Composition, temporary fixing composition, and method for manufacturing wafer using the same

Abstract

To provide a composition capable of forming a temporary fixing layer that is less likely to leave residues on a wafer.SOLUTION: A composition has a peel strength XPI of 0.50 N / mm or less, as measured using a measurement method employing polyimide as a test substrate, a peel strength YPI of 0.10 N / mm or more, as measured using the measurement method employing polyimide as the test substrate, and a ratio XPI / YPI of the peel strength XPI to the peel strength YPI is 1.5 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a temporary fixing composition, and a method for manufacturing a wafer using the same. [Background technology]

[0002] In the manufacturing process of a semiconductor device, a semiconductor substrate or the like (hereinafter simply referred to as a "wafer") is subjected to processing such as forming an insulating film, forming a circuit, thinning by grinding and polishing, etc. In this case, in the thinning step or the like, in order to prevent the wafer from cracking, the wafer and a supporting member such as a glass plate are bonded together via a temporary fixing composition, and after the predetermined processing step, the supporting member is sometimes peeled off from the wafer.

[0003] For example, Patent Document 1 discloses, as such a temporary fixing composition, a monofunctional (meth)acrylate, a polyfunctional (meth)acrylate, a polyisobutene homopolymer and / or a polyisobutene copolymer, each having an alkyl group with 18 or more carbon atoms in the side chain and a homopolymer Tg of −100° C. to 60° C., and a photoradical polymerization initiator. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2021 / 235406 Summary of the Invention [Problem to be solved by the invention]

[0005] When the temporary fixing composition is peeled off from the wafer, a cured product of the temporary fixing composition may remain partially on the surface of the wafer. In addition, in the case of a wafer having a pattern made of polyimide, aluminum, or the like on its surface, the adhesiveness to the temporary fixing composition varies depending on the type of member exposed on the wafer surface, and therefore the degree of remaining cured product varies.

[0006] Further investigations have revealed that even if the type of member exposed on the wafer surface is the same, the degree to which the cured material remains varies depending on the processing process that the bonded body of the wafer and the support member bonded via the temporary fixing composition undergoes. For example, even if the type of member exposed on the wafer surface is the same, that is, polyimide, the degree to which the cured material remains varies depending on whether or not the bonded body has undergone a predetermined heat treatment as a processing process.

[0007] Incidentally, there are various types of temporary fixing compositions, including a type that is cured (bonded) by light irradiation and decomposed (peeled) by laser light irradiation, a type that is cured by heating and decomposed by laser light irradiation, and a type that is cured and decomposed by heating. Among these, the temporary fixing composition that is cured (bonded) by light irradiation and decomposed (peeled) by laser light irradiation has the advantage of being less affected by heat on the semiconductor substrate.

[0008] However, in the first type of temporary fixing composition, if the bondability by light irradiation is improved, the peelability by laser light irradiation is likely to decrease, and there is a risk that a cured product of the temporary fixing composition will remain on the bonding surface of the wafer during peeling. On the other hand, if the wafer bondability is poor, the support member will peel off during the processing step, making it difficult to prevent cracks in the wafer.

[0009] The present invention has been made in view of the above problems, and aims to solve any of the above problems. One object of the present disclosure is to provide a composition capable of forming a temporary fixing layer that is unlikely to remain on a wafer due to the effects of the processing process, a temporary fixing composition, and a wafer manufacturing method using the same. Another object of the present disclosure is to provide a composition capable of forming a temporary fixing layer that has excellent laser releasability and is unlikely to remain on a wafer, a temporary fixing composition, and a wafer manufacturing method using the same. [Means for solving the problem]

[0010] As a result of intensive research to achieve the above object, the present inventors have found that when a wafer is heat-treated, the adhesive strength between the temporary fixing layer and the wafer increases excessively, resulting in the temporary fixing layer remaining. Based on this finding, the present inventors have discovered that a composition that satisfies predetermined conditions for the peel strength when heat-treated and the peel strength when not heat-treated can solve at least one of the above problems, and that it is possible to provide, for example, a composition that can form a temporary fixing layer that is less likely to remain on the wafer due to the effects of the processing process, a temporary fixing composition, and a method for manufacturing a wafer using the same, thereby completing the present invention.

[0011] Furthermore, as a result of intensive research into achieving the above-mentioned object, the present inventors have found that a composition in which the hydrocarbon chain concentration and the aromatic ring concentration are within predetermined ranges can solve at least one of the above-mentioned problems, and can provide, for example, a composition capable of forming a temporary fixing layer that has excellent laser releasability and is unlikely to remain on a wafer, a temporary fixing composition, and a method for manufacturing a wafer using the same, and have completed the present invention.

[0012] That is, the present disclosure includes the following embodiments. [1] Peel strength X measured by the following measurement method (X) using polyimide as the test substrate PI is 0.50N / mm or less, Peel strength Y measured by the following measurement method (Y) using polyimide as the test substrate PI is 0.10 N / mm or more, The peel strength Y PI The peel strength X PI Ratio of X PI / Y PI is less than or equal to 1.5, composition. (X) Peel strength is measured by the following steps (i) to (iv). (i) The composition is applied to a test substrate to a thickness of 70 μm, and after laminating a glass plate, the composition is photocured to form a coating film. (ii) Heat the test substrate on which the coating film is formed at 175°C for 30 minutes. (iii) For the coating film, an energy density of 920 mJ / cm 2 was applied at a wavelength of 355 nm and a frequency of 40 kHz. 2 After irradiating the glass plate with the laser beam, the glass plate is peeled off. (iv) A peeling tape is attached to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under the conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, and the average value of 5 measurements is taken. (Y) In the measurement method (X), the peel strength is measured without carrying out the step (ii). [2] The ratio X PI / Y PI is 0.30 to 1.0, [1] The composition described in [1]. [3] Peel strength X measured by the above measurement method (X) using aluminum as a test substrate Al is 0.60N / mm or less, Peel strength Y measured by the above measurement method (Y) using aluminum as a test substrate Al is 0.10 N / mm or more, The peel strength Y Al The peel strength X Al Ratio of X Al / Y Al is less than or equal to 2.0, The composition according to [1] or [2]. [4] The ratio X Al / Y Al is 1.0 to 2.0, [3] The composition described in [3]. [5] The peel strength X Al The peel strength X PI Ratio of X PI / X Al is 0.10 to 0.50, The composition according to [3] or [4]. [6] Peel strength X measured by the above measurement method (X) using silicon as a test substrate Si is 0.50N / mm or less, Peel strength Y measured by the above measurement method (Y) using silicon as a test substrate Si is 0.10 N / mm or more, The peel strength Y Si The peel strength X Si Ratio of X Si / Y Si is less than 1.6, The composition according to any one of [1] to [5]. [7] The ratio X Si / Y Si is 0.3 to 1.2, [6] The composition described in [6]. [8] comprising a polymerizable compound A and a photopolymerization initiator B, The composition according to any one of [1] to [7]. [9] The polymerizable compound A is a polymerizable compound A1 having a hydrocarbon chain having 3 or more carbon atoms, and containing a polymerizable compound A2 having an aromatic ring, [8] The composition described in [8].

[10] the polymerizable compound A1 contains a (meth)acrylate having a hydrocarbon chain with 3 or more carbon atoms and a functional group equivalent of 200 g / mol or less; [9] The composition described in [9].

[11] the polymerizable compound A1 contains a (meth)acrylate having a hydrocarbon chain having 8 or more carbon atoms; The composition according to [9] or

[10] .

[12] The polymerizable compound A2 contains a (meth)acrylate having an aromatic ring equivalent of 200 g / mol or less. The composition according to any one of [9] to

[11] .

[13] the content of the polymerizable compound A1 is 50 parts by mass to 98 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [9] to

[12] .

[14] the content of the polymerizable compound A2 is 2 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [9] to

[13] .

[15] the content of the photopolymerization initiator B is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [8] to

[14] .

[16] A temporary fixing composition containing the composition according to any one of [1] to

[15] .

[17] a step of bonding a wafer and a support member via the temporary fixing composition according to

[16] ; a step of curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together via the temporary fixing layer; heat treating the wafer; irradiating the temporary fixing layer with laser light; and peeling the support member and the wafer at the interface of the temporary fixing layer, Wafer manufacturing method.

[18] further comprising a step of removing the temporary fixing layer from the wafer after the laser light irradiation.

[17] The manufacturing method described in

[17] .

[19] Peel strength Y measured by the following measurement method (Y) using polyimide as the test substrate PI The peel strength X measured by the following measurement method (X) using polyimide as the test substrate against PI Ratio of X PI / Y PI is less than or equal to 1.5, composition. (X) Peel strength is measured by the following steps (i) to (iv). (i) The composition is applied to a test substrate to a thickness of 70 μm, and after laminating a glass plate, the composition is photocured to form a coating film. (ii) Heat the test substrate on which the coating film is formed at 175°C for 30 minutes. (iii) For the coating film, an energy density of 920 mJ / cm 2 was applied at a wavelength of 355 nm and a frequency of 40 kHz. 2 After irradiating the glass plate with the laser beam, the glass plate is peeled off. (iv) A peeling tape is attached to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under the conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, and the average value of 5 measurements is taken. (Y) In the measurement method (X), the peel strength is measured without carrying out the step (ii).

[0013] [1'] Contains a polymerizable compound A and a photopolymerization initiator B, The concentration of hydrocarbon chains having 3 or more carbon atoms is 2.80 mmol / g or more; The concentration of aromatic rings is 0.60 mmol / g or more. composition. [2'] The crosslink density of the cured product after UV light irradiation is 0.10 mmol / cm 3 That's all. The composition described in [1']. [3'] the ratio of the concentration of the hydrocarbon chain having 3 or more carbon atoms to the concentration of the aromatic ring is 1.5 or more; The composition according to [1'] or [2']. [4'] the polymerizable compound A includes at least one selected from the group consisting of a polymerizable compound A1 having a hydrocarbon chain with 3 or more carbon atoms, a polymerizable compound A2 having an aromatic ring, and a polymerizable compound A3 having a hydrocarbon chain with 3 or more carbon atoms and an aromatic ring; The composition according to any one of [1'] to [3']. [5'] At least one of the polymerizable compound A1 and the polymerizable compound A3 contains a (meth)acrylate having a hydrocarbon chain having 3 or more carbon atoms and a functional group equivalent of 200 g / mol or less. The composition according to [4']. [6'] At least one of the polymerizable compound A1 and the polymerizable compound A3 contains a (meth)acrylate having a hydrocarbon chain having 8 or more carbon atoms. The composition according to [4'] or [5']. [7'] the polymerizable compound A2 and the polymerizable compound A3 each contain at least one (meth)acrylate having an aromatic ring equivalent of 200 g / mol or less; The composition according to any one of [4'] to [6']. [8'] the content of the polymerizable compound A1 is 50 parts by mass to 98 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [4'] to [7']. [9'] the content of the polymerizable compound A2 is 2 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [4'] to [8']. [10'] the content of the polymerizable compound A3 is 0 parts by mass to 48 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [4'] to [9']. [11'] the content of the photopolymerization initiator B is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition according to any one of [1'] to [10']. [12'] the polymerizable compound A contains a monofunctional polymerizable compound and a polyfunctional polymerizable compound, the content of the monofunctional polymerizable compound is 0.01 parts by mass to 60 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional polymerizable compound; The composition according to any one of [1'] to [11']. [13'] The viscosity at 23°C is 500 mPa·s to 10,000 mPa·s. The composition according to any one of [1'] to [12']. [14'] A temporary fixing composition containing the composition according to any one of [1'] to [13']. [15'] a step of bonding a wafer and a support member via the temporary fixing composition according to [14']; a step of curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together via the temporary fixing layer; processing the wafer; irradiating the temporary fixing layer with laser light; and peeling the support member and the wafer at the interface of the temporary fixing layer, Wafer manufacturing method. [16'] further comprising a step of removing the temporary fixing layer from the wafer after the laser light irradiation. The manufacturing method described in [15']. [Effects of the Invention]

[0014] According to one aspect of the present disclosure, it is possible to provide a composition capable of forming a temporary fixing layer that is less likely to remain on a wafer due to the influence of a processing process, a temporary fixing composition, and a method for manufacturing a wafer using the same.

[0015] According to one aspect of the present disclosure, it is possible to provide a composition capable of forming a temporary fixing layer that has excellent laser releasability and is unlikely to remain on a wafer, a temporary fixing composition, and a method for manufacturing a wafer using the same. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is an example of a flowchart showing the wafer manufacturing method of the present embodiment in terms of a surface (front surface) in the thickness direction of the wafer. [Figure 2] 10 is another example of a flowchart showing the wafer manufacturing method of the present embodiment in terms of a surface (front surface) in the thickness direction of the wafer. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. However, the present invention is not limited to the following embodiment, and various modifications are possible without departing from the gist of the present invention.

[0018] In this specification, for example, when a numerical range is expressed as "1 to 100," it is intended to include both the lower limit value "1" and the upper limit value "100." The same applies to other numerical ranges.

