Resin membrane formation film and manufacturing method of work individualized piece with resin membrane

Abstract

To provide a resin membrane formation film capable of suppressing peeling of a resin membrane and a work individualized piece in PCT, and a method of manufacturing a work individualized piece such as a semiconductor chip.SOLUTION: A resin membrane formation film adhered to a work for forming a resin membrane contains at least one selected from among an alkoxysilane compound FA, a silane compound FB and an alkoxysilane compound FC as a silane coupling agent. In the resin membrane formation film, the alkoxysilane compound FA has an alkoxy silyl group, an epoxy group and a coupling group coupling the alkoxy silyl group and the epoxy group, and the total number of carbon and oxygen atoms in a main chain of the coupling group is 10 or more. The silane compound FB has a cyclic siloxane structure and two or more epoxy groups bonded to the cyclic siloxane structure, and the alkoxysilane compound FC has an alkoxy silyl group and a thiourea bond or an urea bond.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a resin film-forming film and a method for manufacturing individual pieces of a workpiece with a resin film. In particular, in an accelerated test for evaluating moisture resistance such as PCT, a resin film-forming film capable of forming a resin film with suppressed peeling from a workpiece, and a method for manufacturing individual pieces of a workpiece with a resin film such as a semiconductor chip with a resin film using the resin film-forming film.

Background Art

[0002] A semiconductor chip is obtained as an individual piece of a workpiece obtained by singulating a workpiece such as a wafer on which a circuit is formed. In recent years, a semiconductor device has been manufactured by a mounting method called flip chip bonding using a semiconductor chip having a circuit surface on which convex electrodes such as bumps are formed. In this mounting method, when mounting the semiconductor chip, the circuit surface side of the semiconductor chip is inverted (face down) and joined to the chip mounting portion. Therefore, the back surface side of the semiconductor chip on which the circuit is not formed is exposed.

[0003] For this reason, on the back surface side of the semiconductor chip, a hard resin film made of an organic material is often formed to protect the semiconductor chip from impacts during transportation or the like. Such a resin film is called a protective film. The protective film is formed, for example, by attaching a protective film-forming film as an example of a resin film-forming film to the back surface of a semiconductor wafer and then curing it or forming it in a non-cured state. The semiconductor chip with the protective film formed thereon is mounted on a substrate or the like as an electronic component.

[0004] In addition, the semiconductor chip may be adhered to the circuit formation surface of the substrate by a resin film attached to its back surface. A resin film forming film for forming and adhering such a resin film is called a die bonding film. The semiconductor chip is placed on the substrate through the die bonding film by die bonding. Thereafter, if necessary, one or more additional semiconductor chips are stacked on this semiconductor chip, wire bonding is performed, and then the whole is sealed with resin to produce a semiconductor package as an electronic component.

[0005] Patent Document 1 discloses a protective film forming film for forming a protective film for protecting a semiconductor chip. Further, Patent Document 1 discloses evaluating the reliability of a semiconductor chip on which a protective film is formed by a thermal shock test.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Workpieces such as wafers are usually composed of inorganic materials. Therefore, the workpiece pieces obtained by fragmenting the workpiece are also usually composed of inorganic materials. Therefore, in a workpiece piece with a resin film in which a resin film is formed on the workpiece piece, the inorganic material and the organic material are in contact.

[0008] At the interface between such an inorganic material and an organic material, since different materials with different constituent elements are adhered to each other, the adhesion tends to be low. Therefore, for example, moisture easily penetrates into the interface, and as a result, peeling between the resin film and the workpiece piece may occur at the interface. When such peeling occurs, the reliability as an electronic component decreases.

[0009] Therefore, in order to improve the adhesion at the interface between the inorganic material and the organic material, a coupling agent having a group that binds to the inorganic material and a group that binds to the organic material, typically a silane coupling agent, is incorporated into the resin film.

[0010] Although the adhesion at the interface between the resin film and the work pieces is improved by incorporating the silane coupling agent, in an accelerated test such as the PCT (Pressure Cooker Test), which is a severe evaluation test that emphasizes the moisture resistance of electronic components, even when a silane coupling agent used in Patent Document 1 is incorporated, there is a problem that peeling occurs between the resin film and the work pieces.

[0011] In view of such a situation, the present invention has been made, and an object thereof is to provide a resin film-forming film capable of suppressing peeling between the resin film and the work pieces even in a severe accelerated test such as PCT, and a method for manufacturing a work piece with a resin film such as a semiconductor chip with a resin film using the resin film-forming film.

Means for Solving the Problems

[0012] Aspects of the present invention are as follows.

[0013] [1] A resin film-forming film for forming a resin film by attaching it to a work, The resin film-forming film has a silane coupling agent, The silane coupling agent is at least one selected from an alkoxysilane compound FA, a silane compound FB, and an alkoxysilane compound FC, The alkoxysilane compound FA has an alkoxysilyl group, an epoxy group, and a linking group that links the alkoxysilyl group and the epoxy group, and is an alkoxysilane compound in which the total number of carbon atoms and oxygen atoms in the main chain of the linking group is 10 or more, The silane compound FB is a silane compound having a cyclic siloxane structure and two or more epoxy groups bonded to the cyclic siloxane structure, The resin film-forming film of the alkoxysilane compound FC is an alkoxysilane compound having an alkoxysilyl group and a thiourea bond or a urea bond.

[0014] [2] The resin film-forming film according to [1], wherein the resin film-forming film has a curable component and a polymer component.

[0015] [3] The resin film-forming film according to [1] or [2], wherein in the resin film-forming film, the arithmetic mean height Sa of the surface to be attached to the work is 0.02 μm or more and 0.1 μm or less.

[0016] [4] The epoxy group contained in the glycidoxy group is the epoxy group contained in the alkoxysilane compound FA, and the linking group contained in the alkoxysilane compound FA is composed of an alkyl group and a glycidoxy group excluding the epoxy group, and the number of carbon atoms in the main chain of the alkyl group is 8 or more. The resin film-forming film according to any one of [1] to [3].

[0017] [5] The resin film-forming film according to any one of [1] to [4], wherein the alkoxysilane compound FC has a heterocyclic ring.

[0018] [6] The resin film-forming film according to any one of [1] to [5], wherein the maximum transmittance of light with a wavelength of 400 to 700 nm for the resin film-forming film is 30% or less.

[0019] [7] Regarding the copper foil peeling strength indicating the peeling strength between the resin film-forming film and the copper foil, the ratio of the copper foil peeling strength at 23 °C and 50% relative humidity to the copper foil peeling strength at 23 °C and 50% after standing at 85 °C and 85% relative humidity for one week is 55% or more. The resin film-forming film according to any one of [1] to [6].

[0020] [8] A step of attaching the resin film-forming film according to any one of [1] to [7] to the work; A step of forming the resin film after the step of attaching to the work; A method for manufacturing a workpiece with a resin film, comprising: after the step of attaching a resin film or a resin film-forming film to a workpiece, fragmenting the workpiece with the resin film or the resin film-forming film attached thereto to obtain a plurality of workpieces with resin films or resin film-forming films attached thereto.

Advantages of the Invention

[0021] According to the present invention, even in a severe acceleration test such as PCT, it is possible to provide a resin film-forming film that can suppress peeling between the resin film and the fragmented workpiece, and a method for manufacturing a workpiece with a resin film such as a semiconductor chip with a resin film using the resin film-forming film.

Brief Description of the Drawings

[0022]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5A

Figure 5B

Figure 6

Embodiments for Carrying Out the Invention

[0023] Hereinafter, the present invention will be described in detail with reference to the drawings based on specific embodiments.

[0024] First, main terms used in this specification will be explained.

[0025] The "work" refers to a plate-like body to which the resin film-forming film according to this embodiment is attached and then fragmented. The resin film-forming film is attached to the back surface of the work. Examples of the work include a circular (including the case having an orientation flat) wafer, a rectangular panel-level package, and a strip (strip-shaped substrate) with a molded resin seal. Among them, from the viewpoint of easily obtaining the effects of the present invention, a wafer made of an inorganic material is preferable. Examples of the wafer include semiconductor wafers such as silicon wafers, gallium arsenide wafers, silicon carbide wafers, gallium nitride wafers, and indium phosphide wafers, and insulator wafers such as glass wafers, lithium tantalate wafers, and lithium niobate wafers. Further, a reconstituted wafer composed of a resin and a semiconductor used for manufacturing a fan-out package or the like may also be used. From the viewpoint of easily obtaining the effects of the present invention, as the wafer, a semiconductor wafer or an insulator wafer is preferable, a semiconductor wafer containing silicon or an insulator wafer containing silicon is more preferable, and a semiconductor wafer containing silicon is even more preferable.

[0026] The fragmentation of the work means dividing the work into individual circuits to obtain fragmented work pieces. For example, when the work is a wafer, the fragmented work pieces are chips, and when the work is a panel-level package or a strip (strip-shaped substrate) with a molded resin seal, the fragmented work pieces are semiconductor packages.

