting of a group represented by 4-3) and a group represented by the following general formula (4-4) is preferable. Among these, a group represented by the following general formula (4-2) is more preferable. Note that the optical isomerism of these groups is not particularly limited, and includes any optical isomerism.

In general formulas (4-1) to (4-4), R ¹ to R ⁸ and R ¹³ to R ²⁰ each independently represent a linear or branched hydrocarbon group. Note that * represents a bond. The bond * bonds with N in the above general formulas (1a) to (1c).

In the above general formulas (4-1) to (4-4), the hydrocarbon groups represented by R ¹ to R ⁸ and R ¹³ to R ²⁰ are not particularly limited, and may be saturated hydrocarbon groups, It may also be an unsaturated hydrocarbon group.
Among them, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R 7 and R ^{8 , R 13 and R 14 , R 15} and R ¹⁶ , R ¹⁷ and ^{R 18 ,} and R ¹⁹ It is preferable that the total number of carbon atoms in R ²⁰ is 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the curable adhesive has improved flexibility as a cured product and can exhibit high conformability to the adherend, and after high-temperature processing. It can be peeled off more easily. Further, the total number of carbon atoms is within the above range, so that the resin (1-I) has the functional group containing the carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain. The compatibility with solvents and other components also increases. The total number of carbon atoms is more preferably 9 or more, still more preferably 12 or more, even more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, still more preferably 25 or less, even more preferably 18 or less.

In the above general formula (1b), Q ² is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. Since ^Q2 is a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms, the above-mentioned curable adhesive can exhibit higher heat resistance and can be processed at high temperatures of 300°C or higher. Even when performing this process, it can be easily peeled off after high-temperature processing.

In the above general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. Since R is a substituted or unsubstituted branched aliphatic group having 2 to 100 carbon atoms or an aromatic group, the above-mentioned curable adhesive improves the flexibility of the cured product and is resistant to the adherend. It can exhibit high followability and can be peeled off more easily after high-temperature processing.

In the above general formula (1c), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or the aromatic ether group in R is bonded to X ³ is preferred.
Here, the term "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and the term "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. . By using an aromatic group in the part that binds to the ester group or ether group, the above-mentioned curable adhesive can exhibit higher heat resistance, and can be used in high-temperature processing at 300°C or higher. Even if there is, it can be easily peeled off after high-temperature processing. On ^{the other hand, since X 3 is} bonded to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in It does not interfere with polymerization and crosslinking when irradiated with.

In the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain, the functional group containing a carbon-carbon double bond (crosslinkable The unsaturated bond may be at least one selected from the group consisting of X ¹ , X ² and X ³ . When any of the above X ¹ , X ^{2 and} X ³ is a functional group other than a functional group containing a carbon-carbon double bond (a functional group having no carbon-carbon double bond), the carbon- Examples of functional groups having no carbon double bond include, each independently, an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, an amine compound, and the like. Specifically, acid anhydrides and diamine compounds that are raw materials for the resin (1-I) that has a functional group containing a carbon-carbon double bond and an imide skeleton as a repeating unit of the main chain are used. Examples include unreacted substances at one end.

In the above general formulas (1a) to (1c), s, t, and u are resins (1 -I), the content of each of the structural units represented by the above general formula (1a), the above general formula (1b), and the above general formula (1c) ( (mol%).
The content (s) of the structural unit represented by the above general formula (1a) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, More preferably it is 80 mol% or less. The content (t) of the structural unit represented by the above general formula (1b) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably is 50 mol% or less, more preferably 30 mol% or less. The content (u) of the structural unit represented by the above general formula (1c) is 0 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably is 30 mol% or less. When the content of each structural unit in the general formulas (1a) to (1c) is within the above range, the curable adhesive can be more easily peeled off after undergoing high-temperature processing.
In addition, the structural unit represented by the above general formula (1a), the structural unit represented by the above general formula (1b), and the structural unit represented by the above general formula (1c), each structural unit is continuous. It may have a block structure made up of block components arranged in such a manner that the constituent units are randomly arranged.

The method for producing the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is not particularly limited. For example, it can be obtained by preparing an imide compound by reacting a diamine compound and an aromatic acid anhydride, and then reacting, for example, maleic anhydride or the like at the end of the imide compound. Further, for example, when preparing an imide compound by reacting a diamine compound and an aromatic acid anhydride, a functional group is introduced into the imide compound, and the functional group in the imide compound is reacted with the functional group. It can also be obtained by reacting a compound having a functional group and a functional group containing a carbon-carbon double bond (also referred to as a functional group-containing unsaturated compound).
The method for introducing a functional group into the above imide compound is not particularly limited. For example, when preparing an imide compound by reacting a diamine compound and an aromatic acid anhydride, a method for introducing a functional group into the imide compound may be added to a hydroxyl group, a carboxyl group, a halogen group, etc. Examples include a method of adding a diamine compound having a functional group. The functional group-containing unsaturated compound is not particularly limited, and may be selected and used depending on the functional group in the imide compound.

As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used.
By using an aliphatic diamine compound as the diamine compound, the curable adhesive has improved flexibility as a cured product and can exhibit high conformability to the adherend. Can be easily peeled off. By using an aromatic diamine compound as the diamine compound, the curable adhesive can exhibit higher heat resistance, and even when subjected to high temperature processing at 300°C or higher, it can be After that, it can be easily peeled off. These aliphatic diamine compounds, aromatic diamine compounds, and diamine compounds having a functional group may be used alone, or two or more types may be used in combination.

Examples of the aliphatic diamine compounds include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diamino Propane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane , 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane, and the like.

Examples of the aromatic diamine compounds include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4- Diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diamino Toluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3- Bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2 , 2'-bistrifluoromethylbiphenyl, bis(amino-3-chloropheny)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis (4-amino-3-ethyldiaminofluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, -5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4- Amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, 2,2-bis(4,(4aminophenoxy)phenyl)sulfone, 2,2-bis( 4-(3-aminophenoxy)phenyl) sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenylsulfide, 3,4'-oxydianiline, 2,2-bis(4-(4- aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4 , 4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-bis(4-aminophenyl)fluorene, o- Toridine sulfone, methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-amino phenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4 , 4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylene diamines (e.g., Huntsman's Jeffamine D-230, D400, D-2000 and D-4000), Examples include 1,3-cyclohexanebis(methylamine), m-xylylene diamine, p-xylylene diamine, and the like.