[0019] [First embodiment] 1. Composition and temporary fixing composition The composition of this embodiment has a peel strength X measured by the following measurement method (X) using polyimide as a test substrate. PI The peel strength Y measured by the following measurement method (Y) using polyimide as the test substrate is 0.50 N / mm or less. PI is 0.10N / mm or more, and the peel strength Y PI Peel strength X against PI Ratio of X PI / Y PI However, it is less than 1.5. (X) Peel strength is measured by the following steps (i) to (iv). (i) A temporary fixing composition is applied to a test substrate to a thickness of 70 μm, and after laminating a glass plate, the temporary fixing composition is photocured to form a coating film. (ii) Heat the test substrate with the coating film formed at 175°C for 30 minutes. (iii) For coatings, the energy density is 920 mJ / cm at a wavelength of 355 nm and a frequency of 40 kHz. 2 After irradiating the glass with the laser beam, the glass plate is peeled off. (iv) Peeling tape is attached to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under the following conditions: peeling direction 180 degrees, peeling width 20 mm, peeling speed 120 mm / min, and temperature 25°C, and the average value of 5 measurements is taken. (Y) In the measurement method (X), the peel strength is measured without performing the step (ii). The composition of the present embodiment is preferably a temporary fixing composition. Hereinafter, the composition will be described using the temporary fixing composition as an example, but its use is not limited to temporary fixing. The temporary fixing composition of the present embodiment may contain the composition of the present embodiment, or may consist solely of the composition of the present embodiment.

[0020] Before describing the temporary fixing composition of this embodiment, first, a description will be given of a mode of use of the temporary fixing composition. Fig. 1 shows an example of a flowchart illustrating the method for manufacturing a wafer of this embodiment in terms of the thickness direction of the wafer.

[0021] First, in step S0 of FIG. 1 , a temporary fixing composition 10 is applied to one surface of a wafer W by spin coating or the like, and the wafer W and a support member 20 are bonded together via the temporary fixing composition 10. Then, in step S1, the temporary fixing composition 10 is irradiated with light such as ultraviolet light via the support member 20. In step S1, the temporary fixing composition 10 is irradiated with light, whereby a polymerization reaction of a polymerizable compound A is initiated by a photopolymerization initiator B in the temporary fixing composition 10, and a photocured temporary fixing layer 11 is formed. This bonds the wafer W and the support member 20 together via the temporary fixing layer 11. The support member 20 is not particularly limited, but examples thereof include a light-transmitting substrate such as glass. The surface of the wafer W to which the temporary fixing composition 10 is applied may be an element-forming surface.

[0022] Here, the element forming surface of the wafer W may have exposed a semiconductor material surface such as silicon, which is the base material of the wafer, or may have exposed an electrode material surface such as aluminum, or an insulating material surface such as polyimide.

[0023] As described above, in this specification, the term "temporary fixing composition" refers to a composition used to temporarily fix the wafer W to the support member 20. In addition, in this specification, a layer of a cured product obtained by irradiating the temporary fixing composition with light is referred to as a "temporary fixing layer."

[0024] Next, in step S2, a desired processing process is performed on the wafer W reinforced by bonding to the support member 20. The example in Fig. 1 shows a step of performing a heat treatment such as annealing on the wafer W, but in addition to this, the back surface of the wafer W may be ground with a grinder to thin the wafer W.

[0025] Then, in step S3, the temporary fixing layer 11 is irradiated with laser light through the support member 20. In step S3, by irradiating the temporary fixing layer 11 with laser light, the polymer of the polymerizable compound in the temporary fixing layer 11 is at least partially decomposed, and the bonding strength between the temporary fixing layer 11 and the support member 20 is reduced, so that in step S4, the support member 20 can be peeled off from the temporary fixing layer 11.

[0026] Finally, in step S5, tape 30 is attached to the temporary fixing layer 11 after the laser light irradiation, and then peeled off in the direction of the arrow, thereby peeling off the temporary fixing layer 11 from the wafer W. At this time, the peel strength of the temporary fixing layer 11 relative to the element-forming surface of the wafer W varies depending on the content of the processing process in step S2, and a cured product remains due to the influence of the processing process. Therefore, it is expected that a certain temporary fixing composition cannot be used in a wide range of processing processes.

[0027] In contrast, in this embodiment, in a peel strength test using polyimide as a test substrate and having steps (i) to (iv) corresponding to the above steps S0 to S5, the peel strength X PI and the peel strength Y without heat treatment step (ii) PI By specifying the ratio of these, it is possible to form a temporary fixing layer that is less likely to remain due to the effects of the processing process. The details of the peel strength test will be described later, but steps S0 and S1 correspond to process (i), step S2 corresponds to process (ii), steps S3 and S4 correspond to process (iii), and step S5 corresponds to process (iv).

[0028] The temporary fixing composition of this embodiment will be described in detail below.

[0029] 1.1.Peel strength Peel strength X obtained by measurement method (X) in which step (ii) of heating at 175°C for 30 minutes is performed in the peel strength test PI is 0.50 N / mm or less, preferably 0.01 to 0.50 N / mm, 0.02 to 0.40 N / mm, 0.03 to 0.30 N / mm, or 0.04 to 0.20 N / mm. PI By keeping the peel strength X at 0.50 N / mm or less, the cured product is less likely to remain due to the influence of the processing process. PI When the adhesive strength is 0.01 N / mm or more, peeling of the wafer W from the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0030] Peel strength Y obtained by measurement method (Y) without step (ii) of heating at 175°C for 30 minutes in the peel strength test PI is 0.10 N / mm or more, preferably 0.10 to 0.70 N / mm, 0.11 to 0.60 N / mm, 0.12 to 0.55 N / mm, or 0.13 to 0.50 N / mm. PI When the peel strength Y is 0.10 N / mm or more, peeling between the wafer W and the support member due to a decrease in the adhesive strength of the temporary fixing layer during processing such as back grinding tends to be less likely to occur. PI When the strength is 0.70 N / mm or less, the cured product tends to be less likely to remain.

[0031] The above ratio X PI / Y PI is 1.5 or less, preferably 0.10 to 1.5, 0.20 to 1.3, 0.23 to 1.2, 0.25 to 1.1, or 0.30 to 1.0. PI / Y PI By keeping the ratio X to 1.5 or less, the hardened material is less likely to remain due to the influence of the processing process. PI / Y PIWhen the thickness is within the above range, peeling between the wafer W and the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0032] Peel strength X PI , peel strength Y PI , and the ratio X PI / Y PI In order to make the content of the polymerizable compound fall within the above range, there are no particular limitations, but examples of the method include adjusting the proportion of hydrophobic components having a hydrocarbon chain with three or more carbon atoms in the components contained in the temporary fixing composition, adjusting the proportion of hydrophilic components having a polar group, or adjusting the proportion of components having an aromatic ring that has high absorbance of laser light and increases the decomposition efficiency by laser light irradiation.

[0033] Specifically, from the viewpoint of reducing the adhesion after heating to highly polar polyimide, the peel strength X can be increased by increasing the amount of polymerizable compounds having a hydrocarbon chain with three or more carbon atoms. PI In addition, the peel strength X may be reduced by adjusting the content of the photopolymerization initiator and the polymerizable compound or by using a polyfunctional polymerizable compound polymer. PI and peel strength Y PI Furthermore, from the viewpoint of reducing the adhesive strength after laser light irradiation, the amount of the polymerizable compound having an aromatic ring may be increased to adjust the peel strength X PI and peel strength Y PI The ratio X may be reduced. PI / Y PI For the peel strength X by the above method PI and peel strength Y PI can be adjusted as a result of the adjustment of

[0034] In addition, although the above description is given of the case where polyimide is used as the test substrate as an example of the insulating part, in a peel strength test using aluminum as an example of the electrode part or silicon as an example of the semiconductor substrate as the test substrate, the peel strength X after the step (ii) of heating at 175°C for 30 minutes was Al ,X siand the peel strength Y when the step (ii) is not performed. Al ,Y si This makes it possible to prevent the hardened material from remaining due to the processing process on patterned wafers having surfaces made of various materials such as aluminum and silicon in addition to polyimide. These peel strengths are described in detail below.

[0035] Peel strength X obtained by measurement method (X) in which step (ii) of heating at 175°C for 30 minutes is performed in the peel strength test Al is preferably 0.60 N / mm or less, 0.10 to 0.60 N / mm, 0.15 to 0.50 N / mm, or 0.20 to 0.40 N / mm. Al By keeping the peel strength X at 0.60 N / mm or less, the cured product is less likely to remain due to the influence of the processing process. Al When the adhesive strength is 0.10 N / mm or more, peeling of the wafer W from the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0036] Peel strength Y obtained by measurement method (Y) without step (ii) of heating at 175°C for 30 minutes in the peel strength test Al is preferably 0.10 N / mm or more, 0.10 to 0.60 N / mm, 0.12 to 0.45 N / mm, or 0.15 to 0.30 N / mm. Al When the peel strength Y is 0.10 N / mm or more, peeling between the wafer W and the support member due to a decrease in the adhesive strength of the temporary fixing layer during processing such as back grinding tends to be less likely to occur. Al When the strength is 0.60 N / mm or less, the cured product tends to be less likely to remain.

[0037] The above ratio X Al / Y Al is preferably 2.0 or less, 1.0 to 2.0, 1.1 to 1.9, 1.2 to 1.8, or 1.3 to 1.7.Al / Y Al By keeping the ratio X below 2.0, the hardened material is less likely to remain due to the influence of the processing process. Al / Y Al When the thickness is within the above range, peeling between the wafer W and the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0038] Peel strength X Al , peel strength Y Al , and the ratio X Al / Y Al In order to make the content of the polymerizable compound fall within the above range, there are no particular limitations, but examples of the method include adjusting the proportion of hydrophobic components having a hydrocarbon chain with three or more carbon atoms in the components contained in the temporary fixing composition, adjusting the proportion of hydrophilic components having a polar group, or adjusting the proportion of components having an aromatic ring that increases the decomposition efficiency by laser light irradiation.

[0039] Specifically, the peel strength X can be increased or decreased by increasing or decreasing the amount of polymerizable compounds having a hydrocarbon chain with three or more carbon atoms. Al The peel strength X may be adjusted by adjusting the content of the photopolymerization initiator and the polymerizable compound or by using a polyfunctional polymerizable compound. Al and peel strength Y Al Furthermore, from the viewpoint of reducing the adhesive strength after laser light irradiation, the amount of the polymerizable compound having an aromatic ring may be increased to adjust the peel strength X Al and peel strength Y Al The ratio X may be reduced. Al / Y Al For the peel strength X by the above method Al and peel strength Y Al can be adjusted as a result of the adjustment of

[0040] Peel strength X obtained by measurement method (X) in which step (ii) of heating at 175°C for 30 minutes is performed in the peel strength test Siis preferably 0.50 N / mm or less, 0.05 to 0.50 N / mm, 0.10 to 0.40 N / mm, or 0.15 to 0.30 N / mm. Si By keeping the peel strength X at 0.50 N / mm or less, the cured product is less likely to remain due to the influence of the processing process. Si When the adhesive strength is 0.05 N / mm or more, peeling of the wafer W from the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0041] Peel strength Y obtained by measurement method (Y) without step (ii) of heating at 175°C for 30 minutes in the peel strength test Si is preferably 0.10 N / mm or more, 0.10 to 0.60 N / mm, 0.12 to 0.45 N / mm, or 0.15 to 0.30 N / mm. Si When the peel strength Y is 0.10 N / mm or more, peeling between the wafer W and the support member due to a decrease in the adhesive strength of the temporary fixing layer during processing such as back grinding tends to be less likely to occur. Si When the strength is 0.60 N / mm or less, the cured product tends to be less likely to remain.

[0042] The above ratio X Si / Y Si is preferably 1.6 or less, 0.2 to 1.6, 0.3 to 1.2, 0.5 to 1.1, or 0.6 to 1.0. Si / Y Si By keeping the ratio X to 1.6 or less, the hardened material is less likely to remain due to the influence of the processing process. Si / Y Si When the thickness is within the above range, peeling between the wafer W and the support member due to a decrease in adhesive strength of the temporary fixing layer tends to be less likely to occur during processing such as heat treatment or back grinding.

[0043] Peel strength X Si , peel strength Y Si , and the ratio XSi / Y Si In order to make the content of the polymerizable compound fall within the above range, there are no particular limitations, but examples of the method include adjusting the proportion of hydrophobic components having a hydrocarbon chain with three or more carbon atoms in the components contained in the temporary fixing composition, adjusting the proportion of hydrophilic components having a polar group, or adjusting the proportion of components having an aromatic ring that increases the decomposition efficiency by laser light irradiation.

[0044] Specifically, the peel strength X can be increased or decreased by increasing or decreasing the amount of polymerizable compounds having a hydrocarbon chain with three or more carbon atoms. Si The peel strength X may be adjusted by adjusting the content of the photopolymerization initiator and the polymerizable compound or by using a polyfunctional polymerizable compound. Si and peel strength Y Si Furthermore, from the viewpoint of reducing the adhesive strength after laser light irradiation, the amount of the polymerizable compound having an aromatic ring may be increased to adjust the peel strength X Si and peel strength Y Si The ratio X may be reduced. Si / Y Si For the peel strength X by the above method Si and peel strength Y Si can be adjusted as a result of the adjustment of

[0045] Furthermore, when the wafer W is a patterned wafer having an insulating portion and an electrode portion, from the viewpoint of ensuring that there is no difference in the degree of remaining cured material in the insulating portion, the electrode portion, and the semiconductor substrate, the peel strength X PI ,X Al ,X Si and peel strength Y PI ,Y Al ,Y Si This makes it possible to prevent the cured material from remaining due to the influence of the processing process on a patterned wafer having two component surfaces of polyimide and aluminum.

[0046] From this perspective, the ratio X PI / X Alis preferably 0.10 to 0.50, 0.11 to 0.40, 0.12 to 0.35, 0.13 to 0.30, or 0.15 to 0.25. PI / X Al By setting the value within the above range, the removal rate of the temporary fixing composition tends to be better.

[0047] Also, the ratio X PI / X Si is preferably 0.10 to 0.50, 0.12 to 0.40, 0.15 to 0.38, 0.16 to 0.35, or 0.18 to 0.30. PI / X Si By setting the value within the above range, the removal rate of the temporary fixing composition tends to be better.