[0027] The "front surface" of the work refers to the surface on which circuits, electrodes, etc. are formed, and the "back surface" of the work refers to the surface on which no circuits, etc. are formed. The electrode may be a convex electrode such as a bump.

[0028] The "main surface" refers to the surface of the plate-like body that has a larger area than other surfaces. Usually, the plate-like body has two main surfaces and other side surfaces, and the two main surfaces face each other. In the workpiece, the "front surface" and the "back surface" are the main surfaces.

[0029] "(Meth)acrylate" is used as a term indicating both "acrylate" and "methacrylate", and the same applies to other similar terms.

[0030] "Energy ray" refers to ultraviolet rays, electron beams, etc., preferably ultraviolet rays.

[0031] Unless otherwise specified, the "weight average molecular weight" is a polystyrene equivalent value measured by the gel permeation chromatography (GPC) method. Measurement by such a method is performed, for example, using a high-speed GPC device "HLC-8120GPC" manufactured by Tosoh Corporation, with a high-speed column "TSK guard column HXL-H", "TSK Gel GMHXL", "TSK Gel G2000 HXL" (all manufactured by Tosoh Corporation) connected in this order, under the conditions of column temperature: 40 °C and liquid feeding rate: 1.0 mL / min, with the detector being a differential refractometer.

[0032] The release film is a film that supports the resin film-forming film in a peelable manner. The film is not limited to thickness and is used in the concept including sheets.

[0033] The mass ratio in the description of the composition such as the composition for the resin film-forming film is based on the active ingredient (solid content), and the solvent is not included unless otherwise specified.

[0034] (1. Resin film-forming film) The resin film-forming film according to this embodiment is used to form a resin film on the workpiece or the workpiece individual pieces after being attached to the workpiece. As a result, a workpiece with a resin film or a workpiece individual piece with a resin film is obtained.

[0035] As described above, in order to suppress the peeling between the resin film and the workpiece or the individual pieces of the workpiece, a silane coupling agent as described in Patent Document 1 is used.

[0036] Since electronic components including individual pieces of the workpiece with a resin film are used in various environments, reliability that can surely exhibit predetermined performance of the electronic components is required in such environments. As tests for evaluating reliability, various tests are known according to the required reliability. For example, as a test for evaluating the moisture resistance of electronic components, PCT (Pressure Cooker Test) is known. PCT is an accelerated test performed under conditions of applying high temperature, high humidity, and pressure so that moisture is more likely to penetrate into interfaces and the like than in normal environments.

[0037] Since PCT is a severe test, peeling may occur even if the adhesion is such that peeling between the resin film and the individual pieces of the workpiece does not occur in a normal environment. Therefore, when emphasizing the moisture resistance of electronic components, adhesion such that peeling does not occur at the interface is also required in PCT.

[0038] However, the present inventor has obtained a finding that good adhesion cannot be obtained in PCT even when using a silane coupling agent as described in Patent Document 1. The reason for the failure to obtain good adhesion is presumably due to the following mechanism, for example.

[0039] The silane coupling agent as described in Patent Document 1 has an alkoxysilyl group and an epoxy group. As shown in FIG. 1, the epoxy group 300b of the silane coupling agent 300 in the protective film 200 binds to the structure 700 composed of organic components, and the alkoxysilyl group 300a of the silane coupling agent 300 binds to the surface of the wafer 100, thereby improving the adhesion between the protective film 200 and the wafer 100.

[0040] However, since there are many silane coupling agents in which the alkoxysilyl group 300a is not bonded to the surface of the wafer 100, it is considered that the adhesion is not improved so much. As a result, in a severe test such as PCT, it is considered that peeling between the protective film 200 and the wafer 100 is likely to occur.

[0041] Therefore, in the present embodiment, by using a resin film-forming film containing a specific silane coupling agent described later, peeling between the resin film and the workpiece individual pieces is suppressed even in a severe test such as PCT. Hereinafter, the resin film-forming film according to the present embodiment will be described.

[0042] Examples of the resin film formed using the resin film-forming film according to the present embodiment include a protective film for protecting a workpiece or a workpiece individual piece, and an adhesive film for adhering a workpiece individual piece to another adherend. In the present embodiment, the resin film is preferably a protective film.

[0043] The resin film is obtained by forming a resin film from the resin film-forming film. "Forming a resin film" means bringing the resin film-forming film into a state having sufficient properties to impart a predetermined function to a workpiece or a workpiece individual piece.

[0044] For example, when the resin film-forming film is a protective film-forming film, "forming a resin film" can be paraphrased as "forming a protective film", and bringing the protective film-forming film into a state having sufficient properties to protect a workpiece or a workpiece individual piece.

[0045] When the protective film-forming film is curable, "forming a protective film" means making the uncured protective film-forming film into a cured product. In other words, the protective film-forming film that has been formed into a protective film is a cured product of the protective film-forming film and is different from the protective film-forming film.

[0046] After overlapping the workpiece on the curable protective film-forming film and then curing the protective film-forming film, the protective film can be firmly adhered to the workpiece, and a protective film having durability can be formed.

[0047] On the other hand, when the protective film forming film does not contain a curable component and is used in an uncured state, the protective film forming film is converted into a protective film when it is attached to the workpiece. In other words, the converted protective film forming film is the same as the protective film forming film.

[0048] When high protective performance is not required, it is not necessary to cure the protective film forming film, so the protective film forming film is easy to use.

[0049] In the present embodiment, the resin film forming film is preferably curable. Therefore, the resin film is preferably a cured product. Examples of the cured product include, for example, a thermoset and an energy ray cured product. That is, examples of the curable resin film forming film include a thermosetting resin film forming film and an energy ray curable resin film forming film.

[0050] Since the resin film forming film preferably contains a filler, a colorant, etc. to be described later, the light transmittance tends to be low. Therefore, when the resin film forming film is cured by irradiation with energy rays to obtain an energy ray cured product, particularly when the thickness of the resin film forming film increases, the energy ray curing tends to be insufficient.

[0051] On the other hand, the thermosetting resin film forming film can be sufficiently cured by heating even when its thickness increases, so that a resin film with high protective performance can be formed. In addition, by using ordinary heating means such as a heating oven, a large number of resin film forming films can be heated and thermally cured collectively. Therefore, in the present embodiment, the resin film forming film is more preferably thermosetting.

[0052] Whether the resin film-forming film is thermosetting can be determined as follows. First, heat the resin film-forming film at room temperature (23°C) until the temperature exceeds room temperature, and then cool it to room temperature to obtain the resin film-forming film after heating and cooling. Next, when comparing the hardness of the resin film-forming film after heating and cooling with the hardness of the resin film-forming film before heating at the same temperature, if the resin film-forming film after heating and cooling is harder, it is determined that this resin film-forming film is thermosetting.

[0053] Also, it is preferable that the resin film-forming film has adhesiveness at room temperature (23°C) or exhibits adhesiveness upon heating. Thereby, when the work is superposed on the resin film-forming film, both can be bonded. Therefore, positioning can be surely performed before curing the resin film-forming film.

[0054] The resin film-forming film may be composed of one layer (single layer) or may be composed of two or more layers. When the resin film-forming film has a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of the layers constituting these plurality of layers is not particularly limited.

[0055] In this embodiment, it is preferable that the resin film-forming film is one layer (single layer). Since a high accuracy can be obtained with respect to the thickness of the single-layer resin film-forming film, production is easy. Further, when the resin film-forming film is composed of a plurality of layers, it is necessary to consider the adhesion between layers and the stretchability of each layer, and there is a risk of peeling from the adherend due to these. When the resin film-forming film is one layer, the above risk can be reduced and the degree of freedom in design is also increased.

[0056] The thickness of the resin film-forming film may be 100 μm or less, or may be 60 μm or less, or may be 50 μm or less, or may be 45 μm or less. Also, the thickness of the resin film-forming film may be 3 μm or more, or may be 5 μm or more, or may be 10 μm or more, or may be 15 μm or more.

[0057] Note that the thickness of the resin film-forming film means the thickness of the entire resin film-forming film. For example, the thickness of a resin film-forming film composed of multiple layers means the total thickness of all the layers constituting the resin film-forming film.

[0058] (1.1. Physical properties of the resin film-forming film and the resin film) The resin film-forming film according to this embodiment preferably has the following physical properties.

[0059] (1.1.1. Arithmetical mean height Sa) In this embodiment, in the resin film-forming film, the arithmetical mean height Sa of the surface adhered to the work is preferably 0.02 μm or more and 0.1 μm or less. The arithmetical mean height of the surface is one of the surface roughness parameters defined in ISO 25178 and is the average value of the absolute values of the peak height and valley depth on the measurement surface.

[0060] When the arithmetical mean height Sa is within the above range, the adhesion suitability between the resin film-forming film and the work (the performance that can be adhered to an appropriate position on the work during adhesion and shows sufficient adhesive force after adhesion) can be further improved.

[0061] The arithmetical mean height Sa may be 0.025 μm or more, or 0.03 μm or more, or 0.035 μm or more. Also, the arithmetical mean height Sa may be 0.07 μm or less, or 0.055 μm or less, or 0.045 μm or less.

