JP2016216571A - Method for producing ground base material, film-shaped adhesive used therefor, and laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-shaped adhesive usable for fixing the base material to be ground such as a silicone wafer to a supporting body, capable of easily being peeled even if there is no application of release components, and having sufficient heat resistance to withstand a high temperature of approximately 200°C.SOLUTION: Provided is a film-shaped adhesive containing thermosetting components. The film-shaped adhesive is cured in a state of being pasted on a glass sheet by heating in the order of at 130°C for 30 min, at 170°C for 30 min and at 200°C for 30 min, and, thereafter, upon the irradiation of light of 1,000 mJ/cm, the 30° peeling strength to the glass sheet of the film-shaped adhesive is 100 N/m or more after the curing of the film-shaped adhesive and before the irradiation of the light, and is 50 N/m or lower after the film-shaped adhesive is irradiated with the light.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a ground substrate, and a film-like pressure-sensitive adhesive and a laminate used for the method. More specifically, the present invention relates to, for example, a film shape that allows a substrate to be ground such as a silicon wafer fixed on a support to be easily ground to a desired thickness and easily peeled from the support. It is related with the manufacturing method of the base material thinned using the adhesive, the laminated body joined through the said film-like adhesive, and a laminated body.

  With the increasing functionality of electronic devices such as smartphones and tablet PCs, stacked MCPs (Multi Chip Packages), in which semiconductor elements are stacked in multiple stages and increased in capacity, have become widespread. Advantageous film adhesives are widely used as adhesives for die bonding. However, in spite of such a trend toward multi-functionality, the current connection method of semiconductor elements using wire bonds tends to slow down the operation of electronic devices due to the limited data processing speed. It is in. In addition, since there is a growing need to keep power consumption low and to use the battery for a longer time without charging, power saving is also being demanded. From such a viewpoint, in recent years, a semiconductor device having a new structure in which semiconductor elements are connected to each other by a through electrode instead of a wire bond has been developed for the purpose of further speeding up and power saving.

  Although a semiconductor device having a new structure has been developed as described above, there is still a demand for higher capacity, and development of a technology capable of stacking semiconductor elements in more stages is progressing regardless of the package structure. However, in order to stack a large number of semiconductor elements in a limited space, it is indispensable to stably reduce the thickness of the semiconductor elements.

  At present, in a grinding process for thinning a semiconductor element, it is a mainstream to apply a support tape called a so-called BG tape to the semiconductor element and perform grinding in a supported state. However, the thinned semiconductor element is easily warped due to the influence of the circuit applied to the surface, and the BG tape, which is a tape material that is easily deformed, cannot sufficiently support the thinned semiconductor element.

  From such a background, a thinning process of a semiconductor element using a silicon wafer or glass, which is a material harder than BG tape, as a support has been proposed, and the semiconductor element and the silicon wafer or glass as a support are adhered to each other. Materials have been proposed. Such an adhesive is required as an important characteristic that it can be peeled from the support without damaging the ground semiconductor element. In order to satisfy such characteristics, intensive studies have been made on the peeling method (see, for example, Patent Documents 1 and 2). Examples thereof include a method using a carrier layer that degrades adhesive properties by heating, dissolving a pressure-sensitive adhesive with a solvent, or a photothermal conversion layer that decomposes by laser irradiation.

Japanese Patent No. 4565804 Japanese Patent No. 4936667

  However, since it takes time to dissolve the pressure-sensitive adhesive with the solvent, the productivity tends to decrease. The method of lowering the adhesion characteristics by heating is concerned about the influence on the semiconductor element due to the heating and is insufficient in heat resistance, so that it is difficult to use in a process application for forming a through electrode or the like. In the method of decomposing the adhesive by laser irradiation, introduction of expensive laser equipment is indispensable, and considerable investment is indispensable for application of such a process.

  As another technique for improving the peelability, a method of subjecting a semiconductor element or a support surface to a mold release treatment in advance is generally employed. However, in this case, since the mold release component is finally removed by washing, it is one of the causes of an increase in manufacturing cost as well as an increase in work steps of application and washing removal of the mold release component.

  Regarding the pressure-sensitive adhesive whose adhesiveness is lowered by heating, it is expected that the application of the mold release component becomes unnecessary by improving the peelability of the pressure-sensitive adhesive after heating. However, in this case, if the peelability of the pressure-sensitive adhesive after heating is increased, problems such as the occurrence of voids are likely to occur when the pressure-sensitive adhesive is exposed to a high temperature of about 200 ° C. in a circuit formation process or the like. It was difficult to obtain heat resistance. For example, when grinding a semiconductor element, the ground semiconductor element may be immediately separated from the support, but after grinding, a circuit may be formed on the surface of the semiconductor element and then separated from the support. In this case, the pressure-sensitive adhesive is strongly required to have high heat resistance that can withstand a high temperature of about 200 ° C. in the circuit forming process.