[0048] As described above, in the peel strength test of this embodiment, the peel strength is measured using polyimide, aluminum, or silicon as the test substrate, but the peel strength should not be interpreted as being a specific value for polyimide, aluminum, or silicon. PI ,Y PI has technical significance as a reference value for the peel strength X, Y of insulating parts made of polyimide-like materials, and the peel strength X of aluminum Al ,Y Al has technical significance as a reference value for the peel strength X, Y of the electrode part made of a material similar to aluminum. Si ,Y Si has technical significance as a reference value for the peel strength X, Y of semiconductor substrates made of silicon-like materials.

[0049] Next, the peel strength test will be described in detail. In this specification, the peel strength when heat treatment is performed is measured by the above-mentioned measurement method (X). The measurement method (X) corresponds to the manufacturing conditions when a wafer is temporarily fixed to a support member using the temporary fixing composition of this embodiment and then the wafer is heat treated.

[0050] In step (i), a temporary fixing composition is applied to a test substrate to a thickness of 70 μm, and after a glass plate is bonded to the test substrate, the temporary fixing composition is photocured to form a coating film. Step (i) corresponds to the bonding step S0 and the curing step S1 in the wafer manufacturing method described below.

[0051] In step (i), the method for applying the temporary fixing composition is not particularly limited as long as it can apply the temporary fixing composition to a thickness of 70 μm, and examples thereof include spin coating, screen printing, and various coaters, among which spin coating is preferred. Spin coating is a method in which the temporary fixing composition, which is a liquid composition, is dropped onto a wafer or a support member and then rotated at a predetermined rotation speed, thereby applying the composition to the surface of a substrate.

[0052] In step (i), when the temporary fixing composition is photocured, for example, ultraviolet light may be irradiated. The wavelength of the ultraviolet light may be in the range of, for example, 350 to 405 nm. The ultraviolet light has an energy amount in the range of 350 to 405 nm of, for example, 1 to 20,000 mJ / cm. 2 , preferably 1000 to 10000 mJ / cm 2 It is preferable to irradiate the film so that the ultraviolet light reaches a temperature of 1000 to 2000° C. The ultraviolet light irradiation conditions may be those described in the Examples. The formed coating film corresponds to a temporary fixing layer formed from the temporary fixing composition of this embodiment.

[0053] In step (ii), the test substrate on which the coating film has been formed is heated for 30 minutes at 175° C. Step (ii) corresponds to the heat treatment step S2 in the wafer manufacturing method described below.

[0054] In step (iii), the coating film is irradiated with light having a wavelength of 355 nm and a frequency of 40 kHz at an energy density of 920 mJ / cm 2 After the laser beam is irradiated, the glass plate is peeled off. Step (iii) corresponds to the laser beam irradiation step S3 and the peeling step S4 in the wafer manufacturing method described below.

[0055] In step (iii), the laser light to be irradiated may be irradiated under the conditions of a spot diameter of 150 μm and a pulse energy of 165 μJ, and may be irradiated under the conditions described in the Examples.

[0056] In step (iv), a peeling tape is applied to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25° C. The average value of five measurements is taken as the measured value. Step (iv) corresponds to the removal step S5 in the wafer manufacturing method described below.

[0057] In step (iv), the peeling tape may be a dicing tape used to fix a workpiece in a dicing process in the manufacture of semiconductors, electronic components, and optical components, and the tape used in the examples may be used. The peel strength in step (iv) may be measured under the conditions described in the examples.

[0058] In this specification, the peel strength without heat treatment is measured by the above-mentioned measurement method (Y). The measurement method (Y) corresponds to the production conditions when a wafer is temporarily fixed to a support member using the temporary fixing composition of this embodiment, and the wafer is processed without being heat treated.

[0059] 1.2.Viscosity The viscosity of the temporary fixing composition at 23° C. is preferably 500 to 10,000 mPa·s, 600 to 9,000 mPa·s, 700 to 8,000 mPa·s, 800 to 7,000 mPa·s, or 1,000 to 6,000 mPa·s. When the viscosity at 23° C. is within the above range, the application properties of the temporary fixing composition are further improved.

[0060] The viscosity at 23° C. can be controlled by adjusting the blending ratio of the components contained in the temporary fixing composition. For example, the viscosity of the temporary fixing composition can be reduced by increasing the blending amount of a component with a low viscosity.

[0061] Viscosity at 23°C is measured according to JIS Z8803:2011 at a temperature of 23°C and a shear rate of 1 sec. -1 The viscosity can be measured, for example, by an E-type viscometer (for example, at a rotation speed of 10 rpm or 2 rpm), and a cone plate can be used as the measuring jig. Specifically, the viscosity can be measured by the method described in the examples.

[0062] 1.3.Composition The temporary fixing composition of this embodiment can be cured by irradiation with ultraviolet light, and the temporary fixing layer formed thereby can be decomposed by irradiation with laser light, and the composition is not particularly limited as long as the peel strength requirement is met. The temporary fixing composition may contain, for example, a polymerizable compound A and a photopolymerization initiator B. In this case, the temporary fixing composition can be cured by irradiation with ultraviolet light. When the temporary fixing composition is irradiated with ultraviolet light, the photopolymerization initiator B is activated by the ultraviolet light, and polymerization of the polymerizable compound A is initiated. When the polymerization of the polymerizable compound A is completed, a temporary fixing layer is formed. The temporary fixing composition may further contain components other than the polymerizable compound A and the photopolymerization initiator B.

[0063] 1.3.1. Polymerizable compound A The polymerizable compound A is not particularly limited as long as it is a compound having one or more polymerizable functional groups, and examples thereof include polymerizable compound A1 having a hydrocarbon chain with 3 or more carbon atoms, polymerizable compound A2 having an aromatic ring, polymerizable compound A3 having a hydrocarbon chain with 3 or more carbon atoms (hereinafter also referred to as a "long hydrocarbon chain") and an aromatic ring, and other polymerizable compounds A4.

[0064] Among these, the polymerizable compound A preferably contains at least one selected from the group consisting of polymerizable compound A1, polymerizable compound A2, and polymerizable compound A3, and more preferably contains at least polymerizable compound A1 and polymerizable compound A2. By adjusting the contents of polymerizable compounds A1 to A3, the concentrations of hydrocarbon chains having 3 or more carbon atoms and aromatic rings in the temporary fixing composition can be controlled. In this embodiment, polymerizable compound A1 does not have an aromatic ring, polymerizable compound A2 does not have a long hydrocarbon chain, and polymerizable compound A4 does not have either an aromatic ring or a long hydrocarbon chain. The polymerizable compounds A1 to A4 may each independently be used alone or in combination of two or more.

[0065] In this embodiment, the polymerizable functional group is not particularly limited, but examples thereof include groups having a carbon-carbon double bond, such as a vinyl group, an allyl group, a butenyl group, an ethynyl group, an acryloyl group, an acryloyloxy group, an acryloylamino group, a methacryloyl group, a methacryloyloxy group, a methacryloylamino group, a vinyloxy group, a vinylamino group, a cyclopropyl group, and a cyclobutyl group. Among these, a group containing an ethylenic double bond is preferred, and a (meth)acryloyl group is more preferred. That is, the polymerizable compound A preferably contains a (meth)acrylate.

[0066] The content of the polymerizable compound A is preferably 50 to 99.9 mass%, 70 to 99.5 mass%, 80 to 99.2 mass%, 90 to 99.0 mass%, or 95 to 98.8 mass%, relative to the total amount of the temporary fixing composition. When the content of the polymerizable compound A is within the above range, there is a tendency that the cured product is less likely to remain.

[0067] Each polymerizable compound will be described in detail below.

[0068] The polymerizable compound A1 is not particularly limited as long as it has a hydrocarbon long chain and one or more polymerizable functional groups. Examples thereof include monofunctional polymerizable compounds such as isostearyl (meth)acrylate; 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate (which may have 1 to 10 repeating units), neopentyl glycol di(meth)acrylate, C1 to C6 20 Examples of suitable polyfunctional polymerizable compounds include alkoxylated hydrogenated bisphenol A di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate; and polymers having polymerizable functional groups (hereinafter also referred to as "macromonomers") containing, as monomer units, (meth)acrylate monomers containing a hydrocarbon long chain in the side chain and (meth)acrylate monomers containing a (meth)acryloyl group in the side chain. Among these, (meth)acrylates containing a hydrocarbon long chain are preferred.

[0069] Examples of (meth)acrylate monomers containing a long hydrocarbon chain in the side chain include propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and among these, butyl (meth)acrylate is preferred.

[0070] The (meth)acrylate monomer containing a (meth)acryloyl group in the side chain may be a (meth)acrylate in which the (meth)acryloyl group is bonded to the side chain via a suitable linker. The linker may be a hydrocarbon chain having 3 to 20 or 4 to 10 carbon atoms and may contain an ether bond and / or an amide bond.

[0071] The number of carbon atoms in the hydrocarbon long chain of the polymerizable compound A1 is 3 or more, preferably 3 to 20, 3 to 18, or 4 to 16, or may be 8 to 12. The polymerizable compound A1 may have hydrocarbon long chains with different numbers of carbon atoms in one molecule, and preferably contains a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms. Such a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms may be a bifunctional (meth)acrylate or a (meth)acrylate having (meth)acryloyl groups at both terminal positions of the molecular chain. The number of carbon atoms in the hydrocarbon chain is preferably 8 to 15. The content of the (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms and the content of the polymerizable compound A1 having a hydrocarbon chain with 8 or more carbon atoms are preferably 0 to 70 parts by mass, 10 to 60 parts by mass, or 20 to 55 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0072] The long hydrocarbon chain functional group equivalent of the polymerizable compound A1 is preferably 100 to 600 g / mol. The polymerizable compound A1 preferably contains a polymerizable compound having a long hydrocarbon chain functional group equivalent of 200 g / mol or less, 100 to 200 g / mol, or 110 to 190 g / mol. When the long hydrocarbon chain functional group equivalent is within the above range, residual residue of the cured product tends to be less likely to occur. The content of the polymerizable compound A1 having a long hydrocarbon chain functional group equivalent within the above range is preferably 3 to 90 parts by mass, 5 to 70 parts by mass, 10 to 60 parts by mass, or 15 to 50 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0073] The content of polymerizable compound A1 is preferably 50 to 98 parts by mass, 55 to 95 parts by mass, 60 to 92 parts by mass, or 64 to 90 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A. By setting the content of polymerizable compound A1 within the above range, there is a tendency that the cured product does not remain.

[0074] The polymerizable compound A2 is not particularly limited as long as it has an aromatic ring and one or more polymerizable functional groups. Examples of the polymerizable compound A2 include monofunctional polymerizable compounds such as phenol ethylene oxide modified (meth)acrylate (the number of repeating units of ethylene oxide is 1 to 5), 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl (meth)acrylate, and 2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole; 9,9-bis[4-(2-hydroxyC1-C 20 Alkoxy)phenyl]fluorene di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C1-C 20 Examples of suitable polyfunctional polymerizable compounds include polyfunctional (meth)acrylates containing an aromatic ring, such as 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2'-dihydroxy-4,4'-diethoxy(meth)acryloyloxybenzophenone, and 1,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tertiaryoctyl]methane.

[0075] The aromatic ring equivalent of the polymerizable compound A2 is preferably 100 to 400 g / mol. The polymerizable compound A2 preferably contains a polymerizable compound having an aromatic ring equivalent of 200 g / mol or less, 100 to 200 g / mol, or 110 to 190 g / mol. When the aromatic ring equivalent is within the above range, decomposition by laser light is further improved, and the cured product tends to be less likely to remain. The content of the polymerizable compound A2 having an aromatic ring equivalent within the above range is preferably 1 to 45 parts by mass, 2 to 40 parts by mass, 3 to 35 parts by mass, or 5 to 25 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0076] The polymerizable compound A2 preferably contains a polymerizable compound A2-1 containing a group that absorbs light with a wavelength of 350 to 385 nm. The polymerizable compound A2-1 more preferably has an absorption peak for light with a wavelength of 350 to 385 nm. While the absorption peak of an aromatic ring generally has absorption at about 200 nm, when the element adjacent to the aromatic ring is a heteroatom such as P, S, or O, the conjugation length increases, and light with a wavelength of 350 to 385 nm is absorbed. By including such a polymerizable compound A2-1, when the temporary fixing layer is irradiated with laser light, the laser light is efficiently absorbed, decomposition by the laser light is further improved, and there is a tendency for the cured product to be less likely to remain.

[0077] Examples of such polymerizable compound A2-1 include compounds having one or more skeletons selected from the group consisting of a benzophenone skeleton, a benzotriazole skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton. Among these, a phenol skeleton is preferred, and a hindered phenol skeleton is more preferred.

[0078] The content of polymerizable compound A2 is preferably 2 to 50 parts by mass, 5 to 45 parts by mass, 8 to 40 parts by mass, or 9 to 35 parts by mass relative to 100 parts by mass of the total amount of polymerizable compound A. By setting the content of polymerizable compound A2 within the above range, decomposition by laser light is further improved, and there is a tendency that the cured product is less likely to remain.

[0079] When the polymerizable compound A2 contains the polymerizable compound A2-1, the content of the polymerizable compound A2-1 is preferably 1 to 30 parts by mass, 2 to 25 parts by mass, 3 to 20 parts by mass, or 5 to 15 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A. By setting the content of the polymerizable compound A2-1 within the above range, decomposition by laser light is further improved, and there is a tendency that the cured product is less likely to remain.

