Method for manufacturing film-like adhesives, film-like adhesive composite sheets, film-like adhesive-coated chips, and method for manufacturing adhesive-cured chips.

Abstract

The present invention provides a film-type adhesive for use in plasma dicing, wherein, if the film-type adhesive or the film-type adhesive is energy-ray curable, the cutting speed of the energy-ray cured product is faster than that of conventional films when cut by irradiation with plasma generated from sulfur hexafluoride gas. [Solution] A film-like adhesive 13 for use in plasma dicing, wherein the film-like adhesive 13 contains a polymer component (a), and the weight-average molecular weight of the polymer component (a) is 250,000 or more.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a film-shaped adhesive, a film-shaped adhesive composite sheet, a chip with a film-shaped adhesive, and a chip with a cured adhesive.

Background Art

[0002] When manufacturing a semiconductor device, for example, a semiconductor chip with a film-shaped adhesive provided on the back surface (the surface opposite to the circuit surface) of the semiconductor chip is manufactured, and this is adhered and fixed to a circuit board by the film-shaped adhesive therein for mounting. The film-shaped adhesive usually has thermosetting properties that are cured by heating. After adhering the semiconductor chip with the film-shaped adhesive to the circuit board, the film-shaped adhesive is thermally cured to fix the semiconductor chip to the circuit board.

[0003] The semiconductor chip with the film-shaped adhesive can be manufactured, for example, by the following method. That is, first, a film-shaped adhesive composite sheet (for example, a die bonding sheet) including a base material and a film-shaped adhesive provided on one surface of the base material is used. The film-shaped adhesive therein is attached to the back surface (the surface opposite to the circuit surface) of the semiconductor wafer. Next, on the base material, the semiconductor wafer is divided to produce semiconductor chips, and the film-shaped adhesive is cut to produce a plurality of the semiconductor chips with the film-shaped adhesive on the base material. Thereafter, the semiconductor chips with the film-shaped adhesive are separated from the base material and picked up, and as described above, are used for manufacturing a semiconductor device.

[0004] The above-mentioned splitting of semiconductor wafers and cutting of film-like adhesives can be carried out by various methods. For example, blade dicing, which uses a blade, is a widely known method for continuously splitting semiconductor wafers and cutting film-like adhesives, but plasma dicing, which uses plasma irradiation, is also known. In the case of plasma dicing, plasma generated from oxygen gas is commonly used (see Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2004-172364 [Overview of the project] [Problems that the invention aims to solve]

[0006] On the other hand, gases other than oxygen, such as sulfur hexafluoride (SF6), are also known as plasma source gases, and being able to use multiple types of gases interchangeably would be highly convenient. However, when using sulfur hexafluoride gas, while wafers can be quickly divided, cutting the film-like adhesive takes time. In other words, plasma generated from sulfur hexafluoride gas is suitable for wafer division, but it has the problem of being slow in cutting the film-like adhesive. Furthermore, energy-ray curable film-like adhesives are sometimes used, in which case plasma dicing is performed after energy-ray curing of the film-like adhesive. However, when plasma generated from sulfur hexafluoride gas is used, the cutting speed of the energy-ray cured film-like adhesive also becomes slow.

[0007] Up to this point, we have explained the problems encountered when manufacturing semiconductor devices, using the example of manufacturing semiconductor chips with film-like adhesives, or semiconductor chips with adhesive-cured products where the film-like adhesive is energy-ray cured, from semiconductor wafers. However, similar problems can also arise when manufacturing chips with film-like adhesives or adhesive-cured products from wafers other than semiconductor wafers.

[0008] The present invention aims to provide a film-like adhesive for use in plasma dicing, which, if the film-like adhesive is energy-ray curable, cuts faster than conventional adhesives when the energy-ray cured material is cut by irradiation with plasma generated from sulfur hexafluoride gas. [Means for solving the problem]

[0009] To solve the above problems, the present invention employs the following configuration. [1] A film-like adhesive for use in plasma dicing, wherein the film-like adhesive contains a polymer component (a), and the weight-average molecular weight of the polymer component (a) is 250,000 or more. [2] The film-like adhesive according to [1], wherein the film-like adhesive substantially does not contain filler (d). [3] The film-like adhesive according to [1] or [2], wherein the thickness of the film-like adhesive is 3 to 25 μm. [4] A film-like adhesive according to any one of [1] to [3], wherein the plasma dicing uses plasma generated from oxygen gas. [5] The film-like adhesive according to any one of [1] to [3], wherein the plasma dicing uses plasma generated from sulfur hexafluoride gas.

[0010] [6] The film-like adhesive according to any one of [1] to [5], wherein the film-like adhesive is energy-ray curable, and after the energy-ray curing of the film-like adhesive, the plasma dicing is used to simultaneously divide the wafer into chips and cut the energy-ray cured film-like adhesive. [7] The film-like adhesive according to any one of [1] to [6], wherein the weight-average molecular weight of the polymer component (a) is less than 1,500,000. [8] comprising a base material and a film-like adhesive provided on one surface of the base material, A film-like adhesive composite sheet wherein the film-like adhesive is the film-like adhesive described in any one of items [1] to [7].

[0011] [9] A method for manufacturing a chip with a film-like adhesive, comprising a chip and a film-like adhesive provided on one side of the chip, wherein the manufacturing method involves attaching a film-like adhesive described in any one of [1] to [7], or a film-like adhesive in a film-like adhesive composite sheet described in [8], to one side of a wafer, irradiating the wafer and the film-like adhesive with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce a chip, and cutting the film-like adhesive, thereby producing the chip with a film-like adhesive.

[10] A method for manufacturing a chip with an adhesive curing agent, comprising a chip and an adhesive curing agent provided on one side of the chip, wherein in the manufacturing method, a film-like adhesive described in any one of [1] to [7], or a film-like adhesive in a film-like adhesive composite sheet described in [8], is applied to one side of a wafer, the film-like adhesive is energy-ray curable, the adhesive curing agent is formed by energy-ray curing the applied film-like adhesive, the wafer and the adhesive curing agent are irradiated with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce a chip, and the adhesive curing agent is cut to produce the adhesive curing agent chip. [Effects of the Invention]

[0012] According to the present invention, a film-like adhesive for use in plasma dicing is provided, and if the film-like adhesive, or the film-like adhesive, is energy-ray curable, the cutting speed is faster than that of conventional films when the energy-ray cured product is cut by irradiation with plasma generated from sulfur hexafluoride gas. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view illustrating a method for measuring the cutting speed during plasma dicing of a film-like adhesive or an energy-ray cured product thereof according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet according to one embodiment of the present invention. [Modes for carrying out the invention]

[0014] ◇Film-type adhesive The film-like adhesive according to an embodiment of the present invention is a film-like adhesive for use in plasma dicing, the film-like adhesive contains a polymer component (a), and the weight average molecular weight of the polymer component (a) is 250,000 or more. The film-like adhesive of the present embodiment can be used in the production of a chip with a film-like adhesive provided with a chip and the film-like adhesive provided on one surface of the chip, and a chip with an adhesive cured product provided with a chip and an energy ray cured product of the film-like adhesive provided on one surface of the chip. At this time, since the film-like adhesive contains the polymer component (a), when the film-like adhesive and the film-like adhesive are energy ray curable, the energy ray cured product is irradiated with plasma generated from sulfur hexafluoride (SF6) gas When cutting, the cutting speed becomes faster than before. Therefore, by plasma dicing, wafer dicing and cutting of the film-like adhesive or its energy ray cured product (adhesive cured product) can be continuously and quickly performed.

[0015] Cutting of the film-like adhesive or its energy ray cured product by irradiation with plasma proceeds by plasma etching, and the cutting speed at this time is synonymous with the etching speed.

[0016] The chip with a film-like adhesive and the chip with an adhesive cured product can be used in the production of a substrate device described later.

[0017] In this specification, the "film-like adhesive" means a film-like adhesive in which neither intentional energy ray curing nor intentional heat curing is performed, unless otherwise specified. The "adhesive cured product" means an energy ray cured product of a film-like adhesive, unless otherwise specified.

[0018] In this specification, the wafers include semiconductor wafers composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulating wafers composed of insulators such as sapphire and glass. For example, if the wafer is a semiconductor wafer, then the chip would be a semiconductor chip. One side of these wafers is the circuit side, on which the circuit is formed, and the side opposite to this is referred to in this specification as the "back side". The same applies to chips manufactured by dividing a wafer through methods such as dicing; the side of the chip opposite the circuit side on which the circuit is formed is called the "back side." Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars.