[0062] The measurement method of the arithmetical mean height Sa can be measured in accordance with ISO 25178. In this embodiment, a non-contact white interference microscope can be used. The specific measurement method will be described in the examples.

[0063] (1.1.2. Maximum transmittance in the visible light region) In this embodiment, it is preferable that the maximum transmittance of light rays with wavelengths of 400 to 700 nm with respect to the resin film-forming film is 30% or less. Since the light rays with wavelengths of 400 to 700 nm correspond to the light rays in the visible light region, the shielding function of the resin film is likely to be exerted when the maximum transmittance is within the above range. As a result, for example, it becomes difficult to observe marks or the like remaining on the workpiece.

[0064] The maximum transmittance may be 25% or less, or may be 16% or less, or may be 10% or less. Further, the maximum transmittance is 0% or more, and may be 0.5% or more, or may be 1% or more. A specific method for measuring the maximum transmittance will be described in the examples.

[0065] (1.1.3. Retention rate of copper foil peel strength) In this embodiment, it is preferable that the retention rate of the copper foil peel strength, which indicates the ratio of the copper foil peel strength at room temperature after standing under high-temperature and high-humidity conditions to the copper foil peel strength at room temperature, is 55% or more. This retention rate of the copper foil peel strength is an index of how much the intrusion of moisture into the interface between the resin film and the silicon wafer can be suppressed during heating. Although the measurement conditions of the retention rate of the copper foil peel strength are different from those of the PCT measurement, when the retention rate of the copper foil peel strength is within the above range, the PCT results tend to be better.

[0066] The retention rate of the copper foil peel strength may be 65% or more, or may be 75% or more, or may be 85% or more.

[0067] Note that the copper foil peel strength at room temperature uses the value measured under the conditions of 23°C and a relative humidity of 50%, and the copper foil peel strength at room temperature after standing under high-temperature and high-humidity conditions uses the value measured under the conditions of 23°C and a relative humidity of 50% after standing for one week under the conditions of 85°C and a relative humidity of 85%. Further, the copper foil peel strength is the peel strength when the copper foil attached to the resin film is peeled off from the silicon wafer together with the resin film. A specific measurement method will be described in the examples.

[0068] In addition, since the copper foil shields energy rays, when an energy ray-curable resin film-forming film is used, the above-mentioned maintenance rate of the copper foil peel strength cannot be measured.

[0069] (1.2. Composition for resin film-forming film) The resin film-forming film is formed using a composition (composition for resin film-forming film) that constitutes the resin film-forming film. That is, the resin film-forming film contains the active ingredients that constitute the composition for resin film-forming film. In the present embodiment, in the PCT, in order to suppress the peeling between the resin film and the work (or the individual pieces of the work), the composition for resin film-forming film has a specific silane coupling agent (F).

[0070] (1.2.1. Silane coupling agent) The silane coupling agent (F) included in the composition for resin film-forming film according to the present embodiment is at least one selected from an alkoxysilane compound FA, a silane compound FB, and an alkoxysilane compound FC. Therefore, the composition for resin film-forming film according to the present embodiment may have one compound out of the alkoxysilane compound FA, the silane compound FB, and the alkoxysilane compound FC as the silane coupling agent, or may use two or more compounds in combination.

[0071] By using the above compounds, the adhesion between the resin film and the work (or the individual pieces of the work) can be improved compared with conventional silane coupling agents. As a result, even in an accelerated test such as PCT, the peeling between the resin film and the work (or the individual pieces of the work) can be suppressed. Each compound will be described below.

[0072] (1.2.2. Alkoxysilane compound FA) The alkoxysilane compound FA has an alkoxysilyl group, an epoxy group, and a linking group that links the alkoxysilyl group and the epoxy group. In addition, the total number of carbon atoms and oxygen atoms in the main chain of the linking group is 10 or more. The linking group may be composed of a single group or a plurality of groups.

[0073] Conventionally, in an alkoxysilane compound having an alkoxysilyl group, an epoxy group, and a linking group that links the alkoxysilyl group and the epoxy group, which has been used as a silane coupling agent, the linking group is short. For example, the total number of carbon atoms and oxygen atoms in the main chain of the linking group was 6 or less. Therefore, as shown in FIG. 1, there were few silane coupling agents having an alkoxysilyl group bonded to the workpiece, and the improvement in adhesion was limited.

[0074] On the other hand, in the present embodiment, since the total number of carbon atoms and oxygen atoms in the main chain of the linking group is 10 or more, the linking group becomes longer. Therefore, as shown in FIG. 2(a), even when the alkoxysilane compound FA is present at a position away from the workpiece 100, the probability that the alkoxysilyl group 3a in the alkoxysilane compound FA is located near the workpiece 100 increases. As a result, since the number of alkoxysilyl groups 3a that form a covalent bond with the workpiece 100 increases, the adhesion between the resin film 2 and the workpiece 100 (or the individual pieces of the workpiece) via the alkoxysilane compound FA is improved. At this time, when the structure 7 composed of an organic component exists in the resin film 2, the epoxy group 3b in the alkoxysilane compound FA can be bonded to the structure 7, so the adhesion is further improved.

[0075] The upper limit of the total number of carbon atoms and oxygen atoms in the main chain of the linking group may be, for example, 40, or 30, or 20, or 15.

[0076] Examples of the groups and bonds that constitute the linking group include an alkyl group, a glycidoxy group excluding an epoxy group, a glycidyl group excluding an epoxy group, a carbonyl group, an ether bond, an ester bond, and the like. That is, in the glycidoxy group or glycidyl group, the epoxy group constitutes the above epoxy group, and carbon, hydrogen, and oxygen other than the epoxy group constitute the linking group. In the present embodiment, the linking group is preferably composed of an alkyl group and a glycidoxy group excluding an epoxy group. In this case, the number of carbon atoms in the main chain of the alkyl group may be 8 or more, whereby the adhesion is further improved. The upper limit of the number of carbon atoms may be, for example, 38, 28, 18, or 13.

[0077] The alkoxysilyl group is represented by Si(OR). 3 Here, R is an alkyl group. The number of carbon atoms contained in R may be 1 to 4, or may be 1 to 2. Thereby, the adhesion between the resin film and the workpiece is further improved.

[0078] Specific examples of the alkoxysilane compound FA include the compounds shown in the following formula 1.

[0079]

Chemical formula

[0080] (1,2,3 - silane compound FB) The silane compound FB has a cyclic siloxane structure and two or more epoxy group - containing organic groups bonded to the cyclic siloxane structure. The cyclic siloxane structure is a structure in which three or more siloxane bonds (Si - O) to which organic groups are bonded are connected in series to form a cyclic siloxane skeleton.

[0081] When the silane compound FB having such a structure is present in the resin film-forming film, as shown in Fig. 2(b), the hydroxyl group formed by the ring-opening of the epoxy group is likely to form a covalent bond with the workpiece 100. As a result, the adhesion to the workpiece 100 is improved. In addition, since the siloxane skeleton 5 has strong properties as an inorganic substance, it has good compatibility with the inorganic workpiece 100. Therefore, when the siloxane skeleton 5 is located near the workpiece 100, the siloxane skeleton 5 is likely to be fixed near the workpiece 100. As a result, it functions to suppress the peeling of the resin film from the workpiece. Furthermore, since the cyclic siloxane structure has little expansion and contraction, even when the resin film is heated, the expansion of the resin film tends to be suppressed. Therefore, it functions to suppress the peeling of the resin film from the workpiece. Also, when a structure 7 composed of an organic component is present in the resin film 2, the epoxy group 3b in the silane compound FB can bind to the structure 7, further improving the adhesion.

[0082] The number of siloxane bonds in the cyclic siloxane structure may be 3 to 6, or may be 4 to 6. Thereby, the adhesion between the resin film and the workpiece is further improved.

[0083] The number of epoxy group-containing organic groups may be 3 or more, or may be 4 or more. Also, the number of epoxy group-containing organic groups may be 8 or less, or may be 6 or less. Thereby, the adhesion between the resin film and the workpiece is further improved.

[0084] Specific examples of the silane compound FB include the compounds shown in the following formula 2.

[0085]

Chemical formula

[0086] (1,2,4-Alkoxysilane compound FC) The alkoxysilane compound FC has an alkoxysilyl group and a thiourea bond or a urea bond. The alkoxysilane compound FC has a site that exhibits non-covalent and non-ionic bonding interactions. Specifically, the site having a thiourea bond or a urea bond forms a coordination bond with an active hydrogen, a metal ion, or the like.

[0087] When the alkoxysilane compound FC having such a structure is present in the resin film-forming film, as shown in Fig. 2(c), the alkoxysilyl group 3a is likely to form a covalent bond with the workpiece 100, and the site 6 that exhibits non-covalent and non-ionic bonding interactions is likely to form a coordination bond with the workpiece 100. As a result, the adhesion to the workpiece 100 is improved. In particular, in the resin film-forming film, when the structure 7 composed of an organic component contains a component having a hydroxyl group or a component that generates a hydroxyl group, the alkoxysilyl group 3a not bonded to the workpiece 100 is likely to form a covalent bond with the hydroxyl group, and the site 6 that exhibits non-covalent and non-ionic bonding interactions not bonded to the workpiece 100 is likely to form a coordination bond with the hydroxyl group.