[0080] The polymerizable compound A3 is not particularly limited, but examples thereof include monofunctional polymerizable compounds such as nonylphenol ethylene oxide modified (meth)acrylate (the number of repeating units of ethylene oxide is 1 to 5); 20 Examples include polyfunctional polymerizable compounds such as alkoxylated bisphenol A di(meth)acrylate.

[0081] The long hydrocarbon chain functional group equivalent of polymerizable compound A3 is preferably 100 to 800 g / mol. Polymerizable compound A3 preferably contains a polymerizable compound having a long hydrocarbon chain functional group equivalent of 500 g / mol or less, 100 to 500 g / mol, or 200 to 400 g / mol. When the long hydrocarbon chain functional group equivalent is within the above range, residual residue of the cured product tends to be less likely to occur. The content of polymerizable compound A3 having a long hydrocarbon chain functional group equivalent within the above range is preferably 0 to 48 parts by mass, 0 to 40 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A.

[0082] The aromatic ring equivalent of the polymerizable compound A3 is preferably 100 to 500 g / mol. The polymerizable compound A3 preferably contains a polymerizable compound having an aromatic ring equivalent of 500 g / mol or less, 100 to 500 g / mol, or 200 to 400 g / mol. When the aromatic ring equivalent is within the above range, decomposition by laser light is further improved, and the cured product tends to be less likely to remain. The content of the polymerizable compound A3 having an aromatic ring equivalent within the above range is preferably 0 to 40 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0083] The number of carbon atoms in the hydrocarbon long chain of polymerizable compound A3 is 3 or more, preferably 3 to 20, 3 to 18, or 4 to 16, or may be 8 to 12. Polymerizable compound A3 may have hydrocarbon long chains with different numbers of carbon atoms in one molecule, and may contain a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms. Such a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms may be a monofunctional (meth)acrylate. The number of carbon atoms in the hydrocarbon chain is preferably 8 to 15.

[0084] The content of polymerizable compound A3 is preferably 0 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more, relative to 100 parts by mass of the total amount of polymerizable compound A. Furthermore, the content of polymerizable compound A3 is preferably 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the total amount of polymerizable compound A. The content of polymerizable compound A3 may be 0 parts by mass. By setting the content of polymerizable compound A3 within the above range, decomposition by laser light is further improved, and there is a tendency that the cured product is less likely to remain.

[0085] The polymerizable compound A4 is not particularly limited, but examples thereof include 1,3-di(meth)acryloyloxyadamantane, tricyclo C 10 ~C 20 Alkanedimethanol di(meth)acrylate, dicyclo C5-C 20 Examples include polyfunctional polymerizable compounds such as di(meth)acrylate.

[0086] The content of polymerizable compound A4 is preferably 10 parts by mass or less, 0 to 5 parts by mass, or 0 to 3 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A. Polymerizable compound A4 may not be included.

[0087] Furthermore, the polymerizable compound A preferably contains a polyfunctional polymerizable compound having two or more polymerizable functional groups per molecule, and more preferably contains a monofunctional polymerizable compound having one polymerizable functional group per molecule and a polyfunctional polymerizable compound having two or more polymerizable functional groups per molecule. By including a polyfunctional polymerizable compound, the adhesive strength of the temporary fixing layer formed by curing the temporary fixing composition tends to be increased. Furthermore, by including a monofunctional polymerizable compound in addition to a polyfunctional polymerizable compound, it tends to be easier to control the concentrations of the hydrocarbon chains and aromatic rings in the temporary fixing composition.

[0088] The polyfunctional polymerizable compound is preferably a polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate may be a monomer, a macromonomer, or a mixture thereof, but preferably contains a macromonomer. The polyfunctional (meth)acrylate can be produced by the methods described in, for example, JP-A Nos. 61-207478, 61-31330, 10-278207, 9-40741, and 8-357621. In this embodiment, the weight-average molecular weight of the polyfunctional (meth)acrylate macromonomer is preferably 5,000 to 500,000, 10,000 to 300,000, 30,000 to 200,000, or 50,000 to 100,000. When the weight-average molecular weight is within the above range, the viscosity of the temporary fixing composition and the crosslink density of the cured product tend to be within preferred ranges. The polyfunctional polymerizable compound may be included as the polymerizable compound A1.

[0089] The weight-average molecular weight in this specification is a value calculated as a standard polystyrene by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight is determined by using tetrahydrofuran as a solvent, a GPC system (SC-8010 manufactured by Tosoh Corporation) under the following conditions, and creating a calibration curve using commercially available standard polystyrene. Flow rate: 1.0ml / min Set temperature: 40℃ Column configuration: One Tosoh "TSK guardcolumn MP(xL)" 6.0 mm ID x 4.0 cm, and two Tosoh "TSK-GELMULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (16,000 theoretical plates), for a total of three columns (total theoretical plate count: 32,000). Sample injection volume: 100 μl (sample solution concentration 1 mg / ml) Liquid delivery pressure: 39 kg / cm 2 Detector: RI detector

[0090] The polymerizable compound A preferably contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. In this case, the content of the monofunctional polymerizable compound is preferably 0.01 to 80 parts by mass, 0.50 to 70 parts by mass, 1.0 to 68 parts by mass, or 3.0 to 67 parts by mass, relative to 100 parts by mass of the total amount of the polyfunctional polymerizable compounds. By setting the content of the monofunctional polymerizable compound within the above range, it tends to be less likely that the cured product will remain, and it also tends to be easier to adjust the viscosity and heat resistance.

[0091] 1.3.2. Photopolymerization initiator B The photopolymerization initiator B is preferably a photoradical polymerization initiator, and more preferably a compound whose molecules are cleaved and split into two or more radicals upon irradiation with ultraviolet light or visible light, for example.

[0092] The photopolymerization initiator B may be selected from compounds that exhibit appropriate absorption characteristics by measuring their absorbance. Specifically, the photopolymerization initiator B may be selected from one or more compounds that, when dissolved at a concentration of 0.1% by mass in a solvent (e.g., acetonitrile, toluene, etc.) that does not have a maximum absorption in the wavelength region of 300 to 500 nm, satisfy one or more of the following conditions: absorbance at a wavelength of 365 nm is 0.5 or more; absorbance at a wavelength of 385 nm is 0.5 or more; and absorbance at a wavelength of 405 nm is 0.5 or more.

[0093] As the photopolymerization initiator B, one or more compounds selected from acylphosphine oxide compounds, titanocene compounds, and α-aminoalkylphenone compounds are preferred because they have excellent reaction speed and heat resistance after curing. These compounds tend to have an absorption wavelength range up to approximately 440 nm and are preferred because they have low absorbance at the wavelength of light used in the process of irradiating the temporary fixing layer with laser light. In other words, the photopolymerization initiator B is a photopolymerization initiator that can initiate radical polymerization with light of a longer wavelength. This allows for a larger difference between the wavelength of the light irradiated when curing the temporary fixing composition and the wavelength of the laser light irradiated when decomposing the temporary fixing layer. Alternatively, an oxime ester compound can be selected as the photopolymerization initiator B.

[0094] Examples of the acylphosphine oxide compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.

[0095] Examples of titanocene compounds include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

[0096] Examples of the α-aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and the like.

[0097] Examples of oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), etc. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.

[0098] From the viewpoint of exhibiting high absorbance in the wavelength region of 365 to 405 nm, the photopolymerization initiator B is preferably 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and more preferably bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0099] Also preferred is bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, which exhibits absorption in the longer wavelength range of 400 to 500 nm.

[0100] The content of the photopolymerization initiator B is preferably 0.01 to 10 parts by mass, 0.01 to 5.0 parts by mass, 0.1 to 3.0 parts by mass, or 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A. When the content of the photopolymerization initiator B is within the above range, the adhesive strength of the temporary fixing layer formed using the temporary fixing composition tends to be further increased.

[0101] 1.3.3. Other ingredients The temporary fixing composition may contain components other than the polymerizable compound A and the photopolymerization initiator B. Examples of such components include compounds that do not fall under the category of polymerizable compounds, such as compounds having an aromatic ring and compounds having a hydrocarbon chain with 3 or more carbon atoms.

[0102] 2.Applications The temporary fixing composition of this embodiment is suitably used in a wafer manufacturing method for temporarily fixing a wafer, particularly a patterned wafer, to a support member. The temporary fixing composition is preferably applied to the front surface of the wafer, and temporarily fixes the wafer to the support member for back surface processing of the wafer. The temporary fixing composition of this embodiment is unlikely to leave a cured product even when the patterned wafer is heat-treated, and therefore can be suitably used in a manufacturing method including a step of heat-treating the patterned wafer.

[0103] 3. Wafer manufacturing method As shown in FIG. 1, the method for manufacturing a wafer of this embodiment includes the steps of bonding a wafer and a support member together via the temporary fixing composition of this embodiment (hereinafter referred to as a bonding step S0), curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together via the temporary fixing layer (hereinafter referred to as a curing step S1), heat-treating the wafer (hereinafter referred to as a heat-treatment step S2), irradiating the temporary fixing layer with laser light (hereinafter referred to as a laser light irradiation step S3), and peeling the support member and the wafer at the interface of the temporary fixing layer (hereinafter referred to as a peeling step S4).

[0104] In the bonding step S0, the wafer and the support member are bonded together. The wafer is a substrate to be processed, such as a silicon substrate. The wafer is preferably a patterned wafer, more preferably a wafer on which a pattern is formed using polyimide and aluminum. The support member is preferably a support member that is at least transparent to ultraviolet light, such as a glass plate.

[0105] The bonding method in the bonding step S0 is not particularly limited, but a method in which the temporary fixing composition of the present embodiment is applied to one surface of a wafer or a support member, and then the other substrate is bonded thereto is preferred.

[0106] As a method for applying the temporary fixing composition, known application methods such as spin coating, screen printing, and various coaters can be used, but spin coating is preferred.

[0107] In the curing step S1, the temporary fixing composition is irradiated with ultraviolet light to cure the temporary fixing composition and bond the wafer and the support member. The temporary fixing composition can be easily irradiated with ultraviolet light by using a transparent substrate that transmits at least ultraviolet light as at least one of the wafer and the support member. When a substrate that transmits ultraviolet light is used as the support member, ultraviolet light may be irradiated from the support member side. Examples of transparent substrates include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic, but inorganic substrates are preferred.

[0108] The wavelength of the ultraviolet light can be appropriately selected depending on the type of photopolymerization initiator B, and may be, for example, in the range of 350 to 405 nm. The ultraviolet light has an energy amount in the range of 350 to 405 nm of, for example, 1 to 20,000 mJ / cm. 2 , preferably 1000 to 10000 mJ / cm 2 It is preferable to irradiate so that

[0109] In the heat treatment step S2, the wafer is heat treated. Heat treatment refers to processing under high temperature conditions of 170°C or higher, and the temperature condition may be 170 to 300°C. In the heat treatment step S2, the wafer may be heated and various processing may be performed. Examples of such processing include insulating film formation, circuit formation, ion implantation, etc. on the surface of the wafer opposite to the surface to which the support member is attached.

[0110] The laser light irradiation step S3 is a step S3 in which a temporary fixing layer, which is a cured temporary fixing composition, is irradiated with laser light to decompose the temporary fixing layer. The wavelength of the laser light is preferably 350 to 385 nm. The laser light may be irradiated from the wafer side or the support member side, but is preferably irradiated from the support member side. As described above, when the temporary fixing composition contains an aromatic ring bonded to a heteroatom, it tends to more easily absorb the energy of the laser light in the laser light irradiation step S3.

[0111] In the peeling step S4, the support member and the wafer are peeled off at the interface of the temporary fixing layer. In the laser light irradiation step, the temporary fixing layer is decomposed, generating gas derived from the decomposed components, and the adhesive strength at the interface between the temporary fixing layer and the wafer or the support member is reduced, allowing the wafer and the support member to be peeled off.

[0112] The wafer manufacturing method of this embodiment preferably includes a step of removing the temporary fixing layer after laser light irradiation from the wafer peeled off from the support member (hereinafter referred to as a removing step S5). By performing the removing step S5, even if the temporary fixing layer remains on the wafer, the temporary fixing layer can be sufficiently removed.

[0113] The removal step S5 can be performed by any method capable of removing the temporary fixing layer remaining on the wafer, but examples thereof include a method in which adhesive tape is applied to the wafer on which the temporary fixing layer remains, and then the adhesive tape is peeled off from the wafer. In this method, the remaining temporary fixing layer adheres to the adhesive tape, so that the temporary fixing layer can be removed when the adhesive tape is peeled off from the wafer. As the adhesive tape, for example, a dicing tape used to fix a workpiece in a dicing process in the manufacture of semiconductors, electronic components, and optical components can be used.

[0114] In the above-described wafer manufacturing method, the processing step S2 in which a desired processing process is performed on the wafer W reinforced by bonding to the support member 20 has been described as the "heat treatment step S2." However, the processing process is not limited to heat treatment, and may further include a step of processing the surface of the wafer opposite to the surface to which the support member is attached under non-heating conditions before or after the heat treatment, particularly before the heat treatment. Examples of such processing include thinning by grinding and polishing. As described above, the temporary fixing composition of this embodiment has a peel strength measured by measurement method (Y) within a predetermined range, and peeling of the wafer from the support member during the processing step described above is suppressed.

[0115] The temporary fixing composition according to the first embodiment may have the features of the temporary fixing composition according to the second embodiment, as long as there is no contradiction.

[0116] [Second embodiment] 1. Composition and temporary fixing composition The composition of the present embodiment contains a polymerizable compound A and a photopolymerization initiator B, and has a concentration of hydrocarbon chains having 3 or more carbon atoms (hereinafter also referred to as "long hydrocarbon chains") of 2.80 mmol / g or more, and a concentration of aromatic rings of 0.60 mmol / g or more. The composition of the present embodiment is preferably a temporary fixing composition. Hereinafter, the composition will be described using the temporary fixing composition as an example, but its use is not limited to temporary fixing. The temporary fixing composition of the present embodiment may contain the composition of the present embodiment, or may consist solely of the composition of the present embodiment.