Among the above aliphatic diamine compounds, resins (1-I Dimer diamine is preferred from the viewpoint of increasing compatibility with the solvent and other components.
The above-mentioned dimer diamine is a diamine compound obtained by reducing and aminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and includes, for example, linear, monocyclic, and polycyclic dimer acids. Examples include dimer diamines such as type. The dimer diamine may contain a carbon-carbon unsaturated double bond, or may be a hydrogenated product to which hydrogen is added. More specifically, the dimer diamine is, for example, a group represented by the above-mentioned general formula (4-1), a group represented by the general formula (4-2), a group represented by the general formula (4-3), etc. and dimer diamines that can constitute a group represented by general formula (4-4).

Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalene Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3, 3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1 -Trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2 , 2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2 ,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2 , 3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetra Carboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4, 3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-( Examples include 4,4'-isopropylidene diphenoxy)-bis(phthalic acid).

When the curable adhesive contains a resin (1-I) having a functional group containing the carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain, the resin (1-I) ) content is not particularly limited. The content of the resin (1-I) is determined by a preferable lower limit based on a total of 100 parts by weight of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2) described below. is 10 parts by weight. If the content of the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is 10 parts by weight or more, the above-mentioned curable adhesive Even when high-temperature processing at 300° C. or higher is performed, the agent can be easily peeled off after the high-temperature processing. From the viewpoint of further improving the releasability, a more preferable lower limit of the content of the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is The lower limit is 20 parts by weight, and the more preferable lower limit is 30 parts by weight.
The upper limit of the content of the resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is not particularly limited. From the viewpoint of further improving the releasability, the content of the resin (1-I) should be determined by combining the above-mentioned resin (1) having an imide skeleton as a repeating unit of the main chain with the polyfunctional monomer or polyfunctional oligomer (2) described below. A preferable upper limit of the total amount of 100 parts by weight is 100 parts by weight, a more preferable upper limit is 90 parts by weight, an even more preferable upper limit is 80 parts by weight, and an even more preferable upper limit is 70 parts by weight.

The resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain has a weight average molecular weight (Mw) of 20,000 or more. is preferred. By having the above-mentioned weight average molecular weight of 20,000 or more, the above-mentioned curable adhesive can exhibit higher heat resistance, and even when performing high-temperature processing at 300°C or higher, it can be used in high-temperature processing. After that, it can be easily peeled off. The weight average molecular weight is more preferably 50,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but from the viewpoint of solubility in a solvent, a preferable upper limit is 600,000, and a more preferable upper limit is 300,000.
The weight average molecular weight is measured in the same manner as the resin (1-I) which has a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain. be able to.

Specifically, as the resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain, for example, the following general formula (1d) is used. A resin having a structural unit represented by the following general formula (1e) (however, s>0, t≧0), and whose both ends are represented by X ⁴ and X ⁵ , respectively (1-ii) is mentioned.

In general formulas (1d) to (1e), P ⁴ and P ⁵ each independently represent an aromatic group, and Q ³ is a substituted or unsubstituted linear, branched or cyclic aliphatic group. represents a group, and Q ⁴ represents a group having a substituted or unsubstituted aromatic structure. X ⁴ and X ⁵ represent a functional group having no carbon-carbon double bond and having energy ray reactivity.

In the above general formulas (1d) to (1e), P ⁴ and P ⁵ are preferably aromatic groups having 5 to 50 carbon atoms. Since P ⁴ and P ⁵ are aromatic groups having 5 to 50 carbon atoms, the above-mentioned curable adhesive can exhibit higher heat resistance, and is resistant to high-temperature processing at 300°C or higher. However, it can be easily peeled off after high-temperature processing.

In the above general formula (1d), Q ³ is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. Since Q ³ is a substituted or unsubstituted linear, branched, or cyclic aliphatic group having 2 to 100 carbon atoms, the above-mentioned curable adhesive has improved flexibility of the cured product and is easy to adhere to. It exhibits high conformability to the body, and can be peeled off more easily after high-temperature processing.
Moreover, it is preferable that Q ³ is an aliphatic group derived from a diamine compound as described above. Among these, from the viewpoint of increasing flexibility, solvents for the resin (1-II) that does not have the above-mentioned functional group containing a carbon-carbon double bond, and has an imide skeleton as a repeating unit of the main chain, etc. From the viewpoint of increasing compatibility with the component, Q ³ is preferably an aliphatic group derived from dimer diamine.
That is, in the above-mentioned curable adhesive, the resin (1-I) has a functional group containing the above carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain, and the above-mentioned carbon-carbon At least one of the resin (1-II) that does not have a functional group containing a double bond and has an imide skeleton as a repeating unit of the main chain has an aliphatic group derived from a dimer diamine. preferable. That is, it is preferable that the resin (1) having the imide skeleton as a repeating unit of the main chain has an aliphatic group derived from dimer diamine.

In the above general formula (1e), Q ⁴ is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. Since ^Q4 is a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms, the above-mentioned curable adhesive can exhibit higher heat resistance and can be processed at high temperatures of 300°C or higher. Even when performing this process, it can be easily peeled off after high-temperature processing.

^The functional groups having no carbon-carbon double bond represented by X ⁴ and Examples include compounds. Specifically, acid anhydrides and diamine compounds that are raw materials for the resin (1-II) that does not have a functional group containing a carbon-carbon double bond and have an imide skeleton as a repeating unit of the main chain. Examples include unreacted products at one end.

In the above general formulas (1d) to (1e), s and t are resins (1 -II) corresponds to the respective contents (mol %) of the structural unit represented by the above general formula (1d) and the structural unit represented by the above general formula (1e).
The content (s) of the structural unit represented by the above general formula (1d) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, More preferably it is 80 mol% or less. The content (t) of the structural unit represented by the above general formula (1e) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably is 50 mol% or less, more preferably 30 mol% or less. When the content of each structural unit in the general formulas (1d) to (1e) is within the above range, the curable adhesive can be more easily peeled off after undergoing high-temperature processing.
The structural unit represented by the above general formula (1d) and the structural unit represented by the above general formula (1e) have a block structure consisting of block components in which the respective structural units are consecutively arranged. It may have a random structure in which each constituent unit is randomly arranged.

The method for producing the resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain is not particularly limited. It can be obtained by reacting with an aromatic acid anhydride. The diamine compound and the aromatic acid anhydride are used in resin (1-I) which has a functional group containing a carbon-carbon double bond as described above and has an imide skeleton as a repeating unit of the main chain. It may be the same as the diamine compound and aromatic acid anhydride.