[0019] In this specification, "substrate device" means a device constructed by bonding and fixing a film-type adhesive chip to a circuit board using the film-type adhesive, or by bonding and fixing a cured adhesive chip to a circuit board using the cured adhesive. For example, if a semiconductor wafer is used as the workpiece, a semiconductor device can be considered as the substrate device.

[0020] A film-like adhesive composite sheet, described later, can be constructed by directly laminating the film-like adhesive of this embodiment onto a substrate, or by using a dicing sheet, which is a laminate of a substrate and an adhesive layer, and laminating the film-like adhesive of this embodiment on the side of the adhesive layer opposite to the substrate. This film-like adhesive composite sheet can be used in the same way as known dicing die bonding sheets.

[0021] The film-like adhesive of this embodiment may or may not be curable (i.e., it may be non-curable). If the film-like adhesive is curable, it is preferably energy-ray curable, and may or may not be thermosetting, but it is more preferable that it is both energy-ray curable and thermosetting. When the film-like adhesive or adhesive curing material used for mounting chips with film-like adhesive or chips with adhesive curing material in a substrate device is thermosetting, the thermosetting material formed by thermosetting them after bonding has high impact resistance and maintains sufficient adhesive properties even under severe high temperature and high humidity conditions.

[0022] In this specification, "energy ray" means an electromagnetic wave or charged particle beam that has an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams, etc. Furthermore, "energy ray curability" refers to the property of hardening when irradiated with energy rays, while "non-energy ray curability" refers to the property of not hardening even when irradiated with energy rays. Furthermore, "thermosetting" refers to the property of hardening when heated. Furthermore, "non-curable" means that it does not harden regardless of whether it is heated or irradiated with energy rays.

[0023] When the cured product of the aforementioned film-like adhesive is actually used, the curing conditions for curing the film-like adhesive to form the cured product are not particularly limited, as long as the degree of curing of the cured product is sufficiently high, and can be appropriately selected according to the type of film-like adhesive. During the energy ray curing of film-type adhesives, the illuminance of the energy rays is 60-320 mW / cm². 2 Preferably, the amount of light from the energy ray during the energy ray curing process is 100 to 1000 mJ / cm². 2 It is preferable that this be the case. The heating temperature during the thermal curing of the adhesive cured product and the film-like adhesive is preferably 100 to 200°C. The heating time during the thermal curing is preferably 0.5 to 5 hours.

[0024] The film-like adhesive of this embodiment is for plasma dicing, and is particularly suitable when plasma generated from SF6 gas is used in plasma dicing. When irradiated with plasma generated from SF6 gas, the cutting speed of film-like adhesives and their energy-ray cured products is usually slow, but the cutting speed of the film-like adhesive and its energy-ray cured product of this embodiment is fast.

[0025] Furthermore, the film-like adhesive of this embodiment is also suitable for use in plasma dicing when plasma generated from oxygen (O2) gas, which is commonly used. Even when irradiated with plasma generated from O2 gas, the cutting speed of the film-like adhesive of this embodiment and its energy-ray cured product is fast.

[0026] Thus, with the film-like adhesive of this embodiment, wafer splitting and cutting of the film-like adhesive or its energy-ray cured product can be performed continuously and quickly, regardless of whether plasma generated from SF6 gas or plasma generated from O2 gas is used.

[0027] <Cutting speed during plasma dicing of film-like adhesives or their energy-ray cured products> The method for measuring the cutting speed during plasma dicing of film-type adhesives will be explained with reference to Figure 1. Please note that the diagrams used in the following explanation may be enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not be the same as in reality.

[0028] First, as shown in Figure 1(a), a test specimen 6 is prepared, comprising a film-like adhesive 13, a mask 7 attached to one side (sometimes referred to as the "first side" in this specification) 13a of the film-like adhesive 13, and a support 8 attached to the other side of the film-like adhesive 13.

[0029] The material of the mask 7 is not particularly limited as long as it can suppress the transmission of plasma, and may be, for example, an adhesive tape containing a high-strength resin such as polyimide as its main component. The shape and size of the mask 7 are not particularly limited, as long as the exposed area of ​​the first surface 13a of the film-like adhesive 13 and the area masked (shielded) by the mask 7 are both of sufficient size.

[0030] The support 8 is not particularly limited as long as it can hold the film-like adhesive 13 when irradiated with plasma, and may be, for example, a sheet or plate made of resin or an inorganic material. The support 8 may be, for example, a semiconductor wafer or a semiconductor chip.

[0031] Then, the test piece 6 is irradiated with plasma P from the first surface 13a of the film-like adhesive 13. This etches the areas of the film-like adhesive that are not masked by the mask 7, as shown in Figure 1(b). After irradiation with plasma P (after etching), as shown in Figure 1(c), the mask 7 is removed from the film-like adhesive 13, and the height difference between the original first surface 13a of the film-like adhesive 13 (the surface of the film-like adhesive 13 that was masked by the mask 7) and the etched surface 13a' of the film-like adhesive 13 (the surface of the film-like adhesive 13 that was not masked by the mask 7), i.e., the etching distance L, is measured. The etching distance L can be measured as surface roughness, for example, using a surface roughness measuring instrument. Then, the etching rate is calculated from the plasma irradiation time (etching time) t and L by L / t, and this is adopted as the cutting rate of the film-like adhesive.

[0032] To improve the accuracy of etching rate measurement, it is preferable that the etching distance L be 3 μm or greater.

[0033] The cutting speed of an energy-ray cured film adhesive during plasma dicing can be measured using the same method as described above, except that an energy-ray cured film adhesive is used instead of the film adhesive (film adhesive 13 shown in Figures 1(a) to (c)).

[0034] For example, by measuring the cutting speed during plasma dicing of the film adhesive of this embodiment or its energy-ray cured product and a comparative film adhesive or its energy-ray cured product under arbitrary and identical conditions, and comparing these measured values, the superiority of the cutting speed of the film adhesive of this embodiment can be determined.

[0035] For example, with respect to the film-like adhesive or its energy-ray cured product according to this embodiment, the cutting speed during plasma dicing, measured using plasma generated from SF6 gas under the conditions described in the later examples, can preferably be 0.2 μm / min or higher, and more preferably 0.24 μm / min or higher. On the other hand, a film-like adhesive with a cutting speed of 0.7 μm / min or lower can be more easily realized.

[0036] For example, with respect to the film-like adhesive or its energy-ray cured product according to this embodiment, the cutting speed during plasma dicing, measured using plasma generated from O2 gas under the conditions described in the later examples, can preferably be 1.6 μm / min or higher, and more preferably 1.9 μm / min or higher. On the other hand, a film-like adhesive with a cutting speed of 3.5 μm / min or lower can be more easily realized.

[0037] Generally, energy-ray cured film adhesives cut faster than film adhesives. Furthermore, using O2 gas results in a faster cutting speed than using SF6 gas.

[0038] When comparing the cutting speed of the film-like adhesive of this embodiment when cut by plasma irradiation without energy ray curing, with the cutting speed of the film-like adhesive when cured by energy rays and then cut by plasma irradiation, the cutting speed of the energy ray-cured material is usually faster, regardless of whether SF6 gas or O2 gas is used. Therefore, the film-like adhesive of this embodiment is particularly suitable for having energy ray curing properties and for performing both the division of a wafer into chips and the cutting of the energy ray cured film-like adhesive by plasma dicing after the energy ray curing of the film-like adhesive.

[0039] The cutting speed of the film-like adhesive and its energy-ray cured product in this embodiment during plasma dicing can be improved regardless of the type of gas used to generate the plasma by increasing the weight-average molecular weight of the polymer component (a), increasing the content of the polymer component (a) in the film-like adhesive, and decreasing the content of the filler (d) described later in the film-like adhesive. The components of the film-like adhesive in this embodiment will be described in detail later.

[0040] <Other components of film-type adhesives> The film-like adhesive of this embodiment is suitable for storage in roll form, for example, by having a first release film on one side and a second release film on the other side opposite to the first side. One of the two surfaces of the film-like adhesive becomes the surface for attachment to the wafer, and the other becomes the surface for attachment to the substrate or dicing sheet, as described later. The first release film and the second release film may both be known types. The first release film and the second release film may be identical to each other, or they may be different, for example, having different peeling forces when peeled from a film-like adhesive.

[0041] The film-like adhesive may consist of one layer (single layer) or of two or more layers. If the film-like adhesive consists of multiple layers, these layers may be identical or different from each other, and there are no particular limitations on the combination of these layers.

[0042] In this specification, not only in the case of film-like adhesives, "multiple layers may be identical or different from one another" means "all layers may be identical, all layers may be different, or only some layers may be identical," and further, "multiple layers are different from one another" means "at least one of the constituent materials and thickness of each layer is different from the other."