[0088] The alkoxysilyl group and the thiourea bond or the urea bond may be directly bonded or may be bonded via an organic group. Examples of the group and bond constituting the organic group include an alkyl group, a carbonyl group, an ether bond, an ester bond, and the like.

[0089] The thiourea bond may have an organic group different from the organic group bonded to the alkoxysilyl group. Examples of such an organic group include a group having a heterocyclic ring and an alkyl group, and an alkyl group is preferred.

[0090] The urea bond may have an organic group different from the organic group bonded to the alkoxysilyl group. Examples of such an organic group include a group having a heterocyclic ring and an alkyl group, and a group having a heterocyclic ring is preferred.

[0091] The alkoxysilyl group is Si(OR) 3It is represented by R is an alkyl group. The number of carbon atoms contained in R may be 1 to 4, or may be 1 to 2. Thereby, the adhesion between the resin film and the work is further improved.

[0092] Specific examples of the alkoxysilane compound FC having a thiourea bond include the compounds shown in the following formula 3.

[0093]

Chemical formula

[0094] Specific examples of the alkoxysilane compound FC having a urea bond include the compounds shown in the following formula 4.

[0095]

Chemical formula

[0096] In 100 parts by mass of the resin film-forming film according to the present embodiment, the content of one or more selected from the alkoxysilane compound FA, the silane compound FB, and the alkoxysilane compound FC (the total content of the alkoxysilane compound FA, the silane compound FB, and the alkoxysilane compound FC) is preferably 0.02 parts by mass or more and 4 parts by mass or less. The content may be 0.05 parts by mass or more, or may be 0.1 parts by mass or more, or may be 0.15 parts by mass or more. Further, the content may be 3 parts by mass or less, or may be 2 parts by mass or less, or may be 1 part by mass or less, or may be 0.5 parts by mass or less.

[0097] In this embodiment, the composition for forming a resin film preferably contains a polymer component (A), a curable component (B), and a filler (E) in addition to the silane coupling agent (F) described above. By including such components, the resin film for forming a resin film can be provided with film-forming properties (film-forming ability) while giving appropriate tack, improving the adhesion suitability between the resin film for forming a resin film and the workpiece, making it easier to form a resin film with high protective performance, making it easier to obtain the effects exerted by the silane coupling agent described above, and making it easier to further improve the adhesion between the resin film and the workpiece.

[0098] The polymer component is a component that can be regarded as being formed by the polymerization reaction of a polymerizable compound. The curable component is a component that can undergo a curing (polymerization) reaction. In the present invention, the polymerization reaction includes a polycondensation reaction.

[0099] Also, the components contained in the polymer component may also correspond to the curable component. In this embodiment, when the composition for forming a resin film contains a component that corresponds to both such a polymer component and a curable component, the composition for forming a resin film is regarded as containing both a polymer component and a curable component.

[0100] (1.2.5. Polymer Component) The polymer component (A) gives the resin film for forming a resin film film-forming properties (film-forming ability) while giving appropriate tack, ensuring uniform attachment of the resin film for forming a resin film to the workpiece. The weight average molecular weight of the polymer component is usually in the range of 50,000 to 2,000,000, preferably 100,000 to 1,500,000, and particularly preferably 200,000 to 1,000,000. As such a polymer component, for example, acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, etc. are used, and acrylic resin is particularly preferably used.

[0101] Examples of the acrylic resin include (meth)acrylic acid ester copolymers composed of a (meth)acrylic acid ester monomer and a structural unit derived from a (meth)acrylic acid derivative. Here, as the (meth)acrylic acid ester monomer, preferably, (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 18 carbon atoms are exemplified, and specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. are exemplified. Further, examples of the (meth)acrylic acid derivative include (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc.

[0102] In this embodiment, it is preferable to introduce a glycidyl group into the acrylic resin using glycidyl methacrylate or the like. The compatibility between the acrylic resin having a glycidyl group introduced therein and the epoxy resin as a thermosetting component described later is improved, uniform film formation becomes easier, and a resin film-forming film with stable performance tends to be easily obtained. Further, in this embodiment, in order to control the adhesiveness and tackiness properties to the work, it is preferable to introduce a hydroxyl group into the acrylic resin using hydroxyethyl acrylate or the like.

[0103] The glass transition temperature of the acrylic resin is preferably -70 to 40°C, -35 to 35°C, -20 to 30°C, -10 to 25°C, -5 to 20°C. By setting the glass transition temperature of the acrylic resin within the above range, the tack of the resin film-forming film is moderately increased, and the adhesion suitability of the resin film-forming film to the work is improved.

[0104] When the acrylic resin has m types (m is an integer of 2 or more) of structural units, the glass transition temperature of the acrylic resin can be calculated as follows. That is, when non-repeating numbers from 1 to m are sequentially assigned to the m types of monomers that induce the structural units in the acrylic resin and named "monomer m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the following Fox's formula.

[0105] [Number] (In the formula, Tg is the glass transition temperature of the acrylic resin; m is an integer of 2 or more; Tgk is the glass transition temperature of the homopolymer of monomer m; Wk is the mass fraction of the structural unit m derived from monomer m in the acrylic resin, provided that Wk satisfies the following formula.)

[0106] [Number] (In the formula, m and Wk are the same as above.)

[0107] As Tgk, values described in a polymer data handbook, an adhesion handbook, Polymer Handbook, etc. can be used. For example, the Tgk of the homopolymer of methyl acrylate is 10 °C, the Tgk of the homopolymer of n-butyl acrylate is -54 °C, the Tgk of the homopolymer of 2-hydroxyethyl acrylate is -15 °C, and the Tgk of the homopolymer of glycidyl methacrylate is 41 °C.

[0108] When the total weight of the composition for forming a resin film is 100 parts by mass, the content of the polymer component may be 5 to 55 parts by mass, 5 to 40 parts by mass, 10 to 55 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass. By setting the content of the polymer component within the above range, it becomes easier to impart film-forming properties (film-forming properties) to the resin film-forming film while giving appropriate tack and adjusting the adhesion suitability between the resin film-forming film and the workpiece.

[0109] (1.2.6. Thermosetting component) The curable component (B) cures the resin film-forming film to form a hard resin film. As the curable component, a thermosetting component, an energy ray curable component, or a mixture thereof can be used. As described above, since the resin film-forming film is preferably thermosetting, the curable component is also preferably a thermosetting component.

[0110] As the thermosetting component, for example, an epoxy resin, a thermosetting polyimide resin, an unsaturated polyester resin, and a mixture thereof are preferably used. The thermosetting polyimide resin is a general term for low molecular weight and low viscosity monomers or precursor polymers that form a polyimide resin by thermosetting. Non-limiting specific examples of the thermosetting polyimide resin are described, for example, in the Journal of the Fiber Society, "Fiber and Industry", Vol. 50, No. 3 (1994), P106 - P118.

[0111] The epoxy resin as the thermosetting component has the property of forming a three-dimensional network structure and a strong film when heated. As such an epoxy resin, various known epoxy resins are used. In this embodiment, the molecular weight (formula weight) of the epoxy resin is preferably 300 or more and less than 50000, 300 or more and less than 10000, 300 or more and less than 5000, 300 or more and less than 3000. Also, the epoxy equivalent of the epoxy resin is preferably 50 to 5000 g / eq, more preferably 100 to 2000 g / eq, and even more preferably 150 to 1000 g / eq.

[0112] Examples of such epoxy resins specifically include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolak, and cresol novolak; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl-type or alkyl glycidyl-type epoxy resins in which active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is substituted with a glycidyl group; so-called alicyclic epoxides in which an epoxy group is introduced by oxidizing a carbon-carbon double bond in the molecule, such as vinyl cyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane. In addition, epoxy resins having a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, etc. can also be used.

[0113] When a thermosetting component is used as the curable component (B), it is preferable to use a curing agent (C) as an auxiliary agent in combination. For example, as a curing agent for an epoxy resin, a thermally active latent epoxy resin curing agent is preferable. The "thermally active latent epoxy resin curing agent" is a type of curing agent that is difficult to react with an epoxy resin at room temperature (23°C) and is activated by heating above a certain temperature to react with the epoxy resin. The activation methods of the thermally active latent epoxy resin curing agent include a method of generating active species (anions, cations) by a chemical reaction by heating; a method in which it is stably dispersed in the epoxy resin near room temperature and is compatible / dissolved with the epoxy resin at high temperature to initiate a curing reaction; a method in which a molecular sieve-encapsulated type curing agent elutes at high temperature to initiate a curing reaction; a method using microcapsules, etc.

[0114] Among the exemplified methods, a method in which it is stably dispersed in the epoxy resin near room temperature and is compatible / dissolved with the epoxy resin at high temperature to initiate a curing reaction is preferable.