[0117] Before describing the temporary fixing composition of this embodiment, a mode of use of the temporary fixing composition will be described. Fig. 2 shows an example of a flowchart illustrating the method for producing a wafer of this embodiment in terms of the thickness direction of the wafer.

[0118] First, in step S1 of FIG. 2 , a temporary fixing composition 10 is applied to one surface of a wafer W by spin coating or the like. The wafer W and a support member 20 are bonded together via the temporary fixing composition 10, and the temporary fixing composition 10 is irradiated with light such as ultraviolet light via the support member 20. In step S1, the temporary fixing composition 10 is irradiated with light, whereby a polymerization reaction of a polymerizable compound A is initiated by a photopolymerization initiator B in the temporary fixing composition 10, and a photocured temporary fixing layer 11 is formed. This bonds the wafer W and the support member 20 via the temporary fixing layer 11. The support member 20 is not particularly limited, but examples thereof include a light-transmitting substrate such as glass. The surface of the wafer W to which the temporary fixing composition 10 is applied may be a device-forming surface.

[0119] As described above, in this specification, the term "temporary fixing composition" refers to a composition used to temporarily fix the wafer W to the support member 20. In addition, in this specification, a layer of a cured product obtained by irradiating the temporary fixing composition with light is referred to as a "temporary fixing layer."

[0120] Next, in step S2, the other surface of the wafer W is ground by a grinder G to thin the wafer W. Before or after step S2, other processes such as annealing may be performed.

[0121] Then, in step S3, the temporary fixing layer 11 is irradiated with laser light through the support member 20. In step S3, by irradiating the temporary fixing layer 11 with laser light, the polymer of the polymerizable compound A in the temporary fixing layer 11 is at least partially decomposed, and the bonding strength between the temporary fixing layer 11 and the support member 20 is reduced, so that in step S4, the support member 20 can be peeled off from the temporary fixing layer 11. At this time, since the concentration of aromatic rings in the temporary fixing composition of this embodiment is equal to or greater than a predetermined value, the absorption of laser light is increased, and therefore the peelability of the support member 20 from the temporary fixing layer 11 by laser light irradiation is further improved.

[0122] Finally, in step S5, tape 30 is attached to the temporary fixing layer 11 after the laser light irradiation and peeled off in the direction of the arrow, thereby peeling off the temporary fixing layer 11 from the wafer W. The wafer W is made of a semiconductor material such as Si, and its surface is generally prone to interactions such as hydrogen bonding, for example, due to oxidation to Si-O or the like. Therefore, by setting the concentration of hydrocarbon chains having three or more carbon atoms in the temporary fixing composition of this embodiment to a predetermined value or higher, interactions such as hydrogen bonding between the temporary fixing layer 11 and the wafer W surface are reduced, and the temporary fixing layer 11 can be prevented from remaining on the wafer W surface.

[0123] As described above, the temporary fixing composition of this embodiment has excellent laser releasability and makes it possible to form a temporary fixing layer that is unlikely to remain on a wafer. The temporary fixing composition of this embodiment will be described in detail below.

[0124] 1.1. Hydrocarbon chain concentration The concentration of hydrocarbon chains having 3 or more carbon atoms is 2.80 mmol / g or more, preferably 2.90 to 50.0 mmol / g, 3.00 to 30.0 mmol / g, 3.10 to 20.0 mmol / g, 3.20 to 10.0 mmol / g, 3.30 to 6.00 mmol / g, or 3.40 to 5.20 mmol / g. A hydrocarbon long chain concentration of 2.80 mmol / g or more reduces the likelihood of residual cured material. Furthermore, a hydrocarbon long chain concentration of 50.0 mmol / g or less tends to further improve adhesion to wafers, i.e., peel strength.

[0125] In this specification, the term "hydrocarbon chain" refers to a linear or branched, saturated or unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon long chain is 3 or more, preferably 3 to 20, 3 to 18, or 4 to 16, or may be 8 to 12.

[0126] The long hydrocarbon chain may be a monovalent group present at the end of a molecule, or a divalent or higher group present within the molecule. The valence of the long hydrocarbon chain is preferably monovalent to tetravalent, monovalent to trivalent, or monovalent to divalent. The long hydrocarbon chain is preferably a saturated hydrocarbon chain, and also preferably a linear hydrocarbon chain. The hydrocarbon chain is particularly preferably a monovalent or divalent linear saturated hydrocarbon group.

[0127] The above-mentioned long hydrocarbon chain is not particularly limited, but examples thereof include monovalent saturated hydrocarbon groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; monovalent unsaturated hydrocarbon groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecinyl, and octadecynyl groups; and divalent saturated hydrocarbon groups such as propylene, butylene, pentylene, hexylene, and heptylene groups, with monovalent saturated hydrocarbon groups or divalent saturated hydrocarbon groups being preferred.

[0128] The long hydrocarbon chain may be derived from either the polymerizable compound A or the photopolymerizable initiator B. The concentration of the hydrocarbon chain having 3 or more carbon atoms can be determined from the molecular structure and content of the component contained in the temporary fixing composition. Conventionally known methods can be used for isolating the component, specifying the molecular structure such as by NMR measurement or IR measurement, and quantifying the content.

[0129] The above-mentioned hydrocarbon long chain may be contained in either the polymerizable compound A or the photopolymerizable initiator B, but is preferably contained in the polymerizable compound A, and may not be contained in the photopolymerizable initiator B.

[0130] 1.2.Aromatic ring concentration The aromatic ring concentration is 0.60 mmol / g or more, preferably 0.64 to 5.0 mmol / g, 0.68 to 4.0 mmol / g, 0.70 to 3.0 mmol / g, 0.80 to 2.5 mmol / g, 0.90 to 2.4 mmol / g, or 1.00 to 2.2 mmol / g. When the aromatic ring concentration is 0.60 mmol / g or more, the absorbency of laser light, particularly UV laser light having a wavelength in the UV region, is increased, and laser removability is further improved. In particular, in the temporary fixing composition of this embodiment, the hydrocarbon chain concentration is specified within the above range in order to reduce the amount of residual cured material. Therefore, the bond energy is high and there are many stable carbon-carbon bonds. By setting the aromatic ring concentration to 0.60 mmol / g or more, excellent laser removability can be achieved. Furthermore, by setting the concentration of aromatic rings to 5.0 mmol / g or less, the interaction between the temporary fixing layer 11 and the surface of the wafer W is reduced, and the hardened material tends to be less likely to remain.

[0131] In this specification, the term "aromatic ring" refers to a cyclic group exhibiting aromaticity. The aromatic ring may be a hydrocarbon aromatic ring composed of carbon and hydrogen, or a heteroaromatic ring containing a heteroatom other than carbon and hydrogen. The heteroaromatic ring preferably contains a nitrogen atom as a heteroatom. The aromatic ring may be a monocyclo ring such as a benzene ring, a bicyclo ring such as a naphthalene ring, or a tricyclo ring such as an anthracene ring, or an aromatic ring consisting of four or more rings, but a monocyclo ring or a bicyclo ring is preferred.

[0132] The concentration of aromatic rings is calculated by counting each ring that exhibits aromaticity as one unit. For example, even if a structure is composed of multiple rings, if a conjugated system is formed across multiple rings, such as in naphthalene or anthracene, it is counted as one aromatic ring. On the other hand, even if a structure is composed of multiple adjacent rings, if a conjugated system is not formed across multiple rings, such as in A-BPEF-2 used in the examples described below, each aromatic ring contained in the structure is counted as one aromatic ring.

[0133] The aromatic ring may be derived from either the polymerizable compound A or the photopolymerizable initiator B. The concentration of the aromatic ring can be determined from the molecular structure and content of the components contained in the temporary fixing composition. Conventionally known methods can be used for isolating the components, specifying the molecular structure such as by NMR measurement or IR measurement, and quantifying the content.

[0134] The aromatic ring may be contained in either the polymerizable compound A or the photopolymerizable initiator B, but is preferably contained in both the polymerizable compound A and the photopolymerizable initiator B.

[0135] The ratio of the concentration of the long hydrocarbon chains to the concentration of the aromatic rings is preferably 0.80 to 15, 1.0 to 10, 1.1 to 9.0, 1.2 to 8.0, or 1.3 to 7.0. When the ratio of the concentration of the long hydrocarbon chains to the concentration of the aromatic rings is within the above range, the laser peelability is further improved, and there is a tendency for the cured product to be less likely to remain.

[0136] 1.3.Crosslink density after curing The crosslink density of the cured product (temporary fixing layer) after ultraviolet light irradiation of the temporary fixing composition is preferably 0.10 mmol / cm 3 or more, 0.10 to 5.0 mmol / cm 3 , 0.20 to 3.0 mmol / cm 3 , 0.30 to 2.0 mmol / cm 3 , 0.35 to 1.0 mmol / cm 3 The crosslink density of the cured product is 0.10 mmol / cm 3 By satisfying the above conditions, the adhesive strength of the temporary fixing layer tends to be maintained even under high-temperature conditions. As a result, even if a desired heat treatment process or the like is performed before or after step S2, peeling between the wafer and the support member is suppressed during back surface processing of the wafer under high-temperature conditions. In addition, the crosslink density of the cured product is 0.10 mmol / cm 3 By satisfying the above conditions, cohesive failure is less likely to occur, and the amount of the cured product remaining tends to be further reduced.

[0137] The crosslink density of the cured product (temporary fixing layer) can be controlled by adjusting the type of polymerizable compound A. Specifically, the crosslink density after curing can be increased by increasing the content of a polymerizable compound with a small polymerizable functional group equivalent (g / mol).

[0138] The crosslink density of the cured product can be indirectly measured by measuring the storage modulus of the cured product obtained by irradiating the temporary fixing composition with ultraviolet light. Specifically, it may be measured by the method described in the examples.

[0139] 1.4.Viscosity The viscosity of the temporary fixing composition at 23° C. is preferably 500 to 10,000 mPa·s, 600 to 9,000 mPa·s, 700 to 8,000 mPa·s, 800 to 7,000 mPa·s, or 1,000 to 6,000 mPa·s. When the viscosity at 23° C. is within the above range, the application properties of the temporary fixing composition are further improved.

[0140] The viscosity at 23° C. can be controlled by adjusting the blending ratio of the components contained in the temporary fixing composition. For example, the viscosity of the temporary fixing composition can be reduced by increasing the blending amount of a component with a low viscosity.

[0141] Viscosity at 23°C was measured according to JIS Z8803:2011 at a temperature of 23°C and a shear rate of 1 sec. -1 The viscosity can be measured, for example, by an E-type viscometer (for example, at a rotation speed of 10 rpm or 2 rpm), and a cone plate can be used as the measuring tool. Specifically, the viscosity can be measured by the method described in the examples.

[0142] 1.5. Composition The temporary fixing composition of the present embodiment only needs to contain the polymerizable compound A and the photopolymerization initiator B, and may further contain other components.

[0143] 1.5.1. Polymerizable compound A The polymerizable compound A is not particularly limited as long as it is a compound having one or more polymerizable functional groups, and examples thereof include polymerizable compound A1 having a hydrocarbon chain with 3 or more carbon atoms, polymerizable compound A2 having an aromatic ring, polymerizable compound A3 having a hydrocarbon chain with 3 or more carbon atoms and an aromatic ring, and other polymerizable compounds A4.

[0144] Among these, it is preferable that the polymerizable compound A includes at least one selected from the group consisting of polymerizable compound A1, polymerizable compound A2, and polymerizable compound A3. By adjusting the contents of polymerizable compounds A1 to A3, it is possible to control the concentrations of hydrocarbon chains having 3 or more carbon atoms and aromatic rings in the temporary fixing composition. In this embodiment, polymerizable compound A1 does not have an aromatic ring, polymerizable compound A2 does not have a long hydrocarbon chain, and polymerizable compound A4 does not have either an aromatic ring or a long hydrocarbon chain. The polymerizable compounds A1 to A4 may each independently be used alone or in combination of two or more.

[0145] In this embodiment, the polymerizable functional group is not particularly limited, but examples thereof include groups having a carbon-carbon double bond, such as a vinyl group, an allyl group, a butenyl group, an ethynyl group, an acryloyl group, an acryloyloxy group, an acryloylamino group, a methacryloyl group, a methacryloyloxy group, a methacryloylamino group, a vinyloxy group, a vinylamino group, a cyclopropyl group, and a cyclobutyl group. Among these, a group containing an ethylenic double bond is preferred, and a (meth)acryloyl group is more preferred. That is, the polymerizable compound A preferably contains a (meth)acrylate.

[0146] The content of the polymerizable compound A is preferably 50 to 99.9 mass %, 70 to 99.5 mass %, 80 to 99.2 mass %, 90 to 99.0 mass %, or 95 to 98.8 mass % relative to the total amount of the temporary fixing composition. When the content of the polymerizable compound A is within the above range, the laser peelability is further improved, and the cured product tends to be less likely to remain.

[0147] Each polymerizable compound will be described in detail below.

[0148] The polymerizable compound A1 is not particularly limited as long as it has a hydrocarbon long chain and one or more polymerizable functional groups. Examples thereof include monofunctional polymerizable compounds such as isostearyl (meth)acrylate; 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate (which may have 1 to 10 repeating units), neopentyl glycol di(meth)acrylate, C1 to C6 20 Examples of suitable polyfunctional polymerizable compounds include alkoxylated hydrogenated bisphenol A di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate; and polymers having polymerizable functional groups (hereinafter also referred to as "macromonomers") containing, as monomer units, (meth)acrylate monomers containing a hydrocarbon long chain in the side chain and (meth)acrylate monomers containing a (meth)acryloyl group in the side chain. Among these, (meth)acrylates containing a hydrocarbon long chain are preferred.