[0043] The thickness of the film-like adhesive is preferably 3 to 25 μm, more preferably 8 to 25 μm, and particularly preferably 12 to 25 μm. A thickness of the film-like adhesive greater than or equal to the lower limit increases the strength of the film-like adhesive and improves the uniformity of its thickness. A thickness of the film-like adhesive less than or equal to the upper limit avoids excessive thickness of the film-like adhesive and its cured product. This allows, for example, the film-like adhesive and its energy-ray cured product to be cut more easily by plasma dicing. Here, "thickness of the film adhesive" refers to the total thickness of the film adhesive. For example, the thickness of a multi-layered film adhesive refers to the total thickness of all the layers that make up the film adhesive. This also applies to other layers such as the substrate, which will be discussed later.

[0044] In this specification, unless otherwise specified, "thickness" refers to the average of the thicknesses measured at five randomly selected locations on the object, and can be obtained using a constant-pressure thickness measuring instrument in accordance with JIS K7130.

[0045] <<Composition of film-like adhesives and adhesive compositions>> The aforementioned film-like adhesive can be formed using an adhesive composition containing its constituent materials. For example, the adhesive composition can be applied to the surface to which the film-like adhesive is to be formed using a known method, and dried as necessary, thereby forming the film-like adhesive in the desired area. The ratio of components that do not vaporize at room temperature in an adhesive composition is usually the same as the ratio of those components in a film-type adhesive.

[0046] In this specification, "room temperature" means a temperature that is neither cooled nor heated, i.e., a normal temperature, such as 18-28°C.

[0047] In a film-type adhesive, the ratio of the total content of one or more of the following components in the film-type adhesive to the total mass of the film-type adhesive shall not exceed 100% by mass. Similarly, in an adhesive composition, the ratio of the total content of one or more of the following components of the adhesive composition to the total mass of the adhesive composition shall not exceed 100% by mass.

[0048] The drying conditions for the adhesive composition are not particularly limited, but if the adhesive composition contains a solvent as described later, it is preferable to heat dry it. For example, adhesive compositions containing a solvent are preferably dried at 70 to 130°C for 10 seconds to 5 minutes. The components of the film-type adhesive and adhesive composition will be described in detail below.

[0049] Examples of the adhesive composition include a composition containing a polymer component (a) (which may be abbreviated as "composition (III)" in this specification), and it is preferable that the adhesive composition further contains an energy ray curable component (g) and a photopolymerization initiator (h). An adhesive composition for forming a film-like adhesive that has both energy ray curability and thermosetting properties preferably contains a polymer component (a), an energy ray curability component (g), and a thermosetting component (b), and more preferably contains a polymer component (a), an energy ray curability component (g), a photopolymerization initiator (h), a thermosetting component (b), and a curing accelerator (c).

[0050] The polymer component (a), energy ray curable component (g), photopolymerization initiator (h), thermosetting component (b), and curing accelerator (c) contained in composition (III) and the film adhesive may each consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0051] <polymer component (a)> Polymer component (a) is a component that can be considered to have been formed by a polymerization reaction of polymerizable compounds, and is a polymer compound for imparting film-forming properties, flexibility, etc., to film-like adhesives. In this specification, polymer compounds also include products of polycondensation reactions. On the other hand, polymer component (a) is also a component that cuts faster during plasma dicing than most other components that are expected to be included in film-type adhesives. Therefore, increasing the content of polymer component (a) in the film-type adhesive increases the cutting speed during plasma dicing of the film-type adhesive or its energy-ray cured product.

[0052] Examples of polymer component (a) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, etc., with acrylic resin being preferred. Examples of the acrylic resin include well-known acrylic polymers.

[0053] The weight-average molecular weight (Mw) of polymer component (a) is 250,000 or more, preferably 280,000 or more, and may be, for example, 400,000 or more, or 600,000 or more. The larger the weight-average molecular weight of polymer component (a), the faster the cutting speed during plasma dicing of the film-like adhesive or its energy-ray cured product tends to be.

[0054] The upper limit of the weight-average molecular weight of polymer component (a) is not particularly limited. For example, in terms of ensuring high uniformity of dispersion of polymer component (a) in composition (III) and the film-like adhesive, the weight-average molecular weight of polymer component (a) is preferably less than 1,500,000, and may be, for example, 1,300,000 or less, or 1,000,000 or less.

[0055] Furthermore, the greater the weight-average molecular weight of polymer component (a) within the above numerical range, the better the shape stability (stable over time during storage) of the film-like adhesive, and the smaller the molecular weight, the easier the film-like adhesive becomes to conform to the uneven surface of the adherend.

[0056] In this specification, not only in the case of polymer component (a), but unless otherwise specified, "weight-average molecular weight" refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0057] Of the polymer component (a), the glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, more preferably -60 to 40°C, and may be, for example, -55 to 10°C. When the Tg of the acrylic resin is above the lower limit, the adhesive strength between the film-like adhesive and the adherend is suppressed, making it easier to pick up the film-like adhesive-coated chip and the adhesive-cured chip from the substrate or dicing sheet described later. When the Tg of the acrylic resin is below the upper limit, the adhesive strength between the film-like adhesive and the chip is improved.

[0058] When an acrylic resin has two or more constituent units, the glass transition temperature (Tg) of the acrylic resin can be calculated using Fox's formula. The Tg of the homopolymer of the monomers that derive the constituent units can be the value specified in the Polymer Data Handbook, Adhesion Handbook, or Polymer Handbook.

[0059] Examples of acrylic resins include polymers of one or more (meth)acrylic acid esters; and copolymers of two or more monomers selected from the (meth)acrylic acid esters, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

[0060] In this specification, "(meth)acrylic acid" is a concept that encompasses both "acrylic acid" and "methacrylic acid." This also applies to terms similar to (meth)acrylic acid, such as (meth)acryloyl group.

[0061] Examples of the (meth)acrylic acid esters that constitute the acrylic resin include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and hydroxyl group-containing (meth)acrylic acid esters. Having a constituent unit derived from the alkyl (meth)acrylate or cycloalkyl (meth)acrylate of the acrylic resin makes it easier to adjust the glass transition temperature (Tg) of the acrylic resin, and thus easier to adjust the adhesive strength of the film-like adhesive. Because the acrylic resin has structural units derived from the hydroxyl group-containing (meth)acrylic acid ester, the acrylic resin is dispersed with high uniformity in composition (III) and the film-like adhesive.

[0062] Examples of the alkyl (meth)acrylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, in which the alkyl group constituting the alkyl ester has a chain structure (linear or branched) with 1 to 18 carbon atoms. The number of carbon atoms in the alkyl group is preferably 1 to 12, and may be any of 1 to 10, 1 to 8, or 1 to 6.

[0063] Examples of the (meth)acrylate cycloalkyl esters include isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate, in which the cycloalkyl group constituting the cycloalkyl ester has a cyclic structure (monocyclic or polycyclic) with 6 to 18 carbon atoms.

[0064] Examples of the hydroxyl group-containing (meth)acrylic acid esters include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, in which the hydroxyalkyl group constituting the hydroxyalkyl ester has a chain structure (linear or branched) with 1 to 18 carbon atoms. The number of carbon atoms in the hydroxyalkyl group is preferably 1 to 12, and may be any of 1 to 10, 1 to 8, or 1 to 6.

[0065] The monomers that make up the acrylic resin may be just one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0066] The acrylic resin may or may not have functional groups that can bond to other compounds, such as vinyl groups, (meth)acryloyl groups, amino groups, carboxyl groups, and isocyanate groups, in addition to the hydroxyl groups mentioned above. The functional groups of the acrylic resin may be bonded to other compounds via a crosslinking agent (f) described later, or they may be directly bonded to other compounds without the crosslinking agent (f).

[0067] The acrylic resin preferably has a structural unit derived from the alkyl (meth)acrylate and a structural unit derived from the hydroxyl group-containing (meth)acrylate. In an acrylic resin having at least two such constituent units, the ratio of the total amount (parts by mass) of the constituent units derived from the alkyl (meth)acrylate and the constituent units derived from the hydroxyl group-containing (meth)acrylate to the mass of the acrylic resin is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass. In an acrylic resin having at least two types of constituent units as described above, and preferably satisfying the above proportions, the mass ratio of [amount of constituent units derived from (meth)acrylate alkyl ester (parts by mass)] / [amount of constituent units derived from hydroxyl group-containing (meth)acrylate ester (parts by mass)] is preferably 1 to 6, and may be any of 1 to 4, 2 to 5, and 3 to 6. By using any of the above acrylic resins as polymer component (a), the film-forming properties and flexibility of the film-like adhesive, as well as the cutting speed of the film-like adhesive or its energy-ray cured product during plasma dicing, are both improved in a well-balanced manner.