[0115] Specific examples of the heat-activated latent epoxy resin curing agent include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, high melting point active hydrogen compounds such as imidazole compounds, and the like. These heat-activated latent epoxy resin curing agents can be used alone or in combination of two or more. In this embodiment, dicyandiamide is particularly preferred.

[0116] In addition, a phenolic resin is also preferred as a curing agent for the epoxy resin. As the phenolic resin, condensates of phenols such as alkylphenols, polyhydric phenols, naphthols and aldehydes are used without particular limitation. Specifically, phenol novolak resin, o-cresol novolak resin, p-cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol resin, polyparavinylphenol resin, bisphenol A type novolak resin, or modified products thereof are used.

[0117] The phenolic hydroxyl groups contained in these phenolic resins can easily undergo an addition reaction with the epoxy groups of the above epoxy resin by heating to form a cured product with high impact resistance.

[0118] The content of the curing agent (C) may be 0.3 to 5 parts by mass, 0.3 to 3 parts by mass, 0.5 to 5 parts by mass, or 0.5 to 3 parts by mass with respect to 100 parts by mass of the curable component (B). By setting the content range of the curing agent (C) within the above range, it is easy to obtain the performance of protecting the work as a resin film (for example, a protective film).

[0119] When using dicyandiamide as the curing agent (C), it is preferable to further use a curing accelerator (D) in combination. Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms) are preferable. Among these, 2-phenyl-4,5-dihydroxymethylimidazole is particularly preferable.

[0120] The content of the curing accelerator (D) may be 0.3 to 5 parts by mass, 0.4 to 4 parts by mass, or 0.5 to 3 parts by mass with respect to 100 parts by mass of the curable component (B). By setting the content range of the curing accelerator (D) within the above range, it is easy to obtain the performance of protecting the work as a resin film (for example, a protective film).

[0121] When the total weight of the resin film-forming film composition is 100 parts by mass, the total content of the thermosetting component and the curing agent may be 5 to 55 parts by mass, 5 to 45 parts by mass, 10 to 35 parts by mass, or 10 to 30 parts by mass. When the thermosetting component and the curing agent are blended in such proportions, it is easy to obtain the performance of protecting the work as a resin film (for example, a protective film).

[0122] In particular, when the thermosetting component is an epoxy resin, the content of the epoxy resin when the total weight of the resin film-forming film composition is 100 parts by mass may be 10 parts by mass or more, 12 parts by mass or more, or 14 parts by mass or more. By containing the epoxy resin in a predetermined amount or more, good curability is easily obtained.

[0123] (1.2.7. Energy ray curable component) When the curable component (B) is an energy ray curable component, the energy ray curable component is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

[0124] The energy ray curable component is a component that cures upon irradiation with energy rays, and is also a component for imparting film-forming properties, flexibility, etc. to the resin film-forming film.

[0125] Examples of the energy ray curable component include polyfunctional monomers or oligomers, etc., and acrylate compounds having a (meth)acryloyl group are preferred. Examples of the acrylate compound having a (meth)acryloyl group include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane and other bifunctional (meth)acrylates; Polyfunctional (meth)acrylates such as tris(2-(meth)acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl) isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate; Examples thereof include polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomer.

[0126] (1.2.8. Filler) When the resin film-forming film contains the filler (E), the resin film obtained by forming the resin film-forming film into a resin film can be easily adjusted in thermal expansion coefficient. By making this thermal expansion coefficient close to that of the work, the adhesion reliability based on the thermal shock test between the resin film and the work is further improved. In addition, when the resin film-forming film contains the filler (E), a hard resin film (for example, a protective film) can be easily obtained and the performance of protecting the work can be obtained, and furthermore, the moisture absorption rate of the resin film can be reduced.

[0127] The filler (E) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler from the viewpoint of shape stability at high temperatures.

[0128] Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers and the like. Among these, silica and surface-modified silica are preferred. The surface-modified silica is preferably surface-modified with a coupling agent, and more preferably surface-modified with a silane coupling agent.

[0129] The average particle size of the filler is preferably 0.02 to 10 μm, 0.05 to 5 μm, or 0.10 to 3 μm.

[0130] By setting the range of the average particle size of the filler within the above range, the handleability of the composition for forming a resin film is improved. As a result, the quality of the composition for forming a resin film and the resin film is likely to be stable.

[0131] In this specification, "average particle size" means, unless otherwise specified, the value of the particle diameter (D50) at the integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method.

[0132] When the total weight of the composition for forming a resin film is 100 parts by mass, the content of the filler may be 10 to 80 parts by mass, 30 to 70 parts by mass, or 45 to 65 parts by mass.

[0133] By setting the lower limit value of the filler content to the above value, the effect of containing the above-described filler is more easily obtained. Further, by setting the upper limit value of the filler content to the above value, the adhesion suitability of the resin film-forming film to the workpiece is improved.

[0134] (1.2.9. Colorant) The resin film-forming film may contain a colorant (G). Thereby, since the back surface of the individual workpieces such as chips is concealed, various electromagnetic waves generated in the electronic device are blocked, and malfunction of the individual workpieces can be reduced.

[0135] As the colorant (G), for example, known ones such as inorganic pigments, organic pigments, and organic dyes can be used. In the present embodiment, inorganic pigments and organic pigments are preferred.

[0136] Examples of inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium tin oxide) pigments, ATO (antimony tin oxide) pigments, and the like. Examples of organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex dyes), dithiol metal complex pigments, indole phenol pigments, triallylmethane pigments, anthraquinone pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments, and threne pigments, and the like.

[0137] The blending amount of the colorant in the resin film-forming film varies depending on the thickness of the resin film-forming film. For example, when the thickness of the resin film-forming film is 25 μm, the content of the colorant when the total weight of the resin film-forming film composition is 100 parts by mass may be 0.1 to 5 parts by mass, or may be 0.2 to 4 parts by mass.

[0138] The average particle size of the inorganic pigment and the organic pigment is preferably 1 to 500 nm, particularly preferably 3 to 100 nm, and more preferably 5 to 50 nm. When the average particle size of the inorganic pigment and the organic pigment is within the above range, it is easy to control the light transmittance within a desired range.

[0139] (1.2.10. Photoinitiator) When the resin film-forming film composition contains an energy ray curable component, a photoinitiator (H) may be contained in order to efficiently advance the polymerization reaction of the energy ray curable component.

[0140] As the photopolymerization initiator (H) in the composition for the film for forming a resin film, for example, α-ketol compounds such as 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one; Acetophenone-based compounds such as acetophenone, dimethylaminoacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; Benzoin ether-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -n-butyl ether, benzoin isobutyl ether, anisoin methyl ether; Ketal-based compounds such as benzyldimethyl ketal, acetophenone dimethyl ketal; Aromatic sulfonyl chloride-based compounds such as 2-naphthalenesulfonyl chloride; Photoactive oxime-based compounds such as 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetoxyoxime); Benzophenone-based compounds such as benzophenone, p-phenylbenzophenone, benzoylbenzoic acid, dichlorobenzophenone, 4,4'-diethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone; Anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone; Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone; p-dimethylaminobenzoic acid ester; camphorquinone; halogenated ketone; acylphosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; acylphosphonates, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], and the like.

[0141] The photoinitiator (H) contained in the composition for resin film-forming film can be used alone or in combination of two or more.

[0142] The content of the photoinitiator (H) may be 0.1 to 20 parts by mass, 1 to 10 parts by mass, or 1.5 to 5 parts by mass with respect to 100 parts by mass of the energy ray curable component.

[0143] (1.2.11. Other Additives) The composition for resin film-forming film may contain, as other additives, for example, ultraviolet absorbers, crosslinking agents, plasticizers, antistatic agents, antioxidants, gettering agents, tackifiers, release agents, etc. within a range not impairing the effects of the present invention. The content of other additives when the total weight of the composition for resin film-forming film is 100 parts by mass may be less than 4 parts by mass or less than 2 parts by mass.

[0144] On the one hand, in the present embodiment, from the perspective of controlling thermosetting properties, it is preferable that the resin film-forming composition substantially does not contain a maleimide resin. Substantially not containing a maleimide resin means that the content of the maleimide resin is less than 1 part by mass in 100 parts by mass of the resin film-forming composition. By substantially not containing a maleimide resin, it becomes easier to control thermosetting properties, and the toughness of the resin film after curing tends to be good.

[0145] Also, in the present embodiment, from the perspective of curability, it is preferable that the resin film-forming composition substantially does not contain a thiol group-containing substance. Substantially not containing a thiol group-containing substance means that the content of the thiol group-containing substance is less than 1 part by mass in 100 parts by mass of the resin film-forming composition. By substantially not containing a thiol group-containing substance, the curability of the resin film tends to be good.

[0146] (2. Sheet for resin film formation and composite sheet for resin film formation) The resin film-forming film is usually used in the form of a sheet for resin film formation or a composite sheet for resin film formation.