When the above-mentioned curable adhesive does not have the above-mentioned functional group containing a carbon-carbon double bond and contains a resin (1-II) having an imide skeleton as a repeating unit of the main chain, the resin (1- The content of II) is not particularly limited. The content of the resin (1-II) is determined by a preferable lower limit based on a total of 100 parts by weight of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2) described below. is 20 parts by weight. If the content of the resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain is 20 parts by weight or more, the curable type Even if the adhesive is subjected to high-temperature processing at 300° C. or higher, it can be easily peeled off after the high-temperature processing. From the viewpoint of further improving the releasability, a more preferable lower limit of the content of the resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain. is 30 parts by weight.
There is no particular upper limit to the content of the resin (1-II) which does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain. From the viewpoint of further improving the releasability, the content of the resin (1-II) should be determined by combining the above-mentioned resin (1) having an imide skeleton as a repeating unit of the main chain with the polyfunctional monomer or polyfunctional oligomer (2) described below. A preferable upper limit of the total amount of 100 parts by weight is 90 parts by weight, and a more preferable upper limit is 80 parts by weight.

Preferably, the curable adhesive further contains a polyfunctional monomer or polyfunctional oligomer having two or more functional groups containing energy ray-reactive carbon-carbon double bonds in the molecule. Among these, polyfunctional monomers or polyfunctional oligomers (2) (hereinafter simply referred to as " It is more preferable to include a polyfunctional monomer or a polyfunctional oligomer (2).
By containing the polyfunctional monomer or polyfunctional oligomer (2), the curable adhesive can be cured more fully when heated or irradiated with energy rays, and its adhesive strength is significantly reduced. , it can be peeled off more easily even after high-temperature processing.

As described above, if the resin (1) itself having the imide skeleton as a repeating unit of the main chain has no reactivity, the curable adhesive may further contain another component having a reactive functional group. Therefore, the curable adhesive as a whole needs to have reactivity. It is preferable to use the above polyfunctional monomer or polyfunctional oligomer (2) as the other component having such a reactive functional group. In the case where the resin (1) itself having the imide skeleton as a repeating unit of the main chain has no reactivity, for example, if the resin (1) having the imide skeleton as a repeating unit of the main chain has the carbon-carbon double Examples include the case where the resin (1-II) contains only the resin (1-II) that does not have a functional group containing a bond and has an imide skeleton as a repeating unit of the main chain.

The functional group containing a carbon-carbon double bond in the polyfunctional monomer or polyfunctional oligomer (2) is not particularly limited, and includes, for example, a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acrylic group, and groups containing these. These carbon-carbon double bond-containing functional groups may be substituted. Among these, maleimide groups, substituted maleimide groups, allyl groups, and substituted allyl groups are preferable because higher heat resistance can be obtained.

It is preferable that the polyfunctional monomer or polyfunctional oligomer (2) has an aliphatic group derived from a diamine compound. As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used, but an aliphatic diamine compound is preferable. By using an aliphatic diamine compound as the diamine compound, the curable adhesive has improved flexibility as a cured product and can exhibit high conformability to the adherend. Can be easily peeled off.

Among the aliphatic diamine compounds, the above-mentioned dimer diamines are preferred from the viewpoint of increasing flexibility and increasing the compatibility of the polyfunctional monomer or polyfunctional oligomer (2) with the solvent and other components. preferable. That is, in the method for manufacturing a semiconductor device of the present invention, at least one selected from the group consisting of the resin (1) having the above-mentioned imide skeleton as a repeating unit of the main chain, and the above-mentioned polyfunctional monomer or polyfunctional oligomer (2) is used. Preferably, one type has an aliphatic group derived from a dimer diamine.

The content of the polyfunctional monomer or oligomer (2) is not particularly limited, but the total content of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or oligomer (2) The preferable lower limit to 100 parts by weight is 5 parts by weight. If the content of the polyfunctional monomer or polyfunctional oligomer (2) is within the above range, the curable adhesive can be more easily peeled off after undergoing high-temperature processing. From the viewpoint of further improving the releasability, the lower limit of the content of the polyfunctional monomer or oligomer (2) is more preferably 10 parts by weight, and the upper limit is 50 parts by weight.

The curable adhesive has a functional group containing the carbon-carbon double bond and an imide skeleton as a repeating unit of the main chain (1-I) and the polyfunctional monomer or polyfunctional oligomer ( 2), the total content thereof is not particularly limited. The above resin (1-I) and the above multifunctional monomer or multifunctional oligomer account for a total of 100 parts by weight of the resin (1) having the above imide skeleton as a repeating unit of the main chain and the above multifunctional monomer or multifunctional oligomer (2). The preferable lower limit of the total content with oligomer (2) is 20 parts by weight, and the preferable upper limit is 80 parts by weight. If the total content of the resin (1-I) and the polyfunctional monomer or polyfunctional oligomer (2) is within the above range, the curable adhesive can be more easily peeled off after high-temperature processing. can do. From the viewpoint of further improving the releasability, the lower limit of the total content of the resin (1-I) and the polyfunctional monomer or polyfunctional oligomer (2) is more preferably 30 parts by weight, and even more preferably 40 parts by weight. A more preferable lower limit is 50 parts by weight, and a more preferable upper limit is 70 parts by weight.

Preferably, the curable adhesive further contains a silicone compound or a fluorine compound.
The silicone compound or fluorine compound has excellent heat resistance, so it prevents the curable adhesive from burning even after high-temperature processing at 300°C or higher, and bleeds out to the interface of the adherend during peeling, preventing peeling. Make it easier.
The above-mentioned silicone compound is not particularly limited, and examples thereof include silicone oil, silicone diacrylate, silicone-based graft copolymer, and the like. The above-mentioned fluorine compound is not particularly limited, and includes, for example, a hydrocarbon compound having a fluorine atom.

The silicone compound or fluorine compound preferably has a functional group capable of crosslinking with the resin (1) having the imide skeleton as a repeating unit of the main chain.
Since the silicone compound or fluorine compound has a functional group that can be crosslinked with the resin (1) having the imide skeleton as a repeating unit of the main chain, the silicone compound or fluorine compound can be The compound chemically reacts with the resin (1) having the imide skeleton as a repeating unit of the main chain. As a result, the silicone compound or fluorine compound is incorporated into the resin (1) having the imide skeleton as a repeating unit of the main chain. Therefore, it is possible to prevent the silicone compound or fluorine compound from adhering to the adherend and contaminating it.