[0068] In the film-like adhesive, the ratio of the acrylic resin content to the polymer component (a) content is preferably 60% by mass or more, more preferably 70% by mass or more, and may be, for example, 80% by mass or more, or 90% by mass or more. When the ratio is above the lower limit, the cutting speed during plasma dicing of the film-like adhesive or its energy-ray cured product becomes faster. On the other hand, the aforementioned ratio is 100% by mass or less.

[0069] In a film-like adhesive, the ratio of the polymer component (a) content to the total mass of the film-like adhesive is preferably 10 to 40% by mass, regardless of the type of polymer component (a), and may be, for example, 10 to 30% by mass and 20 to 40% by mass. When the ratio is above the lower limit, both the film-forming properties and flexibility of the film-like adhesive, and the cutting speed of the film-like adhesive or its energy-ray cured product during plasma dicing, are improved. When the ratio is below the upper limit, excessive use of polymer component (a) is suppressed.

[0070] The above-mentioned statement regarding the ratio of polymer component (a) content to the total mass of the film-like adhesive is equivalent to stating that in composition (III), the ratio of polymer component (a) content to the total content of all components other than the solvent is preferably 10 to 40% by mass, regardless of the type of polymer component (a), and may be, for example, 10 to 30% by mass and 20 to 40% by mass. This is based on the fact that, in the process of removing the solvent from a solvent-containing resin composition to form a resin film, the amount of components other than the solvent usually does not change, and the ratio of the contents of non-solvent components is the same in the resin composition and the resin film. Therefore, in this specification, not limited to the case of film-like adhesives, the content of non-solvent components will mainly refer to the content in the resin film obtained by removing the solvent from the resin composition.

[0071] <Energy ray curing component (g)> When a film-like adhesive containing an energy-ray curable component (g) is cured with energy rays, and the resulting energy-ray cured product is plasma-diced, the cutting speed is usually faster than when a film-like adhesive is plasma-diced. The energy-ray curable component (g) is an energy-ray curable nonpolymer, or an energy-ray curable oligomer or polymer (polymer) that can be considered to have been synthesized from an energy-ray curable nonpolymer.

[0072] The aforementioned energy-ray curable nonpolymer cannot be considered a monomer polymer and is a component that possesses energy-ray curability. Examples of the energy-ray curable nonpolymer include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferred.

[0073] Examples of the aforementioned acrylate compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. Examples include (meth)acrylates containing a chain-like aliphatic skeleton; cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyl di(meth)acrylate and tricyclodecane dimethylol diacrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; and itaconic acid oligomers.

[0074] The molecular weight or weight-average molecular weight of the energy ray-curable component (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

[0075] In a film-like adhesive, the ratio of the energy-ray curable component (g) to the total mass of the film-like adhesive is preferably 4% by mass or more, more preferably 6% by mass or more, and may be, for example, 7% by mass or more. When the ratio is above the lower limit, the energy-ray curing of the film-like adhesive becomes easier. On the other hand, the aforementioned ratio is preferably 20% by mass or less, in that it suppresses the excessive use of the energy ray curable component (g).

[0076] <Photopolymerization initiator (h)> Composition (III) and the film-like adhesive contain a photopolymerization initiator (h), which allows the polymerization reaction of the energy ray-curable component (g) to proceed efficiently.

[0077] Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl Examples include acylphosphine oxide compounds such as diphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone. Furthermore, examples of photopolymerization initiators (h) include photosensitizers such as amines.

[0078] When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in composition (III) and the film adhesive is preferably 0.1 to 12 parts by mass, more preferably 0.5 to 9 parts by mass, and even more preferably 1 to 6 parts by mass, based on the content of 100 parts by mass of the energy ray curable component (g).

[0079] <Thermosetting component (b)> Thermosetting component (b) is a component that has thermosetting properties and is used to heat-cur the film-like adhesive. Examples of the thermosetting component (b) include epoxy-based thermosetting resins, thermosetting polyimide resins, and unsaturated polyester resins, with epoxy-based thermosetting resins being preferred. In this specification, thermosetting polyimide resin is a general term encompassing a polyimide precursor and a thermosetting polyimide, both of which form a polyimide resin through thermosetting.

[0080] [Epoxy thermosetting resin] The epoxy-based thermosetting resin comprises an epoxy resin (b1) and a thermosetting agent (b2). The epoxy resin (b1) and thermosetting agent (b2) contained in composition (III) and the film-like adhesive may each consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0081] (Epoxy resin (b1)) Examples of epoxy resins (b1) include well-known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and other bifunctional or more epoxy compounds.

[0082] The number-average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of the curability of the film-like adhesive and the strength and heat resistance of the cured product of the film-like adhesive. The epoxy equivalent of epoxy resin (b1) is preferably 100 to 1000 g / eq, and may be, for example, 100 to 600 g / eq and 150 to 300 g / eq.

[0083] (Thermosetting agent (b2)) The thermosetting agent (b2) is a curing agent for epoxy resin (b1). Examples of the thermosetting agent (b2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups in which an acid group has been converted to an anhydride. It is preferable that the functional group is a phenolic hydroxyl group, an amino group, or a group in which an acid group has been converted to an anhydride, and more preferably a phenolic hydroxyl group or an amino group.

[0084] Examples of thermosetting agents (b2) that include phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Examples of amine-based curing agents containing an amino group among the thermosetting agents (b2) include dicyandiamide (DICY).

[0085] The hydroxyl group equivalent of the thermosetting agent (b2) is preferably 10 to 120 g / eq, and may be, for example, 10 to 60 g / eq and 10 to 40 g / eq.

[0086] Among the thermosetting agents (b2), the number average molecular weight of the resin components, such as polyfunctional phenolic resins, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins, is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The molecular weight of the non-resin component of the thermosetting agent (b2), such as biphenol or dicyandiamide, is not particularly limited, but is preferably 60 to 500.

[0087] When using a thermosetting component (b), the content of the thermosetting agent (b2) in composition (III) and the film-like adhesive is preferably 0.5 to 10 parts by mass per 100 parts by mass of epoxy resin (b1), for example, it may be 0.5 to 5 parts by mass or 0.5 to 3 parts by mass. When the content of the thermosetting agent (b2) is above the lower limit, the thermosetting of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is below the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

[0088] When using a thermosetting component (b), the content of the thermosetting component (b) in composition (III) and the film-like adhesive (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)) is preferably 50 to 800 parts by mass, more preferably 100 to 600 parts by mass, per 100 parts by mass of polymer component (a). For example, it may be any of 100 to 500 parts by mass and 100 to 400 parts by mass, or any of 200 to 600 parts by mass and 300 to 600 parts by mass, or 200 to 500 parts by mass. Having the content of the thermosetting component (b) within this range makes it easier to adjust the adhesive strength between the film-like adhesive or its energy-ray cured product and the substrate or dicing sheet described later.

[0089] <Curing accelerator (c)> The curing accelerator (c) is an ingredient used to adjust the thermal curing rate of the film-like adhesive. Preferred curing accelerators (c) include, for example, 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); tertiary amines; organophosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylborone salts; and inclusion compounds using the aforementioned imidazoles as guest compounds.

[0090] When a curing accelerator (c) is used, the content of the curing accelerator (c) in composition (III) and the film adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the content of the thermosetting component (b) (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)). When the content of the curing accelerator (c) is above the lower limit, the effect of using the curing accelerator (c) is more pronounced. When the content of the curing accelerator (c) is below the upper limit, for example, the effect of suppressing the migration and segregation of a highly polar curing accelerator (c) to the adhesive interface side with the adherend in the film adhesive under high temperature and high humidity conditions is enhanced, and the reliability of the package obtained using the film adhesive is further improved.

[0091] ○Other ingredients The adhesive composition may contain, or may not contain, any other components that do not fall under any of the following categories: polymer component (a), energy ray curable component (g), photopolymerization initiator (h), thermosetting component (b), or curing accelerator (c). Examples of the aforementioned other components include polymer components other than polymer component (a) (which may be referred to as "other polymer components" in this specification) (a0), fillers (d), coupling agents (e), crosslinking agents (f), colorants (i), general-purpose additives (j), and the like. The other components contained in composition (III) and the film-like adhesive, such as fillers (d), coupling agents (e), crosslinking agents (f), colorants (i), and general-purpose additives (j), may consist of only one type or two or more types, and if there are two or more types, their combinations and ratios can be arbitrarily selected.