[0147] The sheet 10 for resin film formation has the configuration shown in FIG. 3. The resin film-forming film 1 has two opposing main surfaces 1a and 1b. On the main surface 1a, a first release film 21 that supports the resin film-forming film 1 is disposed, and on the main surface 1b, a second release film 22 that supports the resin film-forming film 10 is disposed.

[0148] Also, the composite sheet for resin film formation has a resin film-forming film and a support sheet that supports the resin film-forming film. The support sheet is other than a release film and has a configuration capable of supporting the resin film-forming film. Examples of the support sheet include an adhesive sheet having a base material and an adhesive layer.

[0149] Specifically, as shown in FIG. 4, the composite sheet 11 for forming a resin film includes an adhesive sheet 40 in which an adhesive layer 42 is laminated on one surface of a base material 41 as a support sheet, a resin film forming film 1 laminated on the adhesive layer 42 of the adhesive sheet 40 such that the main surface 1a is in contact therewith, and a release film 23 disposed on the main surface 1b of the resin film forming film 1. Further, a jig adhesive layer (not shown) may be disposed on the peripheral edge of the resin film forming film 1. The jig adhesive layer is a layer for adhering the composite sheet for forming a resin film to a jig such as a ring frame.

[0150] (2.1. Release Film) The release film is a film that can support the resin film forming film in a peelable manner. Examples of such a release film include a film in which a resin film is used as a base material and the surface of the resin film is subjected to a release treatment. The release treatment may be a treatment for modifying the surface of the resin film, or may be a treatment for forming a material (release agent layer) not derived from the resin film on the surface of the resin film.

[0151] As the resin film, a known resin film can be used, and a polyethylene terephthalate film is preferable from the viewpoints of environmental safety, cost, etc. Further, the release agent layer can be formed using a known release agent. Examples of known release agents include alkyd-based release agents, silicone-based release agents, fluorine-based release agents, unsaturated polyester-based release agents, polyolefin-based release agents, and wax-based release agents. Among them, silicone-based release agents are preferable.

[0152] The thickness of the release film may be 15 to 100 μm, may be 25 to 80 μm, or may be 35 to 60 μm.

[0153] In addition, when release films are formed on both main surfaces of the resin film forming film as shown in FIG. 3, it is preferable to increase the release force of one release film to form a double-release type release film, and to decrease the release force of the other release film to form a light-release type release film.

[0154] For example, the first release film 21 can be a double-release type release film, and the second release film 22 can be a light-release type release film. In this case, if the release force when the first release film 21 is peeled from the resin film forming film 1 is F1, and the release force when the second release film 22 is peeled from the resin film forming film 1 is F2, then the relationship F1 > F2 is satisfied.

[0155] Furthermore, the release force F1 may be 60 - 400 mN / 100 mm, or may be 80 - 380 mN / 100 mm, or may be 100 - 360 mN / 100 mm. Also, the release force F2 may be 20 - 250 mN / 100 mm, or may be 25 - 240 mN / 100 mm, or may be 30 - 230 mN / 100 mm. When the release forces F1 and F2 are within the above ranges, the release suitability is improved, and peeling defects during peeling of the release film can be suppressed.

[0156] Also, as shown in FIG. 4, when a release film (release film 23) is formed on one main surface of the resin film forming film, if the release force when the release film 23 is peeled from the resin film forming film 1 is F3, then the release force F3 may be 60 - 400 mN / 100 mm, or may be 80 - 380 mN / 100 mm, or may be 100 - 360 mN / 100 mm. When the release force F3 is within the above range, the release suitability is improved, and peeling defects during peeling of the release film can be suppressed.

[0157] (3. Manufacture of the resin film forming film) The resin film forming film can be manufactured by a known method. For example, it can be manufactured using the coating liquid described above. First, the above-described coating liquid is applied to the release surface of the first release film using a coating machine such as a roll coater, knife coater, roll knife coater, air knife coater, die coater, bar coater, gravure coater, curtain coater, etc. If necessary, the solvent of the coating liquid is removed by drying to form a resin film forming film on the first release film.

[0158] When manufacturing a sheet for forming a resin film, it is obtained by further laminating the release surface of a second release film onto the exposed surface of the resin film-forming film formed on the first release film.

[0159] Also, when manufacturing a composite sheet for forming a resin film, a laminate including an adhesive sheet and a sheet for forming a resin film can be used. The adhesive sheet can be manufactured by a known method. For example, a composition constituting the adhesive layer is prepared, applied to the release surface of a third release film, dried as necessary, and an adhesive layer is formed on the third release film. Next, a substrate is laminated onto the exposed adhesive layer to obtain an adhesive sheet with the third release film disposed on the adhesive layer.

[0160] Subsequently, the second release film of the sheet for forming a resin film is peeled off, the third release film of the adhesive sheet is peeled off, and the resin film-forming film and the adhesive layer are laminated together to obtain a composite sheet for forming a resin film. Note that the resin film-forming film may be cut into a size appropriate for the adherend (e.g., a wafer) to be attached or a size close to that of the adherend at an appropriate timing as necessary.

[0161] (4. Method for manufacturing individual pieces of a workpiece with a resin film) The method for manufacturing individual pieces of a workpiece with a resin film according to this embodiment includes at least the following steps 1 to 3. Step 1: A step of attaching the above-described resin film-forming film to a workpiece Step 2: A step of forming a resin film from the resin film-forming film attached after the step of attaching it to the workpiece Step 3: A step of cutting the workpiece to which the resin film or the resin film-forming film has been attached after the step of attaching it to the workpiece into individual pieces to obtain a plurality of individual pieces of the workpiece with a resin film or a resin film-forming film

[0162] As is clear from the above, after Step 1, Step 2 may be performed before or after Step 3.

[0163] The method for manufacturing individual pieces of a workpiece with a resin film having the above-described steps 1 to 3 will be described with reference to FIGS. 5A, 5B, and 6.

[0164] Hereinafter, as an example of a method for manufacturing individual pieces of a workpiece with a resin film using a sheet for forming a resin film or a composite sheet for forming a resin film according to the present embodiment, a method for manufacturing a chip with a protective film obtained by processing a wafer with a protective film formation film attached thereto will be described.

[0165] As shown in FIG. 5A, the protective film formation film 1 of the protective film formation sheet 10 is attached to the back surface of the wafer 100 (step 1). The first release film 21 may be peeled off if necessary after step 1.

[0166] Also, as shown in FIG. 5B, the protective film formation film 1 of the protective film formation composite sheet 11 is attached to the wafer 100 (step 1). At this time, the jig adhesive layer 50 provided on the outer peripheral portion of the protective film formation film 1 may be attached to and fixed to the ring frame 150. The wafer 100 is attached to the surface of the protective film formation film 1 opposite to the attachment surface with the adhesive layer 42. When attaching the protective film formation film 1 to the wafer 100, the protective film formation film 1 may be heated as desired to exhibit adhesiveness.

[0167] Thereafter, the applied protective film forming film 1 is converted into a protective film to form a protective film (step 2), and a wafer with a protective film is obtained. When the protective film forming film is thermosetting, the protective film forming film may be heated at a predetermined temperature for an appropriate time. For example, the heating temperature during the thermosetting of the protective film forming film may be 100 to 200°C, may be 110 to 170°C, or may be 120 to 150°C. And the heating time during the thermosetting may be 0.5 to 5 hours, may be 0.5 to 4 hours, or may be 1 to 3 hours. It is preferable that the protective film formed by thermosetting is gradually cooled to room temperature. The method of gradual cooling is not particularly limited and may be natural cooling. Also, when the protective film forming film is energy ray curable, energy rays may be incident from the adhesive sheet or the release film side. For example, the illuminance of the energy rays during energy ray curing may be 60 to 320 mW / cm 2 and the light amount of the energy rays may be 100 to 1000 mJ / cm 2 . The energy rays are preferably ultraviolet rays.

[0168] Note that the conversion of the protective film forming film into a protective film may be performed after the dicing process, and the chip with the protective film forming film may be picked up from the adhesive sheet, and then the protective film forming film may be converted into a protective film.

[0169] Next, if necessary, the wafer 100 with a protective film and the ring frame 150 obtained by converting the protective film forming film 1 shown in FIG. 5A into a protective film are attached onto a known dicing sheet 80, and the wafer 100 with a protective film is diced to obtain a chip (chip 101 with a protective film) having the protective film 2 shown in FIG. 6. Or, the wafer 100 with the protective film forming film 1 and the ring frame 150 shown in FIG. 5A are attached onto a known dicing sheet 80, and the wafer 100 with the protective film forming film is diced to obtain a chip (chip with a protective film forming film) having the protective film forming film 1 (step 3).

[0170] Also, by a known method, the wafer 100 with a protective film obtained by forming a protective film on the protective film forming film 1 shown in FIG. 5B is diced to obtain a chip having a protective film 2 (chip 101 with a protective film) shown in FIG. 6. Alternatively, the wafer 100 with the protective film forming film 1 shown in FIG. 5B is diced to obtain a chip having a protective film forming film (chip with a protective film forming film) (Step 3).

[0171] The chip with a protective film or a protective film forming film thus obtained contains the above-described silane coupling agent in the protective film or the protective film forming film, so that peeling between the protective film and the chip is suppressed even in a severe acceleration test such as PCT.