The functional group that can be crosslinked with the resin (1) having the imide skeleton as a main chain repeating unit is not particularly limited, and includes, for example, a functional group containing a carbon-carbon double bond, a carboxy group, a hydroxy group, an amide group, Examples include isocyanate groups and epoxy groups. Among these, functional groups containing carbon-carbon double bonds are preferred. That is, the silicone compound or fluorine compound preferably has a functional group containing a carbon-carbon double bond. The functional group containing a carbon-carbon double bond is not particularly limited as long as it contains a carbon-carbon double bond (radically polymerizable unsaturated bond), and examples thereof include a maleimide group, a citraconimide group, and a vinyl ether group. group, allyl group, (meth)acrylic group, nadimide group, and groups containing these. These carbon-carbon double bond-containing functional groups may be substituted.

Among these, from the viewpoint of being environmentally friendly and easy to dispose of, silicone compounds having a functional group capable of crosslinking with the resin (1) having the imide skeleton as a repeating unit in the main chain are preferred. The silicone compound having a functional group crosslinkable with the resin (1) having an imide skeleton as a repeating unit of the main chain has a siloxane skeleton in the main chain and contains a carbon-carbon double bond in the side chain or terminal. A silicone compound having a functional group is preferred.
The silicone compound having a siloxane skeleton in its main chain and a functional group containing a carbon-carbon double bond in its side chain or terminal is not particularly limited, but includes silicone compounds represented by the following general formula (I), the following: It is preferable to contain at least one selected from the group consisting of a silicone compound represented by the general formula (II) and a silicone compound represented by the following general formula (III). These silicone compounds have particularly high heat resistance and high polarity, so they can be easily bleed out from the curable adhesive.

In the above general formula (I), general formula (II), and general formula (III), X and Y each independently represent an integer of 0 to 1200, and R is a functional group containing a carbon-carbon double bond. represents a group.

In the general formula (I), general formula (II), and general formula (III), examples of the functional group containing a carbon-carbon double bond represented by R include a maleimide group, a citraconimide group, and a vinyl ether group. , an allyl group, a (meth)acrylic group, a nadimide group, and a group containing these. These carbon-carbon double bond-containing functional groups may be substituted. Among these, maleimide groups, substituted maleimide groups, allyl groups, and substituted allyl groups are preferable because higher heat resistance can be obtained. In addition, in the above general formula (I), general formula (II), and general formula (III), when a plurality of R's exist, the plurality of R's may be the same or different.

Commercially available silicone compounds represented by the above general formula (I), general formula (II), and general formula (III) include, for example, EBECRYL350 and EBECRYL1360 (all manufactured by Daicel Cytec). It will be done. Further examples include BYK-UV3500 (manufactured by BYK Chemie), TEGO RAD2250 (manufactured by Evonik) (R is an acrylic group in each case), and Megafac RS-56 (manufactured by DIC, silicone and fluorine atom-containing compound).

The content of the silicone compound or fluorine compound is not particularly limited, but is preferably based on a total of 100 parts by weight of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2). The lower limit is 0.1 parts by weight, and the preferable upper limit is 20 parts by weight. When the content of the silicone compound or fluorine compound is within this range, the curable adhesive can exhibit excellent releasability without contaminating the adherend. From the viewpoint of further improving releasability while suppressing contamination, the lower limit of the content of the silicone compound or fluorine compound is preferably 0.3 parts by weight, and the upper limit is more preferably 10 parts by weight.
In addition, since the above-mentioned curable adhesive has excellent heat resistance, sufficient effects can be exhibited even if the content of the above-mentioned silicone compound or fluorine compound is relatively small. Therefore, the possibility of contamination by the silicone compound or fluorine compound can be further reduced.

It is preferable that the above-mentioned curable adhesive further contains a polymerization initiator.
The polymerization initiator is not particularly limited, but at least one selected from the group consisting of photopolymerization initiators and thermal polymerization initiators is preferable, and photopolymerization initiators are more preferable.

Examples of the above-mentioned photopolymerization initiators include those activated by irradiation with light having a wavelength of 250 to 800 nm. Among these, the absorption wavelength of the resin (1) having the above-mentioned imide skeleton as a repeating unit of the main chain is difficult to overlap, and the above-mentioned photopolymerization is sufficiently activated when the above-mentioned curable adhesive is irradiated with energy rays. The initiator preferably contains a photopolymerization initiator having a molar extinction coefficient of 1 or more at 405 nm. The photopolymerization initiator more preferably contains a photopolymerization initiator with a molar extinction coefficient of 200 or more at 405 nm, and still more preferably contains a photopolymerization initiator with a molar extinction coefficient of 350 or more at 405 nm. . The upper limit of the molar absorption coefficient at 405 nm of the photopolymerization initiator having a molar absorption coefficient at 405 nm of 1 or more is not particularly limited, but the upper limit is, for example, 2000, 1500, etc.
Examples of the photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoinpropyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, and phosphine oxide derivative compounds. etc. Furthermore, initiation of photoradical polymerization of bis(η5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenylpropane, etc. Examples include agents. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the polymerization initiator is not particularly limited, but the preferable lower limit is based on a total of 100 parts by weight of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2). The amount is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the polymerization initiator is within this range, the entire curable adhesive will be uniformly and quickly polymerized and crosslinked by heating or irradiation with energy rays, and the elastic modulus will increase. This can prevent the adhesion from being significantly reduced, resulting in increased adhesion and the occurrence of adhesive residue upon peeling. A more preferable lower limit of the content of the polymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 3 parts by weight.

It is preferable that the above-mentioned curable adhesive further contains a gas generating agent.
The above gas generating agent has a weight loss rate at 300°C when heated from 30°C to 300°C at a heating rate of 10°C/min in a nitrogen atmosphere as measured by TG-DTA (Thermogravimetric-Differential Thermal Analysis). It is preferably 5% or less. If the weight reduction rate is 5% or less, the gas generating agent is unlikely to decompose even when subjected to high-temperature processing at 300°C or higher, and the curable adhesive exhibits higher heat resistance. be able to.
Note that the TG-DTA (thermogravimetric-differential thermal analysis) measurement can be performed using, for example, a TG-DTA device (STA7200RV, manufactured by Hitachi High-Tech Science Co., Ltd., or its equivalent).

Examples of the gas generating agent include gas generating agents that generate gas when heated, gas generating agents that generate gas when irradiated with light, and the like. These gas generating agents may be used alone or in combination of two or more. Among these, gas generating agents that generate gas when irradiated with light are preferred, and gas generating agents that generate gas when irradiated with ultraviolet rays are more preferred.
By containing a gas generating agent that generates gas when irradiated with light, the curable adhesive releases the gas generated when irradiated with light to the interface with the adherend. Thereby, the above-mentioned curable adhesive can be peeled off more easily. Further, even if the adherend is thin, damage to the adherend can be prevented.