[0092] <Other polymer components (a0)> The aforementioned other polymer component (a0) is not particularly limited as long as it is a polymer component with a weight-average molecular weight of less than 250,000.

[0093] In composition (III) and the film-like adhesive, the ratio of the content of other polymer component (a0) to the content of polymer component (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. When the ratio is below the upper limit, the effect obtained by using polymer component (a) is further enhanced. On the other hand, the aforementioned ratio is 0% by mass or more, and the higher the aforementioned ratio, the greater the effect obtained by using other polymer components (a0).

[0094] <Filling material (d)> By using a film-like adhesive containing filler (d), it is possible to reduce the moisture absorption rate and improve the heat dissipation of the cured product, and furthermore, improve the reliability of the package. The average particle size of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm.

[0095] In this specification, "average particle diameter" refers to the particle diameter at 50% of the integrated value in the particle size distribution curve obtained by laser diffraction scattering (D 50 This refers to the value of ).

[0096] The filler (d) may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads formed from these inorganic fillers in a spherical shape; surface-modified products of these inorganic fillers; single-crystal fibers of these inorganic fillers; and glass fibers. Among these, the inorganic filler is preferably silica, alumina, or a surface-modified version thereof.

[0097] In a film-like adhesive, the ratio of the filler (d) content to the total mass of the film-like adhesive is 0% by mass or more. On the other hand, it may be, for example, 5% by mass or less, 3% by mass or less, or 1% by mass or less, but it is preferable that the film-like adhesive substantially contains no filler (d), such as 0% by mass. The lower the ratio, the faster the cutting speed of the film-like adhesive and its energy-ray cured product during plasma dicing tends to be. The statement that a film-like adhesive substantially does not contain filler (d) means that the proportion is 0% by mass, or that filler (d) is not intentionally blended during the manufacture of the adhesive composition, and even if filler (d) is mixed into the adhesive composition and the film-like adhesive, the amount of mixing (the content of filler (d) in the adhesive composition and the film-like adhesive) is trace.

[0098] <Coupling agent (e)> The film-type adhesive exhibits improved adhesion and bonding to the substrate by containing a coupling agent (e). Furthermore, the inclusion of a coupling agent (e) in the film-type adhesive improves the water resistance of the cured product without compromising its heat resistance. The coupling agent (e) has a functional group that can react with inorganic or organic compounds.

[0099] The coupling agent (e) is preferably a compound having a functional group that can react with the functional groups of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0100] Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane (also known as 3-glycidoxypropyltrimethoxysilane; the same applies to other compounds hereafter), 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-(2-aminoethylamino)propyltrimethoxy Examples include sisilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomeric or polymeric organosiloxanes, etc.

[0101] When a coupling agent (e) is used, the content of the coupling agent (e) in composition (III) and the film adhesive is preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and may be, for example, 0.1 to 1 part by mass, based on 100 parts by mass of the total content of polymer component (a) and thermosetting component (b). When the content of the coupling agent (e) is above the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the filler (d) in the resin and improved adhesion of the film adhesive to the adherend, are more pronounced. When the content of the coupling agent (e) is below the upper limit, outgassing is further suppressed.

[0102] <Crosslinking agent (f)> If polymer component (a) has functional groups such as vinyl groups, (meth)acryloyl groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds, such as the acrylic resin mentioned above, the crosslinking agent (f) crosslinks the functional groups in polymer component (a) with other compounds. In this case, the initial adhesive strength and cohesive strength of the film-like adhesive can be adjusted.

[0103] Examples of crosslinking agents (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridinyl group).

[0104] In composition (III) and the film-like adhesive, the content of the crosslinking agent (f) is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of the polymer component (a). On the other hand, the content is 0 parts by mass or more. Since the pickability of the film-like adhesive-coated chip or adhesive-cured chip tends to increase as the amount of crosslinking agent (f) decreases, it is particularly preferable that the amount is 0 parts by mass, that is, that the film-like adhesive does not contain crosslinking agent (f).

[0105] In this specification, the ability to properly pick up an object, such as a chip with a film-like adhesive or a chip with a cured adhesive, from a substrate or dicing sheet is sometimes referred to as "pickup capability."

[0106] <Coloring agent (i)> The coloring agent (i) is a component in the film-like adhesive and its cured product that can adjust the transmittance of light of various wavelengths. Examples of colorants (i) include known ones such as inorganic pigments, organic pigments, and organic dyes.

[0107] When a coloring agent (i) is used, the ratio of the coloring agent (i) content to the total mass of the film adhesive is preferably 0.01 to 10% by mass, regardless of the type of coloring agent (i). When the ratio is above the lower limit, the effect of using the coloring agent (i) is more pronounced. When the ratio is below the upper limit, excessive use of the coloring agent (i) is suppressed.

[0108] <General-purpose additive (j)> The general-purpose additive (j) may be any known additive and can be arbitrarily selected depending on the purpose; it is not particularly limited. Preferred general-purpose additives (j) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, defoaming agents, leveling agents, and the like. In particular, using a film-type adhesive containing an antioxidant (sometimes referred to as "antioxidant (j1)" in this specification) improves the pickability of the film-type adhesive-coated chip and the adhesive-cured chip. This is presumed to be because when plasma is irradiated onto the film-type adhesive and its energy-ray-cured product (adhesive-cured product), radicals that are normally unwanted are captured, and the composition of the film-type adhesive and the adhesive-cured product ultimately becomes desirable. In other words, a preferred general-purpose additive (j) contained in composition (III) and the film-like adhesive is an antioxidant (j1).

[0109] Examples of antioxidants (j1) include hindered amine-based light stabilizers. Examples of the hindered amine-based light stabilizers include p,p'-dioctyldiphenylamine, phenyl-α-naphthylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diallyl-p-phenylenediamine, and 4,4'-(α,α-dimethylbenzyl)diphenylamine. p,p-toluenesulfonylaminodiphenylamine, N-phenyl-N'-(3-methchlorolyloxy-2-hydroxypropyl)-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, alkylated diphenylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[[6-( 1,1,3,3-Tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 1,2,3,Mixed esters of 4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 Examples include mixed esterified products with [5]undecane, mixed esterified products of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate, (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylene carboxylate, etc.

[0110] Among these, the hindered amine light stabilizer is preferably a mixed ester of 1,2,3,4-butanetetracarboxylic acid, which is an N-alkyl type hindered amine light stabilizer, and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0111] The content of composition (III) and the general-purpose additive (i) in the film-like adhesive is not particularly limited and can be appropriately selected depending on the type of general-purpose additive (i), for example.

[0112] When composition (III) and the film-like adhesive contain antioxidant (j1), the ratio of antioxidant (j1) content to the total mass of the film-like adhesive is preferably 0.1 to 5% by mass, and may be, for example, 0.5 to 3.5% by mass. When the ratio is above the lower limit, the pickability of the film-like adhesive-coated chip and the adhesive-cured chip is improved. When the ratio is below the upper limit, excessive use of antioxidant (j1) is suppressed.

[0113] If composition (III) and the film adhesive contain a general-purpose additive (i) other than the antioxidant (j1), the ratio of the content of the general-purpose additive (i) other than the antioxidant (j1) to the total mass of the film adhesive may be, for example, 0.1 to 10% by mass.

[0114] <Solvent> Composition (III) preferably further contains a solvent. Composition (III) containing a solvent has good handling properties. In this specification, unless otherwise specified, the term "solvent" includes not only substances that dissolve the target component but also dispersion media that disperse the target component.

[0115] The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene; alcohols such as methanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The solvent contained in composition (III) may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0116] The solvent content of composition (III) is not particularly limited and may be appropriately selected depending on the type of components other than the solvent.

[0117] <<An example of a film-type adhesive>> An example of a preferred film-like adhesive in this embodiment is a film-like adhesive for use in plasma dicing, The aforementioned film-like adhesive contains a polymer component (a), an energy ray curable component (g), and a thermosetting component (b). The weight-average molecular weight of the polymer component (a) is 250,000 or more. In the aforementioned film-like adhesive, the ratio of the content of the polymer component (a) to the total mass of the film-like adhesive is 10 to 40% by mass. In the aforementioned film-like adhesive, the ratio of the content of the energy ray-curable component (g) to the total mass of the film-like adhesive is 4% by mass or more. In the aforementioned film-like adhesive, the content of the thermosetting component (b) is 50 to 800 parts by mass per 100 parts by mass of the polymer component (a). Examples of film-like adhesives include those that substantially do not contain filler (d).