[0172] The obtained chip with a protective film or a protective film forming film is picked up and mounted on a substrate or the like.

[0173] (5. Modification Example) The resin film forming film may be a die bonding film. The die bonding film is composed of a film-shaped adhesive. The film-shaped adhesive only needs to have the above-described silane coupling agent as in the composition for the resin film forming film.

[0174] Further, the composite sheet for resin film formation may be a dicing die bonding sheet in which a die bonding film is laminated and integrated with a support sheet (dicing sheet) used for fixing a semiconductor wafer during dicing. Any known dicing sheet may be used as the dicing sheet.

[0175] Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments at all, and may be modified in various ways within the scope of the present invention.

Examples

[0176] Hereinafter, the invention will be described in more detail using examples, but the present invention is not limited to these examples.

[0177] (Experiment 1) (Preparation of Sheet for Forming Resin Film) A sheet for forming a thermosetting resin film was prepared as follows using a coating liquid containing the following composition for the resin film-forming film.

[0178] (Coating Liquid Containing Composition for Resin Film-Forming Film) The following components were mixed at the blending ratios (in terms of solid content) shown in Table 1 and diluted with methyl ethyl ketone so that the solid content concentration became 50% by mass to prepare a coating liquid containing a composition for a resin film-forming film.

[0179] (A) Polymer Component (A-1) (Meth)acrylate copolymer obtained by copolymerizing 12 parts by mass of n-butyl acrylate, 65 parts by mass of methyl acrylate, 7 parts by mass of glycidyl methacrylate, and 16 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 500,000, glass transition temperature: -2°C) (A-2) (Meth)acrylate copolymer obtained by copolymerizing 87 parts by mass of methyl acrylate and 13 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 450,000, glass transition temperature: 6°C) (B) Curing Component (Thermosetting Component) (B-1) Bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., BPA328, epoxy equivalent: 230 - 240 g / eq) (B-2) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent: 184 - 194 g / eq) (B-3) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1055, epoxy equivalent: 800 - 900 g / eq) (B-4) Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, Epiklon HP-7200HH, epoxy equivalent: 274 - 286 g / eq) (B-5) Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, Epiklon HP-7200, epoxy equivalent: 254 - 264 g / eq) (C) Hardening agent: Dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7) (D) Hardening accelerator: 2-Phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curezol 2PHZ) (E) Filler (E-1) Epoxy group-modified spherical silica filler (manufactured by Admatechs Co., Ltd., SC2050MA, average particle size 0.5 μm) (F) Silane coupling agent (F-1) 8-Glycidoxy octyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-4803) (F-2) Epoxy-modified cyclic siloxane compound (manufactured by Shin-Etsu Chemical Co., Ltd., KR-470) (F-3) Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1116) (F-4) Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-989MS) (F-5) Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) (G) Colorant (G-1) Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600, average particle size 28 nm) (G-2) Organic black pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., 6377 Black)

[0180]

Table 1

[0181] A first release film (manufactured by Lintec Corporation, SP-PET502150) in which a silicone-based release agent layer is formed on one side of a polyethylene terephthalate (PET) film with a thickness of 50 μm was prepared. Also, a second release film (manufactured by Lintec Corporation, SP-PET381031) in which a silicone-based release agent layer is formed on one side of a polyethylene terephthalate (PET) film with a thickness of 38 μm was prepared.

[0182] The coating liquid containing each composition for forming a resin film was applied to the release-treated surface of the first release film and dried at 100°C for 2 minutes to form a resin film-forming film with a thickness of 25 μm. Subsequently, the release-treated surface of the prepared second release film was attached to the surface of the resin film-forming film to obtain a resin film-forming sheet with release films disposed on both sides of the resin film-forming film. The attachment conditions were a temperature of 60°C, a pressure of 0.4 MPa, and a speed of 1 m / min.

[0183] Subsequently, the following measurements and evaluations were performed.

[0184] (Arithmetic mean height Sa of the resin film-forming film) The second release film was peeled off from the obtained resin film-forming sheet. For the exposed surface of the resin film-forming film (the surface to be attached to the workpiece), in accordance with ISO 25178, the arithmetic mean height Sa was measured as follows.

[0185] Using a scanning white light interference microscope ("VS-1550" manufactured by Hitachi High-Technologies Corporation), the surface of the resin film-forming film to be measured was observed at an observation magnification of 50 times in a multi-field mode. At this time, in the observation field, a region with a length of 0.36 mm in the X-axis direction and a length of 0.27 mm in the Y-axis direction was set, and a total of 12 cells were observed by observing 3 columns in the X-axis direction and 4 rows in the Y-axis direction. Then, the images of the 12 cells were combined into one image of 1.0 mm × 1.0 mm, and Sa was measured for the entire area of the combined one image. The results are shown in Table 2.

[0186] (Retention rate of copper foil peel strength) The retention rate of copper foil peel strength was evaluated by calculating the ratio of the copper foil peel strength at normal temperature (23°C, relative humidity 50%) to the copper foil peel strength at normal temperature (23°C, relative humidity 50%) after standing for one week under high temperature and high humidity conditions (85°C, relative humidity 85%).

[0187] The copper foil peel strength at room temperature was measured as follows. First, the second release film was peeled off from the sheet for resin film formation. The polished surface (thickness: 350 μm) of a silicon wafer whose back surface was polished with a #2000 specification grinding wheel was laminated (lamination speed: 0.3 m / min) on the surface of the exposed resin film formation film while heating to 70°C. Then, the first release film was peeled off from the sheet for resin film formation. A 3 cm × 10 mm area of a copper foil (alloy symbol "C1220R" conforming to JIS H3100) cut into strips (5 cm × 10 mm × 150 μm) was laminated (lamination speed: 0.3 m / min) on the surface of the exposed resin film formation film while heating to 70°C. And then, it was left standing in an environment of 130°C for 2 hours to completely thermoset the resin film formation film, form a resin film, and then cooled to room temperature. After that, a 2 cm × 10 mm area of the strip-shaped copper foil where the resin film was not attached was fixed to the gripping jig of a precision universal testing machine, and while maintaining a peeling angle of 90°, at a peeling speed of 50 mm / min, the peeling strength (unit: N / 10 mm) when the copper foil attached to the resin film was peeled 3 cm in length from the silicon wafer was measured with a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS"). Among the measured values, the average of the measured values excluding the values when peeling the first 5 mm in length and the values when peeling the last 5 mm in length was taken as the copper foil peel strength at room temperature.

[0188] Subsequently, the copper foil peel strength at room temperature after standing in high-temperature and high-humidity conditions was measured as follows. First, the second release film was peeled off from the resin film forming sheet. The polished surface (thickness: 350 μm) of a silicon wafer whose back surface was polished with a #2000 specification grinding wheel was laminated (lamination speed: 0.3 m / min) on the surface of the exposed resin film forming film while heating to 70°C. Then, the first release film was peeled off from the resin film forming sheet. A 3 cm × 10 mm area of a copper foil (alloy symbol "C1220R" conforming to JIS H3100) cut into strip shape (5 cm × 10 mm × 150 μm) was laminated (lamination speed: 0.3 m / min) on the surface of the exposed resin film forming film while heating to 70°C. Then, it was left standing in an environment of 130°C for 2 hours to completely thermoset the resin film forming film, form a resin film, and allowed to cool to room temperature. Thereafter, the copper foil-attached sample was put into a thermostatic and humidistatic chamber at 85°C and relative humidity of 85%. After one week, the sample was taken out from the thermostatic and humidistatic chamber. In the taken-out sample, a 2 cm × 10 mm area where the resin film of the strip-shaped copper foil was not attached was fixed to the gripping jig of a precision universal testing machine, and while maintaining a peeling angle of 90°, at a peeling speed of 50 mm / min, the peeling strength (unit: N / 10 mm) when the copper foil attached to the resin film was peeled 3 cm in length from the silicon wafer was measured with a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS"). Among the measured values, the average of the measured values excluding the first 5 mm in length peeled off and the last 5 mm in length peeled off was taken as the copper foil peel strength at room temperature after standing in high-temperature and high-humidity conditions.

[0189] From the obtained copper foil peel strength at room temperature and the copper foil peel strength at room temperature after standing in high-temperature and high-humidity conditions, the retention rate of the copper foil peel strength was calculated by the following formula. The results are shown in Table 2. Retention rate of copper foil peel strength (%) = 100 × (copper foil peel strength at room temperature after standing in high-temperature and high-humidity conditions) / (copper foil peel strength at room temperature)

[0190] (Peeling force F1 of the first release film) The second release film was peeled off from the obtained sheet for forming a resin film. The good adhesion surface of a good adhesion PET (manufactured by Toyobo Co., Ltd., PET25A-4100) with a thickness of 25 μm was attached to the surface of the resin film forming film exposed by the peeling by thermal lamination (70 °C, 1 m / min) to prepare a laminate sample. The laminate sample was cut into a width of 100 mm to prepare a measurement sample. The back surface of the first release film of the measurement sample was fixed to a rigid support plate with double-sided tape.