[0149] Examples of (meth)acrylate monomers containing a long hydrocarbon chain in the side chain include propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and among these, butyl (meth)acrylate is preferred.

[0150] The (meth)acrylate monomer containing a (meth)acryloyl group in the side chain may be a (meth)acrylate in which the (meth)acryloyl group is bonded to the side chain via a suitable linker. The linker may be a hydrocarbon chain having 3 to 20 or 4 to 10 carbon atoms and may contain an ether bond and / or an amide bond.

[0151] The number of carbon atoms in the hydrocarbon long chain of the polymerizable compound A1 is 3 or more, preferably 3 to 20, 3 to 18, or 4 to 16, or may be 8 to 12. The polymerizable compound A1 may have hydrocarbon long chains with different numbers of carbon atoms in one molecule, and preferably contains a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms. Such a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms may be a bifunctional (meth)acrylate or a (meth)acrylate having (meth)acryloyl groups at both terminal positions of the molecular chain. The number of carbon atoms in the hydrocarbon chain is preferably 8 to 15. The content of the (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms and the content of the polymerizable compound A1 having a hydrocarbon chain with 8 or more carbon atoms are preferably 0 to 70 parts by mass, 10 to 60 parts by mass, or 20 to 55 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0152] The long hydrocarbon chain functional group equivalent of the polymerizable compound A1 is preferably 100 to 600 g / mol. The polymerizable compound A1 preferably contains a polymerizable compound having a long hydrocarbon chain functional group equivalent of 200 g / mol or less, 100 to 200 g / mol, or 110 to 190 g / mol. When the long hydrocarbon chain functional group equivalent is within the above range, residual residue of the cured product tends to be less likely to occur. The content of the polymerizable compound A1 having a long hydrocarbon chain functional group equivalent within the above range is preferably 5 to 70 parts by mass, 10 to 60 parts by mass, or 15 to 50 parts by mass, per 100 parts by mass of the total amount of the polymerizable compound A.

[0153] The content of polymerizable compound A1 is preferably 50 to 98 parts by mass, 55 to 95 parts by mass, 60 to 92 parts by mass, or 64 to 90 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A. By setting the content of polymerizable compound A1 within the above range, there is a tendency that the cured product does not remain.

[0154] The polymerizable compound A2 is not particularly limited as long as it has an aromatic ring and one or more polymerizable functional groups. Examples of the polymerizable compound A2 include monofunctional polymerizable compounds such as phenol ethylene oxide modified (meth)acrylate (the number of repeating units of ethylene oxide is 1 to 5), 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl (meth)acrylate, and 2-(2-(meth)acryloyloxy,5-methyl)phenyl-2H-benzotriazole; 9,9-bis[4-(2-hydroxyC1-C 20 Alkoxy)phenyl]fluorene di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C1-C 20 Examples of suitable polyfunctional polymerizable compounds include polyfunctional (meth)acrylates containing an aromatic ring, such as 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2'-dihydroxy-4,4'-diethoxy(meth)acryloyloxybenzophenone, and 1,1-bis-[2-(meth)acryloyloxy,3-(2H-benzotriazol-2-yl),5-tertiaryoctyl]methane.

[0155] The aromatic ring equivalent of the polymerizable compound A2 is preferably 100 to 400 g / mol. The polymerizable compound A2 preferably includes a polymerizable compound having an aromatic ring equivalent of 200 g / mol or less, 100 to 200 g / mol, or 110 to 190 g / mol. When the aromatic ring equivalent is within the above range, laser peelability tends to be further improved. The content of the polymerizable compound A2 having an aromatic ring equivalent within the above range is preferably 1 to 45 parts by mass, 2 to 40 parts by mass, or 3 to 35 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0156] The polymerizable compound A2 preferably contains a polymerizable compound A2-1 containing a group that absorbs light with a wavelength of 350 to 385 nm. The polymerizable compound A2-1 more preferably has an absorption peak for light with a wavelength of 350 to 385 nm. While the absorption peak of an aromatic ring generally has absorption at about 200 nm, when the element adjacent to the aromatic ring is a heteroatom such as P, S, or O, the conjugation length increases, and light with a wavelength of 350 to 385 nm is absorbed. By including such a polymerizable compound A2-1, when the temporary fixing layer is irradiated with laser light, the laser light is efficiently absorbed, and laser peelability tends to be improved.

[0157] Examples of such polymerizable compound A2-1 include compounds having one or more skeletons selected from the group consisting of a benzophenone skeleton, a benzotriazole skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton. Among these, a phenol skeleton is preferred, and a hindered phenol skeleton is more preferred.

[0158] The content of the polymerizable compound A2 is preferably 2 to 50 parts by mass, 5 to 45 parts by mass, 8 to 40 parts by mass, or 9 to 35 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A. By setting the content of the polymerizable compound A2 within the above range, the laser releasability of the temporary fixing composition can be further improved.

[0159] When the polymerizable compound A2 contains the polymerizable compound A2-1, the content of the polymerizable compound A2-1 is preferably 1 to 30 parts by mass, 2 to 25 parts by mass, 3 to 20 parts by mass, or 5 to 15 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A. By setting the content of the polymerizable compound A2-1 within the above range, the laser releasability of the temporary fixing composition can be further improved.

[0160] The polymerizable compound A3 is not particularly limited, but examples thereof include monofunctional polymerizable compounds such as nonylphenol ethylene oxide modified (meth)acrylate (the number of repeating units of ethylene oxide is 1 to 5); 20 Examples include polyfunctional polymerizable compounds such as alkoxylated bisphenol A di(meth)acrylate.

[0161] The long hydrocarbon chain functional group equivalent of polymerizable compound A3 is preferably 100 to 800 g / mol. Polymerizable compound A3 preferably contains a polymerizable compound having a long hydrocarbon chain functional group equivalent of 500 g / mol or less, 100 to 500 g / mol, or 200 to 400 g / mol. When the long hydrocarbon chain functional group equivalent is within the above range, residual residue of the cured product tends to be less likely to occur. The content of polymerizable compound A3 having a long hydrocarbon chain functional group equivalent within the above range is preferably 0 to 48 parts by mass, 0 to 40 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A.

[0162] The aromatic ring equivalent of the polymerizable compound A3 is preferably 100 to 500 g / mol. The polymerizable compound A3 preferably contains a polymerizable compound having an aromatic ring equivalent of 500 g / mol or less, 100 to 500 g / mol, or 200 to 400 g / mol. When the aromatic ring equivalent is within the above range, laser peelability tends to be further improved. The content of the polymerizable compound A3 having an aromatic ring equivalent within the above range is preferably 0 to 40 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass relative to 100 parts by mass of the total amount of the polymerizable compound A.

[0163] The number of carbon atoms in the hydrocarbon long chain of polymerizable compound A3 is 3 or more, preferably 3 to 20, 3 to 18, or 4 to 16, or may be 8 to 12. Polymerizable compound A3 may have hydrocarbon long chains with different numbers of carbon atoms in one molecule, and may contain a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms. Such a (meth)acrylate having a hydrocarbon chain with 8 or more carbon atoms may be a monofunctional (meth)acrylate. The number of carbon atoms in the hydrocarbon chain is preferably 8 to 15.

[0164] The content of the polymerizable compound A3 is preferably 0 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more, relative to 100 parts by mass of the total amount of the polymerizable compound A. Furthermore, the content of the polymerizable compound A3 is preferably 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable compound A. The content of the polymerizable compound A3 may be 0 parts by mass. By setting the content of the polymerizable compound A3 within the above range, the laser releasability of the temporary fixing composition tends to be further improved.

[0165] The polymerizable compound A4 is not particularly limited, but examples thereof include 1,3-di(meth)acryloyloxyadamantane, tricyclo C 10 ~C 20 Alkanedimethanol di(meth)acrylate, dicyclo C5-C 20 Examples include polyfunctional polymerizable compounds such as di(meth)acrylate.

[0166] The content of polymerizable compound A4 is preferably 10 parts by mass or less, 0 to 5 parts by mass, or 0 to 3 parts by mass, relative to 100 parts by mass of the total amount of polymerizable compound A. Polymerizable compound A4 may not be included.

[0167] Furthermore, the polymerizable compound A preferably contains a polyfunctional polymerizable compound having two or more polymerizable functional groups per molecule, and more preferably contains a monofunctional polymerizable compound having one polymerizable functional group per molecule and a polyfunctional polymerizable compound having two or more polymerizable functional groups per molecule. By including a polyfunctional polymerizable compound, the adhesive strength of the temporary fixing layer formed by curing the temporary fixing composition tends to be increased. Furthermore, by including a monofunctional polymerizable compound in addition to a polyfunctional polymerizable compound, it tends to be easier to control the concentrations of the hydrocarbon chains and aromatic rings in the temporary fixing composition.

[0168] The polyfunctional polymerizable compound is preferably a polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate may be a monomer, a macromonomer, or a mixture thereof, but preferably contains a macromonomer. The polyfunctional (meth)acrylate can be produced by the methods described in, for example, JP-A Nos. 61-207478, 61-31330, 10-278207, 9-40741, and 8-357621. In this embodiment, the weight-average molecular weight of the polyfunctional (meth)acrylate macromonomer is preferably 5,000 to 500,000, 10,000 to 300,000, 30,000 to 200,000, or 50,000 to 100,000. When the weight-average molecular weight is within the above range, the viscosity of the temporary fixing composition and the crosslink density of the cured product tend to be within preferred ranges. The polyfunctional polymerizable compound may be contained as the polymerizable compound A1.

[0169] The weight-average molecular weight in this specification is a value calculated as a standard polystyrene by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight is determined by using tetrahydrofuran as a solvent, a GPC system (SC-8010 manufactured by Tosoh Corporation) under the following conditions, and creating a calibration curve using commercially available standard polystyrene. Flow rate: 1.0ml / min Set temperature: 40℃ Column configuration: One Tosoh "TSK guardcolumn MP(xL)" 6.0 mm ID x 4.0 cm, and two Tosoh "TSK-GELMULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (16,000 theoretical plates), for a total of three columns (total theoretical plate count: 32,000). Sample injection volume: 100 μl (sample solution concentration 1 mg / ml) Liquid delivery pressure: 39 kg / cm 2 Detector: RI detector

[0170] The polymerizable compound A preferably contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. In this case, the content of the monofunctional polymerizable compound is preferably 0.01 to 80 parts by mass, 0.50 to 70 parts by mass, 1.0 to 68 parts by mass, or 3.0 to 67 parts by mass, relative to 100 parts by mass of the total amount of the polyfunctional polymerizable compounds. By setting the content of the monofunctional polymerizable compound within the above range, laser peelability is further improved, the cured product is less likely to remain, and viscosity and heat resistance tend to be easily adjusted.

[0171] 1.5.2. Photopolymerization initiator B The photopolymerization initiator B is preferably a photoradical polymerization initiator, and more preferably a compound whose molecules are cleaved and split into two or more radicals upon irradiation with ultraviolet light or visible light, for example.

[0172] The photopolymerization initiator B may be selected from compounds that exhibit appropriate absorption characteristics by measuring their absorbance. Specifically, the photopolymerization initiator B may be selected from one or more compounds that, when dissolved at a concentration of 0.1% by mass in a solvent (e.g., acetonitrile, toluene, etc.) that does not have a maximum absorption in the wavelength region of 300 to 500 nm, satisfy one or more of the following conditions: absorbance at a wavelength of 365 nm is 0.5 or more; absorbance at a wavelength of 385 nm is 0.5 or more; and absorbance at a wavelength of 405 nm is 0.5 or more.

[0173] As the photopolymerization initiator B, one or more compounds selected from acylphosphine oxide compounds, titanocene compounds, and α-aminoalkylphenone compounds are preferred because they have excellent reaction speed and heat resistance after curing. These compounds tend to have an absorption wavelength range up to approximately 440 nm and are preferred because they have low absorbance at the wavelength of light used in the process of irradiating the temporary fixing layer with laser light. In other words, the photopolymerization initiator B is a photopolymerization initiator that can initiate radical polymerization with light of a longer wavelength. This allows for a larger difference between the wavelength of the light irradiated when curing the temporary fixing composition and the wavelength of the laser light irradiated when decomposing the temporary fixing layer. Alternatively, an oxime ester compound can be selected as the photopolymerization initiator B.

[0174] Examples of the acylphosphine oxide compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.

[0175] Examples of titanocene compounds include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

[0176] Examples of the α-aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and the like.

[0177] Examples of oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), etc. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.

[0178] From the viewpoint of exhibiting high absorbance in the wavelength region of 365 to 405 nm, the photopolymerization initiator B is preferably 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and more preferably bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0179] Also preferred is bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, which exhibits absorption in the longer wavelength range of 400 to 500 nm.

[0180] The content of the photopolymerization initiator B is preferably 0.01 to 10 parts by mass, 0.01 to 5.0 parts by mass, 0.1 to 3.0 parts by mass, or 0.5 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable compound A. When the content of the photopolymerization initiator B is within the above range, the adhesive strength of the temporary fixing layer formed using the temporary fixing composition tends to be further increased.

[0181] 1.5.3.Other Ingredients The temporary fixing composition may contain components other than the polymerizable compound A and the photopolymerization initiator B. Examples of such components include compounds that do not fall under the category of polymerizable compounds, such as compounds having an aromatic ring and compounds having a hydrocarbon chain with 3 or more carbon atoms.