  The present invention has been made in view of the above circumstances, and it is easy for a film-like pressure-sensitive adhesive that can be used for fixing a substrate to be ground such as a silicon wafer to a support without application of a release component. The main object is to provide a film-like pressure-sensitive adhesive that can be peeled off and has sufficient heat resistance to withstand a high temperature of about 200 ° C.

One aspect of the present invention relates to a film-like pressure-sensitive adhesive containing a thermosetting component. The film adhesive is cured by heating in order of 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 30 minutes, and then 1000 mJ / cm ² of light is applied to the glass plate. When irradiated, the film-like pressure-sensitive adhesive has a 30 ° peel strength of 100 N / m or more before being irradiated with light after the film-like pressure-sensitive adhesive is cured. Is 50 N / m or less after being irradiated with light.

  According to the film-like pressure-sensitive adhesive, it can be easily peeled off without applying a release component, and sufficient heat resistance to withstand a high temperature of about 200 ° C. can be obtained.

  The film-like pressure-sensitive adhesive comprises (a1) the thermosetting component containing at least one of an epoxy resin and a phenol resin, (a2) a weight average molecular weight of 150,000 to 1,000,000, and a glass transition temperature of −50 ° C. to 50 ° C. A high molecular weight component having a crosslinkable functional group, (a3) (meth) acrylic monomer, (a4) photoradical polymerization initiator, and (a5) a thiol compound or a thioether compound. Containing sulfur compounds. As a result, the thermosetting component and the high molecular weight component react with heat during heating to increase the shear viscosity of the film-like pressure-sensitive adhesive, making it easier to hold the substrate to be ground even under high temperature and pressure, and the sulfur compound ( ) The thermal reaction of the acrylic monomer is suppressed, and the adhesion to the substrate to be ground is easily maintained. Moreover, after a film-like adhesive is irradiated with light, a (meth) acryl monomer can superpose | polymerize and it can also improve the peelability of a film-like adhesive more easily.

  The film-like pressure-sensitive adhesive may further contain (a6) a release agent. Thereby, the peelability of a film adhesive can be improved more easily.

  When the film-like pressure-sensitive adhesive is cured by sequential heating at 130 ° C. for 15 minutes and 170 ° C. for 15 minutes, the elastic modulus at 200 ° C. of the film-like pressure-sensitive adhesive after curing is 0.1 MPa or more. There may be. Thereby, generation | occurrence | production of the curvature of the base material to be ground thinned can be suppressed more.

  When the shear viscosity of the film-like pressure-sensitive adhesive is measured while raising the temperature from 35 ° C., the temperature at which the shear viscosity becomes 20000 Pa · s or less may be 40 ° C. to 150 ° C. This makes it easier to bond the substrate to be ground to which the film-like pressure-sensitive adhesive has been bonded and the support without causing damage and voids by vacuum pressure bonding.

  In another aspect, the present invention comprises (a) the film-like pressure-sensitive adhesive, (b) a support, and (c) a substrate to be ground, and the film-like pressure-sensitive adhesive is laminated on the substrate to be ground. And providing a laminate in which a substrate to be ground is fixed to a support via a film-like adhesive.

  The support may be a glass plate or a silicon mirror wafer.

  The substrate to be ground may be a silicon mirror wafer.

  In yet another aspect, the present invention provides a step of grinding the ground substrate provided in the laminate, and the film-like adhesive remains on either the ground substrate or the support. There is provided a method for producing a ground substrate, comprising: a step of separating a ground substrate to be ground from a support; and a step of peeling a film adhesive from the substrate to be ground or the support.

  According to the present invention, a film-like pressure-sensitive adhesive that can be used for fixing a substrate to be ground such as a silicon wafer to a support can be easily peeled off without applying a release component, and 200 It is possible to provide a film-like pressure-sensitive adhesive having sufficient heat resistance that can withstand a high temperature of about ° C. If the application of the mold release component can be eliminated, the work process can be shortened and the material cost can be reduced, and the semiconductor element can be manufactured at a lower cost.

  Further, the film adhesive according to the present invention is easier to control the film thickness than the liquid pressure-sensitive adhesive, and can reduce the thickness variation between individual substrates to be ground. Are better. Moreover, since it can form into a film on a semiconductor element or a support body by simple methods, such as a lamination, it can be anticipated that workability | operativity will also become favorable. A general liquid adhesive is applied to a semiconductor element or a support by spin coating or the like, and is used by forming a film by heating or UV irradiation, etc. In addition, there is a problem that the thickness after grinding tends to vary, and the spin coating has to discard the material scattered by the rotation at the time of application. According to the present invention, these problems can also be avoided.