[0191] Using a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph (registered trademark) AG-IS"), the composite (integral type) body of the resin film forming film / good adhesion PET was peeled off from the first release film at a peeling angle of 180° and a peeling speed of 1 m / min in an environment of 23 °C and a relative humidity of 50%, and the load at that time was measured. The measurement distance was 100 mm in total, and the average of the measured values between 80 mm excluding the first 10 mm and the last 10 mm was converted to mN / 100 mm as the peeling force F1. The results are shown in Table 2.

[0192] (Peeling force F2 of the second release film) The obtained sheet for forming a resin film was cut into a width of 100 mm to prepare a measurement sample. The back surface of the first release film of the measurement sample was fixed to a rigid support plate with double-sided tape.

[0193] Using a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph (registered trademark) AG-IS"), the second release film was peeled off from the measurement sample, and the load at that time was measured under the same conditions as the measurement of F1, and the peeling force F2 was obtained. The results are shown in Table 2.

[0194] (Maximum transmittance in the visible light region) The first release film was peeled off from the obtained sheet for forming a resin film. The peeled first release film was placed in the sample folder of a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation). Without using an integrating sphere, in direct light receiving mode, in the visible light region with a wavelength range of 400 to 700 nm, the baseline in the transmittance measurement was measured. By this measurement, the transmittance passing only through the first release film becomes 100% at each wavelength in the range of 400 to 700 nm.

[0195] The second release film was peeled off from a sheet for forming a resin film (second release film / resin film forming film / first release film) different from the sheet for forming a resin film from which the first release film had been peeled. The laminate of the resin film forming film / first release film was placed in the sample folder of a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation). Without using an integrating sphere, in direct light receiving mode, in the visible light region with a wavelength range of 400 to 700 nm, the transmittance was measured. By this measurement, the transmittance of the resin film forming film alone was measured. From the measurement results, the maximum transmittance in the visible light region was calculated. The results are shown in Table 2.

[0196] (PCT) The second release film was peeled off from the obtained sheet for forming a resin film. While heating to 70°C at a speed of 0.3 m / min, the exposed resin film forming film was attached to the polished surface of a silicon wafer (200 mm in diameter, 350 μm thick) polished with a #2000 specification grinding wheel. The first release film was peeled off from the resin film forming film to expose the resin film forming film. The silicon wafer with the resin film forming film attached was heated in an oven under an air atmosphere at 130°C for 2 hours to thermally cure the resin film forming film, producing a wafer with a resin film, and then allowed to cool to room temperature.

[0197] Subsequently, the surface on the resin film side was attached to a dicing tape (Adwill D-676H manufactured by Lintec Corporation), and using a dicing device (DFD6362 manufactured by DISCO Corporation), the silicon wafer with the resin film was diced into a size of 5 mm × 5 mm, and by peeling it from the dicing tape, a chip with a resin film was obtained.

[0198] Out of the obtained chips with resin films, 25 chips with resin films were placed in a PCT chamber (EHS-221MD manufactured by Espec Corporation), and a PCT (Pressure Cooker Test) was conducted by holding them for 168 hours under the conditions of a temperature of 121°C, a relative humidity of 100%, and a pressure of 2 atm. After the test, the chips with resin films were taken out from the PCT chamber, and using a SAT device (D9600 manufactured by Sono scan), the presence or absence of peeling of the resin film from the chips was evaluated according to the following criteria. The results are shown in Table 2. A: No peeling occurred in 25 chips with resin films B: No peeling occurred in 23 to 24 chips with resin films, and peeling occurred in 1 to 2 chips with resin films C: No peeling occurred in 21 to 22 chips with resin films, and peeling occurred in 3 to 4 chips with resin films D: Peeling occurred in 5 or more chips with resin films

[0199]

Table 2

[0200] From Table 2, it was confirmed that when the above-mentioned silane coupling agent was used, no peeling of the resin film occurred in PCT.

[0201] (Experiment 2) (Preparation of a sheet for forming a resin film) A sheet for forming a resin film containing an energy ray-curable resin film-forming film was prepared in the same manner as in Experiment 1, except that a coating solution containing the following composition for the resin film-forming film was used.

[0202] (Coating solution containing a composition for a resin film-forming film) The following components were mixed at the compounding ratios (in terms of solid content) shown in Table 3, and diluted with methyl ethyl ketone so that the solid content concentration became 45% by mass to prepare a coating solution containing a composition for a resin film-forming film.

[0203] (A) Polymer component (A-3) (Meth)acrylate copolymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 400,000, glass transition temperature: 6°C) (B) Curing component (energy ray-curable component) (B-6) Urethane acrylate (manufactured by KJ Chemicals, Quick cure 8100EA70) (B-7) ε-Caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300-1CL) (E) Filler (E-2) Silica filler (fused quartz filler, average particle diameter 8 μm) (F) Silane coupling agent (F-1) 8-Glycidoxy octyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-4803) (F-2) Epoxy-modified cyclic siloxane compound (manufactured by Shin-Etsu Chemical Co., Ltd., KR-470) (F-3) Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1116) (F-4) Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-989MS) (G) Colorant (G-2) Organic black pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., 6377 Black) (H) Photopolymerization initiator (H-1) 2-Hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, Omnirad (registered trademark) 1173) (I) Ultraviolet absorber (I-1) Hydroxyphenyltriazine-based ultraviolet absorber (manufactured by BASF, Tinuvin (registered trademark) 479)

[0204]

Table 3

[0205] Except for not measuring the copper foil peel strength and curing the resin film-forming film by energy rays instead of heat curing during PCT, the same evaluation as in Experiment 1 was carried out using the obtained resin film-forming sheet. Specifically, instead of peeling the first release film from the resin film-forming film to expose the resin film-forming film and heating and thermally curing the silicon wafer with the resin film-forming film attached in an oven under an air atmosphere at 130 °C for 2 hours, without peeling the first release film from the resin film-forming film, an ultraviolet irradiation device (manufactured by Rintec Co., Ltd., product name "RAD-2000m / 12") was used, and the illuminance was 230 mW / cm 2 、and the light quantity was 500 mJ / cm 2 After performing ultraviolet irradiation at to perform energy ray curing and then peeling off the first release film. The results are shown in Table 4.

[0206]

Table 4

[0207] From Table 4, it was confirmed that when the above-described silane coupling agent was used, peeling of the resin film did not occur in PCT.

Explanation of Signs

[0208] 1…Resin film-forming film (protective film-forming film) 2…Resin film (protective film) 10…Resin film-forming sheet 11…Resin film-forming composite sheet

Claims

1. A resin film forming film for forming a resin film by sticking to a workpiece, wherein the resin film forming film has a silane coupling agent, the silane coupling agent is at least one selected from an alkoxysilane compound FA, a silane compound FB, and an alkoxysilane compound FC, the alkoxysilane compound FA has an alkoxysilyl group, an epoxy group, and a linking group that links the alkoxysilyl group and the epoxy group, and is an alkoxysilane compound in which the total number of carbon atoms and oxygen atoms in the main chain of the linking group is 10 or more, the silane compound FB is a silane compound having a cyclic siloxane structure and two or more epoxy groups bonded to the cyclic siloxane structure, the alkoxysilane compound FC is a resin film forming film which is an alkoxysilane compound having an alkoxysilyl group and a thiourea bond or a urea bond.

2. The resin film forming film according to claim 1, wherein the resin film forming film has a curable component and a polymer component.

3. The resin film forming film according to claim 1 or 2, wherein in the resin film forming film, the arithmetic mean height Sa of the surface adhered to the workpiece is 0.02 μm or more and 0.1 μm or less.

4. The resin film forming film according to claim 1 or 2, wherein the epoxy group of the alkoxysilane compound FA is an epoxy group contained in a glycidoxy group, the linking group of the alkoxysilane compound FA is composed of an alkyl group and a glycidoxy group excluding the epoxy group, and the number of carbon atoms in the main chain of the alkyl group is 8 or more.

5. The resin film forming film according to claim 1 or 2, wherein the alkoxysilane compound FC has a heterocyclic ring.

6. The resin film forming film according to claim 1 or 2, wherein the maximum transmittance of light rays having a wavelength of 400 to 700 nm with respect to the resin film forming film is 30% or less.

7. Regarding the copper foil peeling strength indicating the peeling strength between the resin film forming film and the copper foil, the ratio of the copper foil peeling strength at 23°C and 50% relative humidity to the copper foil peeling strength at 23°C and 50% relative humidity after standing at 85°C and 85% relative humidity for one week is 55% or more. The resin film forming film according to claim 1 or 2.

8. A step of sticking the resin film forming film according to claim 1 or 2 to a workpiece, A step of forming a resin film from the resin film forming film after the step of attaching to the workpiece; A method for manufacturing a workpiece piece with a resin film, comprising: a step of fragmenting the workpiece to which the resin film or the resin film forming film is attached after the step of attaching to the workpiece, to obtain a plurality of workpiece pieces with a resin film or a resin film forming film.

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