Examples of the gas generating agent that generates gas upon irradiation with light include a tetrazole compound or a salt thereof, a triazole compound or a salt thereof, an azo compound, an azide compound, a xanthone acetic acid, a carbonate, and the like. These gas generating agents may be used alone or in combination of two or more. Among these, tetrazole compounds or salts thereof are preferred because they have particularly excellent heat resistance.

The content of the gas generating agent is not particularly limited, but the lower limit is preferably based on the total of 100 parts by weight of the resin (1) having the imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2). The amount is 5 parts by weight, and the preferred upper limit is 50 parts by weight. When the content of the gas generating agent is within the above range, the curable adhesive can exhibit particularly excellent releasability. A more preferable lower limit of the content of the gas generating agent is 8 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable adhesive may contain known additives such as inorganic fillers, photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, and waxes. .

When the temporary fixing material is a sheet-like, film-like, etc. temporary fixing material having an adhesive layer containing the above-mentioned curable adhesive, the thickness of the temporary fixing material (if it does not have a base material, the adhesive layer The thickness (or the sum of the thickness of the adhesive layer and the thickness of the base material when the adhesive layer has a base material) is not particularly limited, and the preferable lower limit is 5 μm and the preferable upper limit is 550 μm. When the thickness is 5 μm or more, the adhesive layer can have sufficient adhesive strength in the initial stage. When the thickness is 550 μm or less, the adhesive layer can exhibit high flexibility, can exhibit high conformability to the adherend, and can be peeled off more easily during peeling. A more preferable lower limit of the above thickness is 10 μm, an even more preferable lower limit is 20 μm, and an even more preferable lower limit is 30 μm. A more preferable upper limit of the thickness is 400 μm, an even more preferable upper limit is 300 μm, an even more preferable upper limit is 200 μm, and an even more preferable upper limit is 150 μm.

The temporary fixing material preferably has a weight loss rate of 20% or less after being heated at 280° C. for 1 hour. If the weight loss rate after heating at 280°C for 1 hour is 20% or less, even if high-temperature processing at 300°C or higher is performed with the semiconductor device temporarily fixed to the temporary fixing material, high-temperature processing can be performed. After passing through, the semiconductor device can be easily peeled off from the temporary fixing material while suppressing the residue. It is more preferable that the weight loss rate after heating at 280° C. for 1 hour is 15% or less.
The lower limit of the weight loss rate after heating at 280° C. for 1 hour is not particularly limited, and the lower the weight loss rate, the more preferable.
Incidentally, the weight loss rate of the temporary fixing material after being heated at 280° C. for 1 hour can be measured by the following method.
If the temporary fixing material is a hardening type, the temporary fixing material is cured by heating it in an oven at 170°C for 10 minutes or by irradiating it with ultraviolet rays of 405 nm and an irradiation intensity of 70 mW/ ^cm2 at 1000 mJ/ ^cm2 . . Weigh the cured sample into an aluminum pan, and set the aluminum pan into the device. In a nitrogen atmosphere, the measurement sample was heated from 25°C at a heating rate of 10°C/min using a thermogravimetric measuring device (STA7200 (manufactured by Hitachi High-Tech Science) or equivalent), and after reaching 280°C, it was heated for 1 hour. Hold. The weight loss rate after heating at 280° C. for 1 hour is calculated using the following formula.
Weight reduction rate = (initial weight - weight after heating) / initial weight x 100 (%)

The method for producing the temporary fixing material is not particularly limited, and for example, the blended components such as the resin (1) having the imide skeleton as a repeating unit of the main chain are mixed using a bead mill, ultrasonic dispersion, a homogenizer, a high-output disperser, a roll mill, etc. An example of this method is to mix the materials using a liquid or paste to produce a temporary fixing material such as a liquid or a paste. In addition, a curable adhesive obtained by mixing the compounded components such as the resin (1) having the imide skeleton as a repeating unit of the main chain with a solvent using a bead mill, ultrasonic dispersion, a homogenizer, a high-output disper, a roll mill, etc. Another example is a method in which a temporary fixing material having an adhesive layer is produced by coating an agent solution on the release-treated surface of a release film and drying it.

According to the method for manufacturing a semiconductor device of the present invention, the semiconductor device can be easily peeled off from the temporary fixing material while suppressing residue after high-temperature processing.
The thickness of the semiconductor device is not particularly limited, but a preferable lower limit is 40 μm, a preferable upper limit is 3000 μm, a more preferable lower limit is 50 μm, and a more preferable upper limit is 1500 μm.
The semiconductor device is not particularly limited, and includes, for example, a semiconductor wafer, a semiconductor chip, a semiconductor mounting board, and the like. When the semiconductor device is a semiconductor wafer, a semiconductor chip, etc., the higher the bumps (protruding electrodes) formed on the surface, the more likely the semiconductor device will be damaged and the more likely the residue of the temporary fixing material will be generated. On the other hand, according to the semiconductor device manufacturing method of the present invention, even if the semiconductor wafer, semiconductor chip, etc. has relatively high bumps, the temporary fixing material can be easily peeled off while suppressing the residue. I can do it. The height of the bump is not particularly limited, but a preferable lower limit is 5 μm, a preferable upper limit is 150 μm, a more preferable lower limit is 10 μm, and a more preferable upper limit is 100 μm.

According to the present invention, even when high-temperature processing at 300°C or higher is performed with a semiconductor device temporarily fixed to the temporary fixing material, the semiconductor device can be removed from the temporary fixing material while suppressing residue after the high-temperature processing. A method for manufacturing a semiconductor device that allows the device to be easily peeled off can be provided.

The embodiments of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited only to these Examples.

(Preparation of resin (1-I) having a functional group containing a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain)
(Synthesis example 1)
250 mL of toluene was charged to a 500 mL round bottom flask containing a Teflon stirrer. Then, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of dimer diamine (puriamin 1075, manufactured by Croda) and 19.1 g (0.09 mol) of pyromellitic anhydride were added in this order. A Dean-Stark tube and condenser were attached to the flask and the mixture was refluxed for 2 hours to form the amine-terminated diimide. After cooling the reaction mixture to room temperature or below, 12.8 g (0.13 mol) of maleic anhydride was added, followed by 5 g (0.05 mol) of methanesulfonic anhydride. The mixture was further refluxed for 12 hours, then cooled to room temperature, 300 mL of toluene was added to the flask, and impurities were precipitated and removed by standing. The resulting solution was filtered through a glass fritted funnel filled with silica gel, and the solvent was removed in vacuo, resulting in an amber wax-like product having maleimide groups at both ends represented by the following formula (A), and A resin (1-I) having an imide skeleton as a repeating unit of the main chain was obtained.
The weight average molecular weight of the obtained resin was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Inc.) as a column, and the weight average molecular weight was 5,000.