  Furthermore, according to the present invention, there are provided a laminate in which a substrate to be ground and a support are joined via the film adhesive, and a method for producing a thinned substrate using such a laminate. can do.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The upper limit value and the lower limit value of the numerical ranges described in this specification can be arbitrarily combined. Numerical values described in the examples can also be used as the upper limit value or the lower limit value of the numerical range.

  The film adhesive which concerns on this embodiment contains a thermosetting component. The film-like pressure-sensitive adhesive can be used, for example, for fixing a substrate to be ground such as a silicon wafer to a support.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research on the selection of the resin of the film-like pressure-sensitive adhesive to be used and the adjustment of the physical properties. And when the present inventors are irradiated with light after being cured by predetermined heating, the present inventors control the 30 ° peel strength of the film-like adhesive with respect to the glass plate before and after being irradiated with light. While holding the substrate to be ground such as semiconductor elements at the time of grinding, without special pretreatment such as laser irradiation, and prior application of the release component to the substrate to be ground or the support surface for conveyance, It has been found that a film-like pressure-sensitive adhesive that can be easily peeled can be obtained without substantially generating a residue on the surface of the substrate to be ground and the support after peeling.

Specifically, the film-like pressure-sensitive adhesive is cured by heating in order of 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 30 minutes, and then 1000 mJ / cm after being attached to the glass plate. ^When the light of ² is irradiated, the 30 ° peel strength of the film-like adhesive with respect to the glass plate is 100 N / m or more before the light is irradiated after the film-like adhesive is cured. It may be 50 N / m or less after the agent is irradiated with light. Since the 30 ° peel strength before being irradiated with light after being cured is 100 N / m or more, good adhesion to the substrate to be ground in the grinding step can be obtained. Moreover, the favorable peelability from a to-be-ground base material and a support body can be acquired because the 30 degree peel strength after being irradiated with light is 50 N / m or less. From the same viewpoint, the 30 ° peel strength of the film-like pressure-sensitive adhesive with respect to the glass plate is preferably 300 N / m or more before being irradiated with light after the film-like pressure-sensitive adhesive is cured. Is preferably 30 N / m or less after being irradiated with light. The upper limit of the 30 ° peel strength is not particularly limited, but may be, for example, 10,000 N / m after the film-like pressure-sensitive adhesive is cured and before being irradiated with light.

  In order to obtain such peel strength, for example, to a film mainly composed of a thermosetting component, a high molecular weight component, and a (meth) acryl monomer, a photo radical polymerization initiator and a sulfur compound are added as photo reaction control components, If necessary, a release agent may be added as a release component to form a film-like pressure-sensitive adhesive.

  The film-like pressure-sensitive adhesive contains a thermosetting component, and by controlling the fluidity before curing and the elastic modulus after curing, it is possible to form a laminate without generating voids, and at the time of grinding Wafer retention and heat resistance at 200 ° C. can be achieved.

  Furthermore, the film-like pressure-sensitive adhesive contains a sulfur compound containing at least one of a thiol compound or a thioether compound often used as a secondary antioxidant, so that high peel strength and light after curing by heating can be obtained. Both low peel strength after irradiation can be achieved.

  In addition, the film-like pressure-sensitive adhesive contains a release agent, thereby facilitating peeling without prior application of the release component and further suppressing the generation of residues after peeling.

  The release agent is preferably a silicone compound. The silicone compound is a silicone compound having a crosslinkable functional group or a silicone compound having a functional group capable of interacting with a hydroxy group formed by the reaction of an epoxy resin that is a thermosetting component. This is preferable from the viewpoint of preventing elution and suppressing the generation of residues after peeling.

  From the above viewpoint, the film-like pressure-sensitive adhesive (thermosetting resin composition) according to the present embodiment includes, for example, (a1) a thermosetting component, (a2) a high molecular weight component, and (a3) (meth) acrylic. It contains a monomer, (a4) a photoradical polymerization initiator, (a5) a sulfur compound, and (a6) a release agent as required. The high molecular weight component may have a weight average molecular weight of 150,000 to 1000000 and / or a glass transition temperature of −50 ° C. to 50 ° C. From the viewpoint of obtaining an appropriate peel strength after the heat treatment, the content of the (a2) high molecular weight component is 25 to 1200 parts by mass with respect to 100 parts by mass of the (a1) thermosetting component, and (a3) (meta ) The acrylic monomer content is 25 to 1400 parts by mass, (a4) the radical photopolymerization initiator content is 0.05 to 10 parts by mass, and (a5) the sulfur compound content is 0.05 to It is 10.0 mass parts, and it is preferable that (a6) content of a mold release agent is 8-430 mass parts.