[0118] Another example of a preferred film adhesive of this embodiment is a film adhesive for use in plasma dicing, The aforementioned film-like adhesive contains polymer component (a), The weight-average molecular weight of the polymer component (a) is 250,000 or more. The aforementioned film-like adhesive contains, as the polymer component (a), an acrylic resin having a structural unit derived from an alkyl (meth)acrylate and a structural unit derived from a hydroxyl group-containing (meth)acrylate. A film-like adhesive is provided in which, in the acrylic resin, the ratio of the total amount of constituent units derived from the alkyl (meth)acrylate and the constituent units derived from the hydroxyl group-containing (meth)acrylate to the mass of the acrylic resin is 60 to 100% by mass.

[0119] <<Method for manufacturing adhesive composition>> An adhesive composition (for example, composition (III)) is obtained by blending the components that constitute it. The temperature and time during the addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and can be adjusted as appropriate, but a temperature of 15 to 30°C is preferred.

[0120] ◇Film-type adhesive composite sheet A film-like adhesive composite sheet according to one embodiment of the present invention comprises a base material and a film-like adhesive provided on one surface of the base material, wherein the film-like adhesive is the film-like adhesive according to the above-described embodiment of the present invention. A film-like adhesive composite sheet according to another embodiment of the present invention comprises a dicing sheet and a film-like adhesive provided on one surface of the dicing sheet, wherein the dicing sheet comprises a substrate and an adhesive layer provided on one surface of the substrate, the adhesive layer is disposed between the substrate and the film-like adhesive, and the film-like adhesive is the film-like adhesive according to the above-described embodiment. The film-like adhesive composite sheet of this embodiment can be used, for example, as a sheet for cutting a film-like adhesive or its energy-ray cured product attached to a wafer by plasma irradiation. In either case, ultimately, as will be described later, the film-like adhesive chip or adhesive-cured chip obtained after plasma irradiation is separated from the substrate or dicing sheet and picked up. In the film-like adhesive composite sheet of this embodiment, the film-like adhesive contains a polymer component (a) with a weight-average molecular weight of 250,000 or more. Therefore, when the film-like adhesive, or if the film-like adhesive is energy-ray curable, is cut by plasma irradiation, the cutting speed is faster than in conventional methods. As a result, the wafer can be divided and the film-like adhesive or its energy-ray cured material can be cut continuously and quickly by plasma dicing.

[0121] The film-like adhesive composite sheet of this embodiment may be the same as a conventional film-like adhesive composite sheet, except that it comprises the film-like adhesive of this embodiment described above.

[0122] Each layer constituting the film-like adhesive composite sheet, such as the base material, adhesive layer, and film-like adhesive, may consist of one layer (single layer) or two or more layers. If it consists of multiple layers, these layers may be identical or different, and the combination of these layers is not particularly limited.

[0123] A film-like adhesive composite sheet, comprising a base material and a film-like adhesive, but without an adhesive layer, can have a lower overall content of low-molecular-weight components than a film-like adhesive composite sheet with a dicing sheet. When using such a film-like adhesive composite sheet without an adhesive layer, the volatilization of the contained components is suppressed when the plasma irradiation device is evacuated for plasma dicing, allowing the desired vacuum level to be achieved in a short time. Furthermore, contamination due to the adhesion of volatile components within the plasma irradiation device can also be suppressed.

[0124] Figure 2 is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet according to this embodiment. The film-like adhesive composite sheet 101 shown in Figure 2 comprises a base material 11 and a film-like adhesive 13 provided on one surface 11a of the base material 11. The film-like adhesive 13 is the film-like adhesive 13 shown in Figure 1.

[0125] The film-like adhesive composite sheet 101 further includes a release film 15 on the first surface 13a of the film-like adhesive 13. In the film-like adhesive composite sheet 101, the release film 15 has any configuration.

[0126] The film-like adhesive composite sheet 101 is used by attaching a wafer to the first surface 13a of the film-like adhesive 13 after the release film 15 has been removed.

[0127] The film-like adhesive composite sheet of this embodiment is not limited to that shown in Figure 2, and for example, some components of this film-like adhesive composite sheet may be modified, deleted, or added without departing from the spirit of the present invention.

[0128] For example, the film-like adhesive composite sheet of this embodiment may or may not include other layers at any location that do not fall under any of the following categories: the base material, the adhesive layer, the film-like adhesive, or the release film. The aforementioned other layers can be arbitrarily selected depending on the purpose and are not particularly limited.

[0129] <Base material> The substrate may be in the form of a sheet or a film, and may be one of known types. The substrate is preferably one that allows energy rays to pass through. Examples of constituent materials for the base material include various resins. The resin constituting the base material may consist of only one type, or two or more types. If there are two or more types, their combination and ratio can be arbitrarily selected.

[0130] Examples of the aforementioned resins include polyolefins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer and ethylene-(meth)acrylic acid copolymer (polymers obtained using ethylene as a monomer); vinyl chloride resins (resins obtained using vinyl chloride as a monomer); polyester; and polyimide. The aforementioned resin may be any of the following: a polymer alloy such as a mixture of two or more of the above-mentioned resins; a crosslinked resin obtained by crosslinking one or more of the above-mentioned resins; or a modified resin such as an ionomer using one or more of the above-mentioned resins.

[0131] In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and plasticizers.

[0132] The surface of the substrate may or may not be treated with oxidation, lipophilicity, hydrophilicity, or primer treatment, and may or may not have other layers deposited on it.

[0133] The substrate thickness is preferably 50 to 300 μm. A substrate thickness within this range improves the flexibility of the film-like adhesive composite sheet and its suitability for adhesion to wafers.

[0134] The substrate can be manufactured by known methods. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the resin.

[0135] <Adhesive layer> The adhesive layer contains an adhesive resin, which may be either energy-ray curable or non-energy-ray curable, and may be a known type.

[0136] <Release film> The release film may be a known type, for example, one or both sides of a release film substrate being a release surface.

[0137] ◇Method of manufacturing a film-like adhesive composite sheet The film-like adhesive composite sheet of this embodiment can be manufactured by laminating the above-mentioned layers in corresponding positional relationships and, if necessary, adjusting the shape of some or all of the layers. The method for forming each layer is as described above. The film-like adhesive composite sheet of this embodiment can be manufactured in the same way as a conventional film-like adhesive composite sheet, except that the film-like adhesive is used.

[0138] For example, when laminating a film-like adhesive onto a substrate, the adhesive composition is applied to a release film and dried as needed to form a film-like adhesive on the release film. Then, the exposed surface of this film-like adhesive is bonded to one side of the substrate.

[0139] ◇Manufacturing method for chips with film-like adhesive (Method of using film-like adhesive and film-like adhesive composite sheet (1)) The aforementioned film-like adhesive and film-like adhesive composite sheet can be used to manufacture film-like adhesive-coated chips, and the resulting film-like adhesive-coated chips can further be used to manufacture substrate devices. By using the aforementioned film-like adhesive or film-like adhesive composite sheet, the wafer can be divided and the film-like adhesive cut continuously and quickly by plasma dicing.

[0140] <<Manufacturing method (1)>> A method for manufacturing a chip with a film-like adhesive according to one embodiment of the present invention is a method for manufacturing a chip with a film-like adhesive comprising a chip and a film-like adhesive provided on one side of the chip, In the above manufacturing method, the film-like adhesive according to the above embodiment of the present invention, or the film-like adhesive in a film-like adhesive composite sheet, is attached to one side of a wafer, and the wafer and the film-like adhesive (in this specification, this laminate may be referred to as a "film-like adhesive wafer") are irradiated with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce chips, and the film-like adhesive is cut to produce the film-like adhesive chips (in this specification, this manufacturing method may be referred to as "manufacturing method (1)").

[0141] The manufacturing method (1) may be the same as the conventional method for manufacturing chips with film adhesive, except that the film adhesive or film adhesive composite sheet of this embodiment described above is used instead of the conventional film adhesive or film adhesive composite sheet.

[0142] In manufacturing method (1), either an energy ray-curable adhesive or a non-energy ray-curable adhesive can be used as the film adhesive.

[0143] In manufacturing method (1), when using a film-like adhesive that does not constitute a film-like adhesive composite sheet, a dicing sheet is attached to the exposed surface of the film-like adhesive (the side opposite to the wafer side) in the film-like adhesive-coated wafer, and then plasma is irradiated.

[0144] In manufacturing method (1), the attachment of the film-like adhesive or film-like adhesive composite sheet to the wafer can be carried out by known methods, for example, at room temperature (e.g., room temperature) or under heated conditions.