(Preparation of resin (1-II) that does not have a functional group containing a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain)
(Synthesis example 2)
250 mL of toluene was charged to a 500 mL round bottom flask containing a Teflon stirrer. Then, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of dimer diamine (puriamin 1075, manufactured by Croda) and 21.8 g (0.1 mol) of pyromellitic anhydride were added in this order. A Dean-Stark tube and condenser were attached to the flask, the mixture was refluxed for 2 hours, cooled to room temperature, 300 mL of toluene was added to the flask, and impurities were precipitated and removed by standing. After filtering the resulting solution through a glass fritted funnel filled with silica gel, the solvent was removed in vacuo to form a brown solid free of functional groups containing carbon-carbon double bonds, represented by the following formula: , and a resin (1-II) having an imide skeleton as a repeating unit of the main chain was obtained.
The weight average molecular weight of the resulting resin was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Inc.) as a column, and the weight average molecular weight was 4,000.

(Preparation of polyfunctional monomer or polyfunctional oligomer (2))
(Synthesis example 3)
250 mL of toluene was charged to a 500 mL round bottom flask containing a Teflon stirrer. 56 g (0.1 mol) of dimer diamine (puriamin 1075, manufactured by Croda) and 19.6 g (0.2 mol) of maleic anhydride were added, and then 5 g of methanesulfonic anhydride was added. After the solution was refluxed for 12 hours, it was cooled to room temperature, 300 mL of toluene was added to the flask, and the salt was precipitated and removed by standing still. After filtering the obtained solution through a glass fritted funnel filled with silica gel, the solvent was removed in vacuo to obtain a brown liquid bismaleimide monomer (2) represented by the following formula (E).

(Example 1)
(1) Production of temporary fixing material To 100 parts by weight of anisole, add 100 parts by weight of the resin (1-I) obtained above, and further add 2 parts by weight of EBECRYL350 (manufactured by Daicel Cytec) as a silicone compound, and A curable adhesive solution was prepared by adding 5 parts by weight of Omnirad 819 (manufactured by IGM Resins) as a polymerization initiator.
The obtained curable adhesive solution was coated with a doctor knife on the release-treated side of a 50 μm PET film that had been subjected to release treatment on one side so that the dry film thickness was 40 μm, and heated at 130°C. , and dried by heating for 10 minutes. As a result, a temporary fixing material (non-support type) having an adhesive layer was obtained.

(2) Weight loss rate after heating at 280° C. for 1 hour The temporary fixing material was cured by irradiating it with 1000 mJ/cm ² of ultraviolet light having a wavelength of 405 nm and an irradiation intensity of 70 mW/cm ² . The sample after curing was weighed into an aluminum pan, and the aluminum pan was set in the device. In a nitrogen atmosphere, the measurement sample was heated from 25°C at a temperature increase rate of 10°C/min using a thermogravimetric analyzer (STA7200 (manufactured by Hitachi High-Tech Science)), and after reaching 280°C, it was held for 1 hour. The weight loss rate after heating at 280° C. for 1 hour was calculated using the following formula.
Weight reduction rate = (initial weight - weight after heating) / initial weight x 100 (%)

(3) Manufacture of semiconductor devices After cutting the temporary fixing material to a width of 1 inch, TEG wafers as semiconductor devices (manufactured by WALTS Corporation, WALTS-TEG FBW100-0001JY (PI), wafer thickness 725 ± 25 μm, bump height [Temporary fixing step (1)] was carried out using a laminator (manufactured by Lamy Corporation, Leon 13DX, speed memory 5) at 100°C.
After lamination, the temporary fixing body consisting of the temporary fixing material and the semiconductor device was irradiated with 1000 mJ/cm ² of 405 nm ultraviolet light with an irradiation intensity of 70 mW/cm ² from the temporary fixing material side using an ultra-high pressure mercury lamp [curing process] (4)].
After curing, the temporary fixing body consisting of the temporary fixing material and the semiconductor device was further heated at 300° C. for 10 minutes using a hot plate [heat treatment step (2)].
Thereafter, the semiconductor device was peeled off from the temporary fixing material by a normal mechanical peeling method [peeling step (3)]. At this time, the temperature T1 of the temporary fixing material, the peeling angle of the temporary fixing material, the storage elastic modulus E'(T1) of the temporary fixing material at the temperature T1 of the temporary fixing material, and the temperature of the temporary fixing material at the temperature T1 of the temporary fixing material. The tensile elongation rate L (T1) and the peeling force of the temporary fixing material against the silicon wafer are shown in the table. In the above peeling step (3), the temporary fixing material and the semiconductor device are placed on a hot plate with the semiconductor device side in contact with the hot plate, and the temporary fixing material is peeled off. The temperature T1 was measured by measuring the temperature of the surface of the semiconductor device in contact with the temporary fixing material. The methods for measuring the storage modulus, tensile elongation, and peeling force against silicon wafers are shown below.

The storage modulus of the temporarily fixed material at a specific temperature was measured by the following method.
A test piece of 5 mm x 35 mm x 0.03 mm in thickness was prepared for the temporary fixing material. When the temporary fixing material was a curable type, the obtained test piece was cured under the conditions for performing the above-mentioned curing step (4). The sample after hardening was heat treated under the conditions for performing the above heat treatment step (2). The heat-treated sample was immersed in liquid nitrogen to cool to -50°C, and then measured using a viscoelastic spectrometer (e.g., DVA-200, manufactured by IT Kansei Control Co., Ltd.) in constant-rate heating tensile mode. The temperature was raised to 300°C at a heating rate of 10°C/min and a frequency of 10Hz, and the storage modulus was measured.

The tensile elongation rate of the temporarily fixed material at a specific temperature was measured by the following method.
Two marked lines were provided for the temporary fixing material after the temporary fixing step (1). At this time, the temporary fixing material was peeled in one direction, and the two gauge lines were set to be perpendicular to the peeling direction. Thereafter, a curing step (4), a heat treatment step (2), and a peeling step (3) were performed in the same manner as in the manufacture of the semiconductor device. The distance between the gauge lines before peeling at temperature T1 was set as A(T1), the distance between the gauge lines after peeling at temperature T1 was set as B(T1), and the tensile elongation rate L(T1) was calculated using the following formula.
L(T1)=(B(T1)-A(T1))/A(T1)

The peeling force of the temporary fixing material to the silicon wafer was measured by the following method.
After cutting the temporary fixing material into a width of 1 inch, a silicon wafer (manufactured by Aites, 8 inch silicon dummy wafer: thickness 725 ± 25 μm, P type (Boron), crystal orientation (100), resistivity 1 to 100 Ω cm , mirror finish) with a 100° C. laminator (Leon 13DX, speed memory 5, manufactured by Lamy Corporation). When the temporary fixing material was a hardening type, the temporary fixing material was cured under the conditions for performing the above-mentioned curing step (4). The sample after hardening was heat treated under the conditions for performing the above heat treatment step (2). A 180° peel test was performed on the heat-treated sample under conditions of 25° C. and a tensile speed of 300 mm/min, and the peel force (N/inch) was measured.