[0182] 2.Applications The temporary fixing composition of this embodiment is suitably used for temporarily fixing a wafer and a support member in a wafer manufacturing method. The temporary fixing composition is preferably applied to the front surface of a wafer, and the wafer and the support member are temporarily fixed together for back surface processing of the wafer. The temporary fixing composition of this embodiment has high laser releasability, and therefore can be suitably used for manufacturing thin wafers having a thickness of several hundred μm. Furthermore, the temporary fixing composition of this embodiment is less likely to leave a cured product, and therefore, even if a temporary fixing layer is formed on the front surface of a wafer, traces of the temporary fixing layer can be suppressed. Therefore, the temporary fixing composition of this embodiment can be suitably used when processing the back surface of a thin wafer.

[0183] 3. Wafer manufacturing method As shown in FIG. 2, the method for manufacturing a wafer of this embodiment includes the steps of bonding a wafer and a support member together via the temporary fixing composition of this embodiment (hereinafter referred to as a bonding step S0), curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together with the temporary fixing layer (hereinafter referred to as a curing step S1), processing the wafer (hereinafter referred to as a processing step S2), irradiating the temporary fixing layer with laser light (hereinafter referred to as a laser light irradiation step S3), and peeling the support member and the wafer at the interface of the temporary fixing layer (hereinafter referred to as a peeling step S4).

[0184] In the bonding step S0, a wafer is bonded to a support member. The wafer is a substrate to be processed, such as a silicon substrate. The support member is preferably a support member that is at least transparent to ultraviolet light, such as a glass plate.

[0185] The bonding method in the bonding step S0 is not particularly limited, but a method in which the temporary fixing composition of the present embodiment is applied to one surface of a wafer or a support member, and then the other substrate is bonded thereto is preferred.

[0186] As a method for applying the temporary fixing composition, known application methods such as spin coating, screen printing, various coaters, etc. can be used, but spin coating is preferred. Spin coating is a method in which the temporary fixing composition, which is a liquid composition, is dropped onto a wafer or a support member and then rotated at a predetermined rotation speed, thereby applying the composition to the surface of a substrate.

[0187] In the curing step S1, the temporary fixing composition is irradiated with ultraviolet light to cure the temporary fixing composition and bond the wafer and the support member. The temporary fixing composition can be easily irradiated with ultraviolet light by using a transparent substrate that transmits at least ultraviolet light as at least one of the wafer and the support member. When a substrate that transmits ultraviolet light is used as the support member, ultraviolet light may be irradiated from the support member side. Examples of transparent substrates include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic, but inorganic substrates are preferred.

[0188] The wavelength of the ultraviolet light can be appropriately selected depending on the type of photopolymerization initiator B, and may be, for example, in the range of 350 to 405 nm. The ultraviolet light has an energy amount in the range of 350 to 405 nm of, for example, 1 to 20,000 mJ / cm. 2 , preferably 1000 to 10000 mJ / cm 2 It is preferable to irradiate so that

[0189] In the processing step S2, the surface of the wafer opposite to the surface to which the support member is attached is processed. Examples of such processing include insulating film formation, circuit formation, ion implantation, thinning by grinding and polishing, etc. The processing step may include, for example, a thinning step by grinding and polishing, and at least one of insulating film formation, circuit formation, and ion implantation. The insulating film formation, circuit formation, and ion implantation may be performed under high-temperature conditions, for example, at 170 to 300°C.

[0190] The laser light irradiation step S3 is a step of irradiating the temporary fixing layer, which is the cured temporary fixing composition, with laser light to decompose the temporary fixing layer. The wavelength of the laser light is preferably 350 to 385 nm. The laser light may be irradiated from the wafer side or the support member side, but is preferably irradiated from the support member side. As described above, when the temporary fixing composition contains an aromatic ring bonded to a heteroatom, it tends to more easily absorb the energy of the laser light in the laser light irradiation step.

[0191] In the peeling step S4, the support member and the wafer are peeled off at the interface of the temporary fixing layer. In the laser light irradiation step, the temporary fixing layer is decomposed, generating gas derived from the decomposed components, and the adhesive strength at the interface between the temporary fixing layer and the wafer or the support member is reduced, allowing the wafer and the support member to be peeled off.

[0192] The wafer manufacturing method of this embodiment preferably includes a step of removing the temporary fixing layer after laser light irradiation from the wafer peeled off from the support member (hereinafter referred to as a removing step S5). By performing the removing step, even if the temporary fixing layer remains on the wafer, the temporary fixing layer can be sufficiently removed.

[0193] The removal step is not particularly limited as long as it can remove the temporary fixing layer remaining on the wafer, but an example is a method in which an adhesive tape is attached to the wafer on which the temporary fixing layer remains, and then the adhesive tape is peeled off from the wafer. In this method, the remaining temporary fixing layer adheres to the adhesive tape, so that the temporary fixing layer can be removed when the adhesive tape is peeled off from the wafer. As the adhesive tape, for example, a dicing tape used to fix a workpiece in a dicing process in the manufacture of semiconductors, electronic components, and optical components can be used.

[0194] The temporary fixing composition according to the second embodiment may have the features of the temporary fixing composition according to the first embodiment, as long as there is no contradiction. [Example]

[0195] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0196] [Example A] 1.1. Raw materials As the polymerizable compound A, the following compound was used. 1.1.1. Polymerizable compound A1 A1-1: Multifunctional acrylate polymer (weight average molecular weight 72,000, hydrocarbon long chain equivalent: 154.2 g / mol) A-DOD-N: 1,10-decanediol diacrylate ("A-DOD-N" manufactured by Shin-Nakamura Chemical Co., Ltd., where R = -(CH2) in the structural formula shown below) 10 -, Hydrocarbon long chain equivalent: 282.4g / mol) HBPE-4: Ethylene oxide-modified hydrogenated bisphenol A diacrylate ("HBPE-4" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., in the structural formula below, m + n = 4, hydrocarbon long chain equivalent: 524.7 g / mol) ISTA: Isostearyl acrylate ("ISTA" manufactured by Osaka Organic Chemical Industry, Ltd., hydrocarbon long chain equivalent: 324.5 g / mol)

[0197] 1.1.2. Polymerizable compound A2 A-BPEF-2: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate ("NK Ester A-BPEF-2" manufactured by Shin-Nakamura Chemical Co., Ltd., aromatic ring equivalent weight: 136.7 g / mol) RUVA-93: 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole (Otsuka Chemical Co., Ltd. "RUVA-93", aromatic ring equivalent: 160.7 g / mol) DAINSORB P-66: 2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone (Daiwa Kasei Co., Ltd. "DAINSORB P-66", aromatic ring equivalent: 221 g / mol)

[0198] 1.1.3. Polymerizable compound A3 M-113: Nonylphenol ethylene oxide modified acrylate ("Aronix M-113" manufactured by Toagosei Co., Ltd., n = 4 in the structural formula below, hydrocarbon long chain equivalent: 386.6 g / mol, aromatic ring equivalent: 386.6 g / mol)

[0199] As the photopolymerization initiator B, the following compound was used. Omnirad819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF "Omnirad819", aromatic ring equivalent: 137.5 g / mol) was used.

[0200] The structural formula of the above compound is shown below. [Table 1]

[0201] 1.2. Preparation of temporary fixing composition As shown in Table 2, for the Examples and Comparative Examples, the materials were heated and mixed at 60°C to form a uniform liquid composition.

[0202] [Table 2]

[0203] 1.3. Measurement of physical properties of temporary fixing composition (viscosity) The viscosity of each composition was measured according to the following method, and the results are shown in Table 2. Measurement equipment: E-type viscometer DV3T-HB (manufactured by Eiko Seiki Co., Ltd.) Measuring tool: Cone plate CPA-40Z (manufactured by Eiko Seiki Co., Ltd.) Measurement temperature: 23℃ Rotation speed: 10 rpm (500 mPa·s to 2500 mPa·s); 2 rpm (2501 mPa·s to 10000 mPa·s)

[0204] 1.4. Peel strength measurement The peel strength X was measured when heat treatment was performed according to the following steps (i) to (iv). The results are shown in the "heating" column of Table 3.

[0205] (i) A test substrate (aluminum-coated silicon substrate, polyimide-coated silicon substrate, or silicon substrate) was coated with the temporary fixing composition of the Examples or Comparative Examples by spin coating to a thickness of 70 μm, and a glass plate was attached to the coated substrate. The temporary fixing composition was then photocured to form a coating film. The photocuring conditions were a curing wavelength of 405 nm and an illuminance of 350 mW / cm. 2 , cumulative irradiation dose 5,600mJ / cm 2 The following substrates were used: Aluminum-coated silicon substrate: Ti / Al coating (lower layer Ti film 50 μm, upper layer Al film 100 μm) manufactured by Seiren KST. Polyimide-coated silicon substrate: wafer with 5 μm of non-photosensitive polyimide film manufactured by Seiren KST. Silicon substrate: Silicone Technology P-type <100> (Crystalline axis) TTV standard wafer.

[0206] (ii) The test substrate on which the coating film was formed was heated at 175°C for 30 minutes.

[0207] (iii) For a test substrate on which a coating film was formed, an energy density of 920 mJ / cm was applied under the conditions of a wavelength of 355 nm, a frequency of 40 kHz, a spot diameter of 150 μm, and a pulse energy of 165 μJ. 2 After irradiation with the laser beam, the glass plate was peeled off. The laser beam was irradiated so as to scan the entire surface of the test substrate.

[0208] (iv) Peeling tape was applied to the coating film, and a slit was made in the tape and the cured product so that the peel width was 20 mm. The tape with the cured product attached was then pulled under conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, and the peel strength when peeling the coating film from the test substrate was measured, and the average value of five measurements was calculated. The measurement conditions were as follows: Device: Tensilon RTG1210A Tape: Elegrip Tape P Tape (made by Denka) Peeling direction: 180 degrees Peel width: 20mm Peeling speed: 120mm / min Temperature: 25℃

[0209] The peel strength Y without heat treatment was measured in the same manner as in the measurement of peel strength X, except that the above step (ii) was not performed. The results are shown in the "Unheated" column of Table 3.

[0210] 1.5. Survivability Assessment The temporary fixing composition of the Example or Comparative Example was applied to a 4-inch patterned wafer (diameter 10 cm × thickness 0.47 mm) by spin coating to a thickness of 70 μm, and after laminating a glass plate, the temporary fixing composition was photocured to form a test piece. The photocuring conditions were a curing wavelength of 405 nm and an illuminance of 350 mW / cm. 2 , cumulative irradiation dose 5,600mJ / cm 2 The test piece was then placed on a hot plate heated to 175°C and subjected to heat treatment for 30 minutes.

[0211] The pattern on the patterned wafer consisted of 4mm square rounded aluminum rectangles spaced 1mm apart, surrounded by polyimide. In this pattern, the aluminum occupied 64% of the total area, and the polyimide occupied 36%.

[0212] Next, the test piece was irradiated with an energy density of 920 mJ / cm under the conditions of a wavelength of 355 nm, a frequency of 40 kHz, a spot diameter of 150 μm, and a pulse energy of 165 μJ. 2 After irradiation with the laser beam, the glass plate was peeled off. The laser beam was irradiated so as to scan the entire surface of the test substrate.

[0213] Next, a peeling tape was attached to the temporary fixing layer, and the tape with the attached temporary fixing layer was pulled under conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, to peel the temporary fixing layer from the test substrate. The residual rate (area %) of the temporary fixing layer (referred to as residual rate in the table) was calculated from the residual area of ​​the temporary fixing layer. The results are shown in Table 3.

[0214] [Table 3]

[0215] [Example B] 2.1. Raw materials As the polymerizable compound A, the following compound was used. 2.1.1.Polymerizable compound A1 A1-1: Multifunctional acrylate polymer (weight average molecular weight 72,000, hydrocarbon long chain equivalent: 154.2 g / mol) A-DOD-N: 1,10-decanediol diacrylate ("A-DOD-N" manufactured by Shin-Nakamura Chemical Co., Ltd., where R = -(CH2) in the structural formula shown below) 10 -, Hydrocarbon long chain equivalent: 282.4g / mol) HBPE-4: Ethylene oxide-modified hydrogenated bisphenol A diacrylate ("HBPE-4" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., in the structural formula below, m + n = 4, hydrocarbon long chain equivalent: 524.7 g / mol) A-PTMG65: Polytetramethylene glycol diacrylate ("A-PTMG65" manufactured by Shin-Nakamura Chemical Co., Ltd., hydrocarbon long chain equivalent: 86.1 g / mol) HX620: Caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate ("Kayarad HX-620" manufactured by Nippon Kayaku Co., Ltd.; in the structural formula below, m+n=4, and both bonds are bonded; hydrocarbon long-chain equivalent: 111.4 g / mol) ISTA: Isostearyl acrylate ("ISTA" manufactured by Osaka Organic Chemical Industry, Ltd., hydrocarbon long chain equivalent: 324.5 g / mol)

[0216] 2.1.2.Polymerizable compound A2 A-BPEF-2: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate ("NK Ester A-BPEF-2" manufactured by Shin-Nakamura Chemical Co., Ltd., aromatic ring equivalent weight: 136.7 g / mol) RUVA-93: 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole (Otsuka Chemical Co., Ltd. "RUVA-93", aromatic ring equivalent: 160.7 g / mol) P-66: 2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone (Daiwa Kasei Co., Ltd. "DAINSORB P-66", aromatic ring equivalent: 221 g / mol)

[0217] 2.1.3. Polymerizable compound A3 ABE300: Ethoxylated bisphenol A diacrylate ("NK Ester ABE-300" manufactured by Shin-Nakamura Chemical Co., Ltd., in the structural formula below, R = -CH2CH2O-, m + n = 3, hydrocarbon long chain equivalent: 468.5 g / mol, aromatic ring equivalent: 234.3 g / mol) A-BPE-2: Ethoxylated bisphenol A diacrylate ("NK Ester A-BPE-2" manufactured by Shin-Nakamura Chemical Co., Ltd., in the structural formula below, R = -CH2CH2O-, m = n = 1, hydrocarbon long chain equivalent: 424.5 g / mol, aromatic ring equivalent: 212.2 g / mol) A-BPE-10: Ethoxylated bisphenol A diacrylate ("NK Ester A-BPE-10" manufactured by Shin-Nakamura Chemical Co., Ltd., in the structural formula below, R = -CH2CH2O-, m + n = 10, hydrocarbon long chain equivalent: 776.9 g / mol, aromatic ring equivalent: 388.5 g / mol) M-113: Nonylphenol ethylene oxide modified acrylate ("Aronix M-113" manufactured by Toagosei Co., Ltd., n = 4 in the structural formula below, hydrocarbon long chain equivalent: 386.6 g / mol, aromatic ring equivalent: 386.6 g / mol)

[0218] 2.1.4. Polymerizable compound A4 A-DCP: Tricyclodecane dimethanol diacrylate ("A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0219] As the photopolymerization initiator B, the following compound was used. Omnirad819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF "Omnirad819", aromatic ring equivalent: 137.5 g / mol)

[0220] The structural formula of the above compound is shown below. [Table 4]

[0221] 2.2. Preparation of temporary fixing composition As shown in Tables 5 to 7, for each of the Examples and Comparative Examples, the materials were heated and mixed at 60° C. to prepare a uniform liquid composition. In Tables 5 to 7, the concentration of aromatic rings and the concentration of hydrocarbon chains having 3 or more carbon atoms (referred to as "long hydrocarbon chain concentration" in the tables) were calculated from the aromatic ring equivalent and hydrocarbon chain equivalent weights and contents of the raw materials.