[0145] In manufacturing method (1), the plasma irradiation conditions can be adjusted as appropriate. The flow rate of the gas used to generate the plasma is preferably 50 to 300 cc. The output power during plasma irradiation is preferably 200 to 400 watts.

[0146] In manufacturing method (1), prior to plasma irradiation, a patterned mask is laminated on the side of the wafer to which the film-like adhesive is attached, opposite to the side with the film-like adhesive (exposed side), in order to produce a chip of the desired size and shape. Then, plasma is irradiated onto the wafer with the film-like adhesive and the laminated mask from the mask side. This plasma dicing process continuously divides the wafer and cuts the film-like adhesive. The cutting speed of the film-like adhesive in this process is faster than in conventional methods. After plasma dicing, the mask laminated on the chip can be removed by known methods, such as using adhesive tape. As a result, the desired film-like adhesive-coated chip can be obtained.

[0147] In manufacturing method (1), if an energy-ray curable film-like adhesive is used, after both wafer division and cutting of the film-like adhesive are performed, the cut film-like adhesive may be energy-ray cured as needed to produce an adhesive-cured chip from the film-like adhesive-coated chip. In this case, the energy-ray irradiation conditions (illuminance, light intensity) when energy-ray curing the film-like adhesive are as described above.

[0148] In manufacturing method (1), other steps not corresponding to the above-described steps (attaching the film-like adhesive to the wafer, dividing the wafer and cutting the film-like adhesive, and energy ray curing of the film-like adhesive) may be performed or omitted, as long as they do not impair the effects of the present invention. The types and timings of the aforementioned other processes can be arbitrarily selected according to the purpose, and further arbitrarily selected according to the type of film adhesive or wafer, and are not particularly limited.

[0149] ◇Manufacturing method for chips with cured adhesive (Method of using film-like adhesive and film-like adhesive composite sheet (2)) The aforementioned film-like adhesive and film-like adhesive composite sheet can also be used to manufacture chips with cured adhesive, and the resulting chips with cured adhesive can further be used to manufacture substrate devices. By using the aforementioned film-like adhesive or film-like adhesive composite sheet, the division of the wafer and the cutting of the energy-ray cured film-like adhesive can be performed continuously and quickly by plasma dicing.

[0150] <<Manufacturing method (2)>> A method for manufacturing a chip with an adhesive curing product according to one embodiment of the present invention is a method for manufacturing a chip with an adhesive curing product comprising a chip and an adhesive curing product provided on one side of the chip, In the above manufacturing method, a film-like adhesive according to the above embodiment of the present invention, or a film-like adhesive in a film-like adhesive composite sheet, is attached to one side of a wafer (to produce a wafer with film-like adhesive). The film-like adhesive is energy-ray curable, and the attached film-like adhesive is energy-ray cured to form an adhesive-cured product (an energy-ray cured product of the film-like adhesive). The wafer and the adhesive-cured product are irradiated with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce chips, and the adhesive-cured product is cut to produce chips with adhesive-cured product (in this specification, this manufacturing method may be referred to as "manufacturing method (2)").

[0151] Manufacturing method (2) is the same as manufacturing method (1), except that the film adhesive is limited to one that is energy ray curable, and the energy ray curing of the film adhesive, which is an optional step, is made an essential step and performed before plasma dicing instead of after.

[0152] In manufacturing method (2), the attachment of the film-like adhesive or film-like adhesive composite sheet to the wafer can be carried out in the same manner as in manufacturing method (1).

[0153] The irradiation conditions for energy rays and plasma in manufacturing method (2) are the same as those for energy rays and plasma in manufacturing method (1), respectively.

[0154] In manufacturing method (2), when the wafer is divided and the energy-ray cured film adhesive is cut continuously by plasma dicing, the cutting speed of the cured material is faster than in the conventional method.

[0155] In manufacturing method (2), prior to plasma irradiation, a patterned mask is laid on the side of the wafer, which is equipped with the adhesive cured material (energy-ray cured film adhesive), opposite to the side with the adhesive cured material (exposed side), in order to produce a chip of the desired size and shape. The method for removing the mask laid on the chip after plasma dicing is the same as in manufacturing method (1).

[0156] As a result, the desired adhesive-cured chip can be obtained.

[0157] In manufacturing method (2), other steps not corresponding to the above-described steps (attaching the film-like adhesive to the wafer, energy ray curing of the film-like adhesive, and dividing the wafer and cutting the cured adhesive product) may be performed or omitted, as long as they do not impair the effects of the present invention. The types and timings of the aforementioned other processes can be arbitrarily selected according to the purpose, and further arbitrarily selected according to the type of film adhesive or wafer, and are not particularly limited.

[0158] ◇Manufacturing method for substrate devices (Method of using chips with film-like adhesive or chips with cured adhesive) A substrate device can be manufactured using the film-like adhesive-coated chip or adhesive-cured chip obtained by manufacturing method (1), or the adhesive-cured chip obtained by manufacturing method (2). First, a chip with a film-like adhesive or a chip with a cured adhesive is separated from a dicing sheet or substrate and picked up. Then, the substrate device can be manufactured by known methods, except that this chip with the film-like adhesive or cured adhesive is used. For example, the chip with the film-like adhesive or the chip with a cured adhesive is attached to a circuit board using the film-like adhesive or cured adhesive contained within it. If the film-like adhesive is thermosetting, the film-like adhesive or cured adhesive is further thermoset after attachment. Furthermore, the desired substrate device can be manufactured by adding other processes as needed. [Examples]

[0159] The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited in any way to the examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, the desired measurements can be performed using other instruments with equivalent performance.

[0160] In this example and comparative example, "BA" is abbreviated as n-butyl acrylate, and "HEA" is abbreviated as 2-hydroxyethyl acrylate.

[0161] <<Raw materials for manufacturing adhesive compositions>> The raw materials used in the manufacture of the adhesive composition are listed below. [Polymer component (a)] (a)-1: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 800,000, glass transition temperature -49°C). (a)-2: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature -49°C). (a)-3: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 300,000, glass transition temperature -49°C). [Other polymer components (a0)] (a0)-1: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 100,000, glass transition temperature -49°C). [Epoxy resin (b1)] (b1)-1: Dicyclopentadiene type epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., softening point 68-78°C, epoxy equivalent 245-260 g / eq) (b1)-2: Mixture of liquid bisphenol F type epoxy resin and acrylic rubber fine particles (Nippon Shokubai Co., Ltd. "Acryset (registered trademark) BPF307", epoxy equivalent 235 g / eq) [Thermosetting agent (b2)] (b2)-1: Dicyandiamide (ADEKA Hardener® EH-3636AS, manufactured by ADEKA Corporation, solid dispersion latent curing agent, softening point 209°C, hydroxyl group equivalent 21 g / eq) [Curing accelerator (c)] (c)-1:2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemicals Co., Ltd. "Curesol (registered trademark) 2PHZ-PW") [Filler (d)] (d)-1: Silica filler (SC2050MA, manufactured by Admatex, silica filler surface modified with epoxy compounds, average particle size 0.5 μm) [Coupling agent (e)] (e)-1:3-Glycidoxypropyltrimethoxysilane-added silicate compound ("MKC® Silicate MSEP-2" manufactured by Mitsubishi Chemical Corporation) [Energy ray curing component (g)] (g)-1: Tricyclodecanedimethylol diacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD® R-684", molecular weight 304) [Photopolymerization initiator (h)] (h)-1:2-Hydroxy-1-(4-(4-(2-Hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (CIBA Specialty Chemicals "IRGACURE® 127") [Antioxidant (j1)] (j1)-1: Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (hindered amine light stabilizer, ADEKA Corporation's "ADEKA Stab (registered trademark) LA-63P")

[0162] [Example 1] <<Manufacturing of film-type adhesives>> <Manufacturing of adhesive compositions> Adhesive compositions were prepared by dissolving or dispersing each component in methyl ethyl ketone and stirring at 23°C, so that the types and amounts of components contained in the film-like adhesive were as shown in Table 1, and the mixture was stirred to obtain an adhesive composition in which the total concentration of all components other than the solvent was 50% by mass.

[0163] <Manufacturing of film-type adhesives> A release film (second release film, Lintec Corporation's "SP-PET381031", 38 μm thick) made of polyethylene terephthalate film with one side treated with silicone release was used. The adhesive composition obtained above was applied to the treated surface and dried at 100°C for 1 minute to produce a 20 μm thick film-like adhesive having both energy ray curability and thermosetting properties. Furthermore, by laminating the treated surface of a separate release film (first release film, Lintec Corporation's "SP-PET502150", 50 μm thick) to the exposed surface of the obtained film-like adhesive, a film-like adhesive with release films provided on both sides was produced.