(Examples 2-6, 9-14, Comparative Examples 1-3)
A temporary fixing material was obtained in the same manner as in Example 1 except for the changes shown in Tables 1 and 2. We also manufactured semiconductor devices. Note that the materials shown below were used.
・Acrylic adhesive (SK-1, manufactured by Shin Nakamura Chemical Co., Ltd.)
・Multifunctional acrylate (trifunctional acrylate, NK ester A-TMPT, manufactured by Shin Nakamura Chemical Co., Ltd.)
・Crosslinking agent (isocyanate-based crosslinking agent, L45-K, manufactured by Soken Chemical Co., Ltd.)

(Example 7)
(1) Production of temporary fixing material precursor (polyimide resin fluid) A reaction vessel equipped with a heating and cooling device and a stirring device was prepared. In this reaction vessel, in a nitrogen atmosphere, 12.89 g of aromatic diamine oligomer (manufactured by Ihara Chemical Co., Ltd., Elasmer 1000, molecular weight 1229.7) was added to 68.33 g of N,N-dimethylacetamide (DMAc). 7.08 g of 4,4'-diaminodiphenyl ether (DDE, molecular weight 200.2) and 10.0 g of pyromellitic dianhydride (PMDA) were reacted by stirring at 70° C. for 5 hours. As a result, a temporary fixing material precursor (polyimide resin fluid) was obtained.

(2) Weight loss rate after heating at 280°C for 1 hour The temporary fixing material precursor (polyimide resin fluid) was applied to a slide glass and dried at 90°C for 20 minutes. Thereafter, the temporary fixing material precursor (polyimide resin fluid) was heated and cured at 300° C. for 2 hours in a nitrogen atmosphere, thereby forming a film made of the temporary fixing material with a thickness of 50 μm. The sample after film formation was peeled off or scraped off the slide glass, weighed into an aluminum pan, and the aluminum pan was set in the apparatus. In a nitrogen atmosphere, the measurement sample was heated from 25°C at a temperature increase rate of 10°C/min using a thermogravimetric analyzer (STA7200 (manufactured by Hitachi High-Tech Science)), and after reaching 280°C, it was held for 1 hour. The weight loss rate after heating at 280° C. for 1 hour was calculated using the following formula.
Weight reduction rate = (initial weight - weight after heating) / initial weight x 100 (%)

(3) Manufacture of semiconductor devices The temporary fixing material precursor (polyimide resin fluid) was used as a TEG wafer (manufactured by WALTS Corporation, WALTS-TEG FBW100-0001JY (PI), wafer thickness 725 ± 25 μm, bump height 50 μm) and dried at 90° C. for 20 minutes. Thereafter, the temporary fixing material precursor (polyimide resin fluid) was cured by heating at 300°C for 2 hours in a nitrogen atmosphere to form a film of the temporary fixing material with a thickness of 50 μm [temporary fixing step (1)]. )].
After the film formation, the temporary fixing body consisting of the temporary fixing material and the semiconductor device was further heated at 300° C. for 10 minutes using a hot plate [heat treatment step (2)].
Thereafter, the semiconductor device was peeled off from the temporary fixing material by a normal mechanical peeling method [peeling step (3)]. At this time, the temperature T1 of the temporary fixing material is 50°C, the peeling angle of the temporary fixing material is 120°, and the storage elastic modulus E'(T1) of the temporary fixing material at the temperature T1 of the temporary fixing material is 2.56×10 ⁶ Pa, the tensile elongation rate L (T1) of the temporary fixing material at the temperature T1 of the temporary fixing material was 0.6, and the peeling force of the temporary fixing material against the silicon wafer was 0.4 N/inch. The methods for measuring the storage modulus, tensile elongation, and peeling force against the silicon wafer were the same as in Example 1.

(Example 8)
(1) Production of temporary fixing material precursor (silicone resin fluid) 900 parts by weight of toluene was placed in a four-necked flask, and 90 parts by weight of raw rubber-like dimethylpolysiloxane with both molecular chain ends blocked with hydroxyl groups, (CH ₃ ) ₃ 10 parts by weight of a methylpolysiloxane resin consisting of 0.75 mol of SiO _1/2 units and 1 mol of SiO _4/2 units and containing 1.0 mol % of hydroxyl groups in 100% solid content was dissolved. To the obtained solution, 1 part by weight of 28% aqueous ammonia was added, and the mixture was stirred at room temperature for 24 hours to cause a condensation reaction. Next, the mixture was heated to 180° C. under reduced pressure to remove toluene, condensed water, ammonia, etc., to obtain a solidified partial condensate. To 100 parts by weight of this partial condensate, 900 parts by weight of toluene was added and dissolved. 20 parts by weight of hexamethyldisilazane was added to this solution, and the mixture was stirred at 130° C. for 3 hours to block the remaining hydroxyl groups. Next, the mixture was heated to 180° C. under reduced pressure to remove the solvent and the like to obtain a solidified non-reactive partial condensate. Further, 900 parts by weight of hexane was added to 100 parts by weight of the above non-reactive partial condensate and dissolved, and then this was poured into 2000 parts by weight of acetone, the precipitated resin was collected, and then the mixture was dissolved under vacuum. By removing hexane and the like, a dimethylpolysiloxane polymer having a weight average molecular weight of 900,000 and containing 0.05% by mass of low molecular weight components having a molecular weight of 740 or less was obtained. 20 g of this polymer was dissolved in 80 g of isododecane and filtered through a 0.2 μm membrane filter to obtain a solution of dimethylpolysiloxane polymer in isododecane.