[0222] 2.3. Measurement of physical properties of temporary fixing composition (viscosity) The viscosity of each composition was measured according to the following method, and the results are shown in Tables 5 to 7. Measurement equipment: E-type viscometer DV3T-HB (manufactured by Eiko Seiki Co., Ltd.) Measuring tool: Cone plate CPA-40Z (manufactured by Eiko Seiki Co., Ltd.) Measurement temperature: 23℃ Rotation speed: 10 rpm (500 mPa·s to 2500 mPa·s); 2 rpm (2501 mPa·s to 10000 mPa·s)

[0223] (Crosslink density of cured product) To measure the crosslink density of the cured product of each composition, the storage modulus was measured according to the following method. Next, the storage modulus at 200°C, which is the rubbery plateau region, was calculated as E' [Pa], and the gas constant was calculated as R = 8.31 × 10 7The crosslink density was calculated using the following formula, where kJ / (K mol) is the viscosity [Pa·L / (K·mol)] and absolute temperature [K] is the crosslink density. The results are shown in Tables 5 to 7. Examples and comparative examples for which no measurement was performed are indicated by "-" in the tables. Crosslink density n =E' / 3RT Measurement device: RSA-3 (TA Instruments) Measurement mode: Tensile Measurement temperature: 23~250℃ Measurement frequency: 1Hz Measurement strain: 0.1% Heating rate: 3℃ / min Test piece: 0.5mm x 15mm x 0.07mm temporary fixing composition Chuck distance: 10mm

[0224] 2.4. Performance measurement of temporary fixing composition (Evaluation of heat resistance) A 6-inch silicon wafer (10 cm diameter × 0.63 mm thickness) and a 6-inch glass support member (10 cm diameter × 0.7 mm thickness) were bonded together using the prepared temporary fixing composition. During bonding, the thickness of the temporary fixing composition was adjusted to 70 μm. After bonding, the wafer was irradiated with a UV LED with a wavelength of 405 nm at an illuminance of 100 mW / cm. 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 The specimen was cured under the above conditions, placed on a hot plate heated to 175°C, and heated for 30 minutes to prepare a test specimen for evaluation. The temporary fixing composition was applied to the entire surface of the bonding surface. After heating, the test specimen was visually observed, and heat resistance was evaluated based on whether peeling occurred at the adhesive interface. The presence or absence of peeling at the adhesive interface is shown in Tables 5 to 7.

[0225] (Evaluation of laser peelability) Test specimens for evaluation were prepared in the same manner as in the evaluation of heat resistance. A UV laser beam with a wavelength of 355 nm was irradiated onto a circular area with a diameter of 160 mm fixed at the center of the obtained 6-inch test specimen, scanning the entire surface of the test specimen from the glass support member side. The laser beam irradiation conditions were a frequency of 40 kHz, a spot diameter of 150 μm, a pulse energy of 165 μJ, and an energy density of 920 mJ / cm. 2The sample was irradiated with laser light.

[0226] After laser irradiation, the test piece was placed on a suction table (porous chuck type) with the silicon wafer facing downwards and fixed in place. A suction arm with three 10 mm diameter suction cups was attached to the top surface (glass support member side) of the test piece in this state. The glass support member was peeled off by vertically pulling the suction arm upward at 0.5 mm / s to evaluate laser peelability. Tables 5 to 7 show whether or not laser peelability was achieved. If peeling was possible, it was rated as "pass", and if peeling was not possible, it was rated as "fail".

[0227] (Survival assessment) In the evaluation of laser peelability, the test pieces in which the wafer had been peeled off from the support member were evaluated for the residual properties of the temporary fixing layer as follows. Tape was applied to the temporary fixing layer side of the wafer from which the support member had been peeled off, and a cut was made in the tape and the cured product so that the peel width was 20 mm. The tape with the cured product attached was then pulled and peeled off. The average value of five measurements was calculated. In addition, the residual rate (area %) of the cured product after the tape had been peeled off (represented as residual rate in the table) was calculated. The results are shown in Tables 5 to 7.

[0228] Device: Tensilon RTG1210A Tape: Elegrip Tape P Tape (made by Denka) Peeling direction: 180 degrees Peel width: 20mm Peeling speed: 120mm / min Temperature: 25℃

[0229] [Table 5]

[0230] [Table 6]

[0231] [Table 7]

Claims

1. Peel strength X measured by the following measurement method (X) using polyimide as a test substrate PI is 0.50 N / mm or less, Peel strength Y measured by the following measurement method (Y) using polyimide as a test substrate PI is 0.10 N / mm or more, The peel strength Y PI The peel strength X PI Ratio of X PI / Y PI is 1.5 or less, composition. (X) Peel strength is measured by the following steps (i) to (iv). (i) The composition is applied to a test substrate to a thickness of 70 μm, and after laminating a glass plate, the composition is photocured to form a coating film. (ii) Heat the test substrate on which the coating film is formed at 175°C for 30 minutes. (iii) The coating film is irradiated with an energy density of 920 mJ / cm under conditions of a wavelength of 355 nm and a frequency of 40 kHz. 2 After irradiating the glass plate with the laser beam, the glass plate is peeled off. (iv) A peeling tape is attached to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under the conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, and the average value of five measurements is taken. (Y) In the measurement method (X), the peel strength is measured without carrying out the step (ii).

2. The ratio X PI / Y PI is 0.30 to 1.0, The composition of claim 1.

3. Peel strength X measured by the above measurement method (X) using aluminum as a test substrate Al is 0.60 N / mm or less, Peel strength Y measured by the above measurement method (Y) using aluminum as a test substrate Al is 0.10 N / mm or more, The peel strength Y Al The peel strength X Al Ratio of X Al / Y Al is 2.0 or less, The composition of claim 1.

4. The ratio X Al / Y Al is 1.0 to 2.0, The composition of claim 3.

5. The peel strength X Al The peel strength X PI Ratio of X PI / X Al is 0.10 to 0.50, The composition of claim 3.

6. Peel strength X measured by the above measurement method (X) using silicon as a test substrate Si is 0.50 N / mm or less, Peel strength Y measured by the above measurement method (Y) using silicon as a test substrate Si is 0.10 N / mm or more, The peel strength Y Si The peel strength X Si Ratio of X Si / Y Si is 1.6 or less, The composition of claim 1.

7. The ratio X Si / Y Si is 0.3 to 1.2, The composition of claim 6.

8. comprising a polymerizable compound A and a photopolymerization initiator B, The composition of claim 1.

9. The polymerizable compound A is a polymerizable compound A1 having a hydrocarbon chain having 3 or more carbon atoms, and containing a polymerizable compound A2 having an aromatic ring, The composition of claim 8.

10. the polymerizable compound A1 contains a (meth)acrylate having a hydrocarbon chain having 3 or more carbon atoms and a functional group equivalent weight of 200 g / mol or less; The composition of claim 9.

11. the polymerizable compound A1 contains a (meth)acrylate having a hydrocarbon chain having 8 or more carbon atoms; The composition of claim 9.

12. The polymerizable compound A2 contains a (meth)acrylate having an aromatic ring equivalent of 200 g / mol or less. The composition of claim 9.

13. the content of the polymerizable compound A1 is 50 parts by mass to 98 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition of claim 9.

14. the content of the polymerizable compound A2 is 2 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition of claim 9.

15. the content of the photopolymerization initiator B is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; The composition of claim 8.

16. A temporary fixing composition comprising the composition according to any one of claims 1 to 15.

17. a step of bonding a wafer and a support member via the temporary fixing composition according to claim 16; a step of curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together via the temporary fixing layer; heat treating the wafer; irradiating the temporary fixing layer with laser light; and peeling the support member and the wafer at the interface of the temporary fixing layer, Wafer manufacturing method.

18. further comprising a step of removing the temporary fixing layer from the wafer after the laser light irradiation. The method of claim 17.

19. Peel strength Y measured by the following measurement method (Y) using polyimide as a test substrate PI The peel strength X measured by the following measurement method (X) using polyimide as a test substrate against PI Ratio of X PI / Y PI is 1.5 or less, composition. (X) Peel strength is measured by the following steps (i) to (iv). (i) The composition is applied to a test substrate to a thickness of 70 μm, and after laminating a glass plate, the composition is photocured to form a coating film. (ii) Heat the test substrate on which the coating film is formed at 175°C for 30 minutes. (iii) The coating film is irradiated with an energy density of 920 mJ / cm under conditions of a wavelength of 355 nm and a frequency of 40 kHz. 2 After irradiating the glass plate with the laser beam, the glass plate is peeled off. (iv) A peeling tape is attached to the coating film, and the peel strength is measured when peeling the coating film from the test substrate under the conditions of a peeling direction of 180 degrees, a peeling width of 20 mm, a peeling speed of 120 mm / min, and a temperature of 25°C, and the average value of five measurements is taken. (Y) In the measurement method (X), the peel strength is measured without carrying out the step (ii).

20. Contains a polymerizable compound A and a photopolymerization initiator B, The concentration of hydrocarbon chains having 3 or more carbon atoms is 2.80 mmol / g or more; The concentration of aromatic rings is 0.60 mmol / g or more. composition.

21. The crosslink density of the cured product after ultraviolet light irradiation is 0.10 mmol / cm 3 That's all.

21. The composition of claim 20.

22. a ratio of the concentration of the hydrocarbon chain having 3 or more carbon atoms to the concentration of the aromatic ring is 1.5 or more; 21. The composition of claim 20.

23. the polymerizable compound A includes at least one compound selected from the group consisting of a polymerizable compound A1 having a hydrocarbon chain with 3 or more carbon atoms, a polymerizable compound A2 having an aromatic ring, and a polymerizable compound A3 having a hydrocarbon chain with 3 or more carbon atoms and an aromatic ring, 21. The composition of claim 20.

24. At least one of the polymerizable compound A1 and the polymerizable compound A3 contains a (meth)acrylate having a hydrocarbon chain having 3 or more carbon atoms and a functional group equivalent of 200 g / mol or less.

24. The composition of claim 23.

25. At least one of the polymerizable compound A1 and the polymerizable compound A3 contains a (meth)acrylate having a hydrocarbon chain having 8 or more carbon atoms.

24. The composition of claim 23.

26. the polymerizable compound A2 and the polymerizable compound A3 each contain at least one (meth)acrylate having an aromatic ring equivalent of 200 g / mol or less; 24. The composition of claim 23.

27. the content of the polymerizable compound A1 is 50 parts by mass to 98 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; 24. The composition of claim 23.

28. the content of the polymerizable compound A2 is 2 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; 24. The composition of claim 23.

29. the content of the polymerizable compound A3 is 0 parts by mass to 48 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; 24. The composition of claim 23.

30. the content of the photopolymerization initiator B is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound A; 21. The composition of claim 20.

31. the polymerizable compound A contains a monofunctional polymerizable compound and a polyfunctional polymerizable compound, the content of the monofunctional polymerizable compound is 0.01 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional polymerizable compound; 21. The composition of claim 20.

32. The viscosity at 23°C is 500 mPa·s to 10,000 mPa·s.

21. The composition of claim 20.

33. A temporary fixing composition comprising the composition according to any one of claims 20 to 32.

34. a step of bonding a wafer and a support member via the temporary fixing composition according to claim 33; a step of curing the temporary fixing composition by irradiating it with ultraviolet light to form a temporary fixing layer, and bonding the wafer and the support member together via the temporary fixing layer; processing the wafer; irradiating the temporary fixing layer with laser light; and peeling the support member and the wafer at the interface of the temporary fixing layer, Wafer manufacturing method.

35. further comprising a step of removing the temporary fixing layer from the wafer after the laser light irradiation. The method of claim 34.

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