[0164] <<Evaluation of film-type adhesives>> <Measurement of cutting speed of film-like adhesive (1) (when plasma is irradiated using SF6 gas)> A silicon chip (30mm x 30mm, 300μm thick) was fabricated from a silicon wafer whose back surface was ground with a #2000 wheel. The first release film was removed from the film-like adhesive obtained above, and the exposed surface of the film-like adhesive was attached to the grinding surface of the silicon chip obtained above. Furthermore, by cutting and removing the area of ​​the film-like adhesive that protruded from the silicon chip after attachment, a silicon chip with a release film and film-like adhesive attached was simply fabricated, in which the entire surface of the grinding surface of the silicon chip was covered with film-like adhesive of the same size as the grinding surface.

[0165] The cutting speed of the film-like adhesive was measured using the method previously described with reference to Figure 1. More specifically, a test specimen was prepared by removing the second release film from the film-like adhesive-coated silicon chip obtained above, and then applying a polyimide-based adhesive tape (10 mm wide strip) to a strip-shaped region of the exposed surface of the film-like adhesive that was parallel to one pair of opposing sides and connecting the other pair of opposing sides, thereby forming a strip-shaped mask on the exposed surface of the film-like adhesive. Next, a dry etching apparatus (Samco RIE apparatus) was used as the plasma irradiation device, and the test piece was irradiated with plasma from the side of the film-like adhesive. At this time, SF6 gas was used, with a flow rate ratio of SF6 gas (sccm) / argon gas (sccm) set to 50 / 3, and the plasma was irradiated under reduced pressure conditions of 20 Pa, with an RF (Radio Frequency) power of 250 W and a processing time of 15 min. As a result, the areas of the film-like adhesive that were not covered by adhesive tape (not masked) were etched.

[0166] After plasma irradiation (etching), the test piece was removed from the plasma irradiation device, the adhesive tape was removed, and the surface roughness of the film adhesive side of the silicon chip with film adhesive was measured using a contact surface roughness meter (Mitutoyo SV-3000S4). This allowed for the measurement of the height difference (etching distance L) between the original first surface of the film adhesive and the etched area of ​​the film adhesive. The etching rate was then calculated from this measurement and the plasma irradiation time (etching time) and adopted as the cutting rate of the film adhesive. The results are shown in Table 1. The etching distance L was 4.65 μm.

[0167] <Measurement of cutting speed of film-like adhesive (2) (when plasma is irradiated using O2 gas)> The cutting speed of the film-like adhesive was measured in the same manner as in the measurement of the cutting speed of the film-like adhesive (1) described above, except that O2 gas was used instead of SF6 gas. The results are shown in Table 1.

[0168] <Evaluation of film-forming properties of film-like adhesives> During the manufacturing of the above-mentioned film-like adhesive, the coating layer of the adhesive composition and the formed film-like adhesive were visually observed after coating the adhesive composition onto a release film, and the film-forming properties of the film-like adhesive were evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: A coating layer of the adhesive composition can be formed on the entire surface of the release treatment surface of the release film, and as a result, a film-like adhesive with high thickness uniformity can be formed on the entire surface of the release treatment surface of the release film. B: In some areas of the release surface of the release film, the adhesive composition repelled, preventing the formation of a coating layer. As a result, a film-like adhesive could not be formed in some areas of the release surface of the release film.

[0169] <<Manufacturing and Evaluation of Film-Type Adhesives>> [Examples 2-3, Comparative Examples 1-2] The film adhesive was manufactured in the same manner as in Example 1, except that the type and amount of components in the adhesive composition were changed, or both, so that the types and amounts of components in the film adhesive were as shown in Table 1. In Table 1, a "-" in the column for the components of the film-type adhesive means that the film-type adhesive does not contain that component. Furthermore, these film-like adhesives were evaluated using the same method as in Example 1. The results are shown in Table 1.

[0170] [Table 1]

[0171] As is clear from the results above, in Examples 1 to 3, the cutting speed when cutting the film-like adhesive by irradiation with plasma generated from SF6 gas was 0.26 μm / min or higher, which was fast. Furthermore, the cutting speed when cutting the film-like adhesive by irradiation with plasma generated from O2 gas was also 2.11 μm / min or higher, which was fast. The film-like adhesives of Examples 1 to 3 contained polymer component (a) with a weight-average molecular weight of 300,000 or more.

[0172] In Examples 1 to 3, the repulsion of the adhesive composition during coating onto the release film was suppressed, and a highly uniform coating layer was formed across the entire release surface of the release film. As a result, a film-like adhesive with high thickness uniformity was formed. In other words, the film-like adhesives of Examples 1 to 3 exhibited excellent film-forming properties.

[0173] In contrast, in Comparative Example 1, the cutting speed when cutting the film-like adhesive was slow regardless of whether the plasma was generated from SF6 gas or O2 gas. The film-like adhesive of Comparative Example 1 contained another polymer component (a0) with a weight-average molecular weight of 100,000, but did not contain a polymer component (a) with a weight-average molecular weight of 250,000 or more.

[0174] In Comparative Example 1, the adhesive composition repelled during application to the release film, preventing the formation of a coating layer in a portion of the release surface of the release film (particularly the area near the periphery). As a result, a film-like adhesive could not be formed in that area of ​​the release surface of the release film. In other words, the film-like adhesive of Comparative Example 1 had poor film-forming properties.

[0175] In Comparative Example 2, the cutting speed when cutting the film-like adhesive was slow regardless of whether the plasma was generated from SF6 gas or O2 gas. The film-like adhesive of Comparative Example 2 is equivalent to the film-like adhesive of Comparative Example 1 in which a portion of the epoxy resin (b1)-1 is replaced with filler (d)-1, and the cutting speed of the film-like adhesive was even slower than that of Comparative Example 1. Furthermore, the film-forming adhesive of Comparative Example 2 differed from the film-forming adhesive of Comparative Example 1 in that it contained filler (d), resulting in better film-forming properties. [Industrial applicability]

[0176] This invention can be used in the manufacture of substrate devices. [Explanation of symbols]

[0177] 101...Film-type adhesive composite sheet 11...Substrate, 11a...One side of the substrate 13. Film-type adhesive

Claims

1. A film-like adhesive for use in plasma dicing, The aforementioned film-like adhesive contains polymer component (a), A film-like adhesive wherein the weight-average molecular weight of the polymer component (a) is 250,000 or more.

2. The film-like adhesive according to claim 1, wherein the film-like adhesive substantially does not contain filler (d).

3. The film-like adhesive according to claim 1 or 2, wherein the thickness of the film-like adhesive is 3 to 25 μm.

4. The film-like adhesive according to claim 1 or 2, wherein the plasma dicing uses plasma generated from oxygen gas.

5. The film-like adhesive according to claim 1 or 2, wherein the plasma dicing uses plasma generated from sulfur hexafluoride gas.

6. The aforementioned film-like adhesive has energy ray curing properties, The film-like adhesive according to claim 1 or 2, wherein the film-like adhesive is used to perform both the division of the wafer into chips and the cutting of the energy-ray cured film-like adhesive by plasma dicing after the energy-ray curing of the film-like adhesive.

7. The film-like adhesive according to claim 1 or 2, wherein the weight-average molecular weight of the polymer component (a) is less than 1,500,000.

8. The invention comprises a base material and a film-like adhesive provided on one surface of the base material, A film-like adhesive composite sheet wherein the film-like adhesive is the film-like adhesive described in claim 1.

9. A method for manufacturing a chip with a film-like adhesive, comprising a chip and a film-like adhesive provided on one side of the chip, A method for manufacturing a chip with a film-like adhesive, comprising: attaching the film-like adhesive described in claim 1, or the film-like adhesive in the film-like adhesive composite sheet described in claim 8, to one side of a wafer; irradiating the wafer and the film-like adhesive with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce chips, and cutting the film-like adhesive, thereby producing the chip with the film-like adhesive.

10. A method for manufacturing a chip with an adhesive curing agent, comprising a chip and an adhesive curing agent provided on one side of the chip, A method for manufacturing a chip with an adhesive curing agent, comprising: applying the film-like adhesive described in claim 1, or the film-like adhesive in the film-like adhesive composite sheet described in claim 8, to one side of a wafer; the film-like adhesive being energy-ray curable; forming the adhesive curing product by energy-ray curing the applied film-like adhesive; and irradiating the wafer and the adhesive curing product with plasma generated from oxygen gas or sulfur hexafluoride gas to divide the wafer and produce chips, and cutting the adhesive curing product to produce chips with the adhesive curing product.

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