(2) Weight loss rate after heating at 280°C for 1 hour By applying a temporary fixing material precursor (fluid silicone resin) to a slide glass and curing it by heating at 150°C for 5 minutes, the temporary fixing material can be removed. A film was formed. The sample after film formation was peeled off or scraped off the slide glass, weighed into an aluminum pan, and the aluminum pan was set in the apparatus. In a nitrogen atmosphere, the measurement sample was heated from 25°C at a temperature increase rate of 10°C/min using a thermogravimetric analyzer (STA7200 (manufactured by Hitachi High-Tech Science)), and after reaching 280°C, it was held for 1 hour. The weight loss rate after heating at 280° C. for 1 hour was calculated using the following formula.
Weight reduction rate = (initial weight - weight after heating) / initial weight x 100 (%)

(3) Manufacture of semiconductor devices The temporary fixing material precursor (fluid silicone resin) is used as a TEG wafer (manufactured by WALTS Corporation, WALTS-TEG FBW100-0001JY (PI), wafer thickness 725 ± 25 μm, bump height A film made of the temporary fixing material was formed by applying the film to a thickness of 50 μm) and curing by heating at 150° C. for 5 minutes [temporary fixing step (1)].
After the film formation, the temporary fixing body consisting of the temporary fixing material and the semiconductor device was further heated at 300° C. for 10 minutes using a hot plate [heat treatment step (3)].
Thereafter, the semiconductor device was peeled off from the temporary fixing material by a normal mechanical peeling method [peeling step (3)]. At this time, the temperature T1 of the temporary fixing material is 50°C, the peeling angle of the temporary fixing material is 120°, and the storage elastic modulus E'(T1) of the temporary fixing material at the temperature T1 of the temporary fixing material is 2.56×10 ⁶ Pa, the tensile elongation rate L (T1) of the temporary fixing material at the temperature T1 of the temporary fixing material was 0.6, and the peeling force of the temporary fixing material against the silicon wafer was 0.4 N/inch. The methods for measuring the storage modulus, tensile elongation, and peeling force against the silicon wafer were the same as in Example 1.

<Evaluation>
The manufacturing of semiconductor devices in Examples and Comparative Examples was evaluated by the following method. The results are shown in Tables 1 and 2.

(1) Damage to semiconductor devices (yield)
The manufacturing of semiconductor devices performed in Examples and Comparative Examples was performed on 20 semiconductor devices, and the failure rate of the semiconductor devices after the peeling step (3) was determined.
◎: Damage rate of semiconductor devices is less than 5% 〇: Damage rate of semiconductor devices is 5% or more, less than 25% △: Damage rate of semiconductor devices is 25% or more, less than 50% ×: Damage rate of semiconductor devices is 50% or more

(2) Residue Regarding the manufacturing of semiconductor devices conducted in Examples and Comparative Examples, the ratio of the area to which the residue was attached to the area of the surface of the semiconductor device after the peeling step (3) (residue adhesion rate) was determined. .
◎: Residue adhesion rate on the surface of the semiconductor device less than 5% 〇: Residue adhesion rate on the surface of the semiconductor device 5% or more but less than 25% △: Residue adhesion rate on the surface of the semiconductor device 25% or more and less than 50% ×: Residue on the surface of the semiconductor device Adhesion rate 50% or more

According to the present invention, even when high-temperature processing at 300°C or higher is performed with a semiconductor device temporarily fixed to the temporary fixing material, the semiconductor device can be removed from the temporary fixing material while suppressing residue after the high-temperature processing. A method for manufacturing a semiconductor device that allows the device to be easily peeled off can be provided.

Claims (10)

a temporary fixing step (1) of temporarily fixing the temporary fixing material to the semiconductor device;
a heat treatment step (2) of performing heat treatment on the semiconductor device;
a peeling step (3) of peeling off the heat-treated semiconductor device from the temporary fixing material, in this order;
A method for manufacturing a semiconductor device, characterized in that in the peeling step (3), the heat-treated semiconductor device is peeled from the temporary fixing material under conditions that satisfy the following formulas (F1) and (F2).
E'(T1)≦3×10 ⁷ (F1)
0.080<L(T1)<2.0 (F2)
In formula (F1), T1 represents the temperature (°C) of the semiconductor device that the temporary fixing material contacts in the peeling step (3), and E'(t) represents the temperature t in the peeling step (3). represents the storage elastic modulus (Pa) of the temporarily fixed material, and E'(T1) represents the value of E'(t) when the temperature t=T1. In formula (F2), T1 represents the temperature (°C) of the semiconductor device with which the temporary fixing material comes into contact in the peeling step (3), and L(t) represents the temperature (°C) at the temperature t in the peeling step (3). It represents the tensile elongation rate of the temporary fixing material, and L(T1) represents the value of L(t) when the temperature t=T1. 2. The method of manufacturing a semiconductor device according to claim 1, wherein the temporary fixing material has a weight reduction rate of 20% or less after being heated at 280° C. for 1 hour. In the temporary fixing step (1), after applying a temporary fixing material precursor to the semiconductor device, the temporary fixing material precursor is cured by heating to form the temporary fixing material on the semiconductor device. The method of manufacturing a semiconductor device according to claim 1 or 2, characterized in that: 4. The temporary fixing material precursor is a fluid of silicone resin or a fluid of polyimide resin having an unreacted group of an acid dianhydride and an unreacted group of a diamine compound. A method for manufacturing a semiconductor device. 3. The method of manufacturing a semiconductor device according to claim 1, wherein in the temporary fixing step (1), the temporary fixing material is bonded to the semiconductor device. The temporary fixing material has an adhesive layer containing a curable adhesive, and the curable adhesive includes a resin (1) having an imide skeleton as a repeating unit of the main chain, and a resin (1) containing an energy ray reaction in the molecule. The semiconductor according to claim 5, characterized in that it contains a polyfunctional monomer or polyfunctional oligomer (2) having two or more functional groups containing a carbon-carbon double bond having a property and a molecular weight of 5000 or less. Method of manufacturing the device. The resin (1) has the imide skeleton as a repeating unit of the main chain, and the resin (1) has two or more functional groups containing a carbon-carbon double bond having energy ray reactivity in the molecule, and has a molecular weight of 5000 or less. 7. The method of manufacturing a semiconductor device according to claim 6, wherein at least one selected from the group consisting of a certain polyfunctional monomer or polyfunctional oligomer (2) has an aliphatic group derived from dimer diamine. 3. The method of manufacturing a semiconductor device according to claim 1, wherein in the peeling step (3), the T1 is 25° C. or more and 120° C. or less. 3. The method of manufacturing a semiconductor device according to claim 1, wherein in the peeling step (3), the peeling angle of the temporary fixing material is 90° or more and 180° or less. 3. The method of manufacturing a semiconductor device according to claim 1, wherein the peeling force of the temporary fixing material against the silicon wafer at the temperature T1 in the peeling step (3) is 1 N/inch or less.