  In this specification, the glass transition temperature refers to a value measured by thermal differential scanning calorimetry (DSC). The temperature increase rate when measuring Tg is set to 10 ° C./min. As the DSC measuring apparatus, for example, “Thermo Plus 2” manufactured by Rigaku Corporation is used.

  In this specification, a weight average molecular weight is a polystyrene conversion value using a calibration curve by standard polystyrene measured by gel permeation chromatography (GPC).

  It is necessary to produce a laminate without damaging the substrate to be ground typified by semiconductor elements and without generating voids, but this can be achieved by controlling the film adhesive before curing I found. More specifically, by measuring the shear viscosity of the film-like pressure-sensitive adhesive while raising the temperature from 35 ° C., the temperature at which the shear viscosity becomes 20000 Pa · s or less is controlled to be 40 ° C. to 150 ° C. , 80 to 150 ° C., 0.01 to 0.2 MPa, 1 to 5 minutes, 1 to 15 mbar under a mild condition by vacuum pressing the substrate to be ground and the support to which the film-like adhesive is attached. A laminate can be produced without damaging and without generating voids.

  The shear viscosity was measured for a film-like test piece formed from a film-like pressure-sensitive adhesive using a viscoelasticity measuring device at a rate of temperature increase of 10 ° C./min while giving a strain of 5%. Means the measured value when. For example, ARES (manufactured by Rheometric Scientific) is used as the viscoelasticity measuring apparatus.

  Further, it is preferable to securely fix and maintain the substrate to be ground on the support even during the heat treatment at 200 ° C. When the film adhesive is cured by heating in order of 15 minutes at 130 ° C. and 15 minutes at 170 ° C. Moreover, it is preferable that the elastic modulus at 200 ° C. of the cured film-like pressure-sensitive adhesive is 0.1 MPa or more. If the elastic modulus at high temperature is 0.1 MPa or more, the warpage of the substrate to be ground thinned and the occurrence of warpage at a high temperature due to the difference in linear expansion coefficient between the substrate to be ground and the support are suppressed. There is a tendency to. The upper limit of the elastic modulus is not particularly limited, but is, for example, 10 MPa.

Hereinafter, each component will be described.
<(A1) Thermosetting component>
A thermosetting component is comprised from the compound which can form a crosslinked structure by heating. A thermosetting component contains at least any one among an epoxy resin or a phenol resin, for example. From the viewpoint of obtaining a film-like pressure-sensitive adhesive having a shear viscosity of 20000 Pa · s or less at any temperature of 40 to 150 ° C. as described above, the thermosetting component is phenol with respect to 100 parts by mass of the thermosetting component. It is preferable to contain 40 parts by mass or more of at least one of a resin and an epoxy resin having a softening point of 110 ° C. or lower or room temperature (for example, 23 ° C.). The phenol resin preferably has a softening point of 110 ° C. or lower or is liquid at room temperature. By containing such a thermosetting component, the remaining of voids after pressure bonding can be further suppressed without excessively increasing the shear viscosity of the film-like pressure-sensitive adhesive.

  There are no particular limitations on the epoxy resin and phenol resin that can satisfy such characteristics. Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin (for example, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. And novolak type epoxy resins such as YDCN-700-10). Examples of the phenol resin include Milex XLC series and XL series (for example, Milex XLC-LL) manufactured by Mitsui Chemicals, Inc., and HE series (for example, HE-200C-10) manufactured by Air Water Corporation.

  Other epoxy resins and phenol resins are not particularly limited as long as smooth curability can be obtained at a temperature of 200 ° C. or lower, but YDF2001 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., GPH103 manufactured by Nippon Kayaku Co., Ltd. Etc.

<(A2) High molecular weight component>
The weight average molecular weight of the high molecular weight component is preferably 150,000 to 1,000,000, more preferably 500,000 to 900,000. The glass transition temperature (Tg) of the high molecular weight component is preferably -50 ° C to 50 ° C, more preferably -30 ° C to 30 ° C. If the Tg of the high molecular weight component is −50 ° C. or higher, or the weight average molecular weight is 150,000 or higher, it does not cause an excessive decrease in shear viscosity and can suppress excessive protrusion of the film-like pressure-sensitive adhesive. There is little possibility to do. On the other hand, if Tg is 50 ° C. or lower, or if the weight average molecular weight is 1000000 or lower, excessive increase in shear viscosity is unlikely to occur, and shear viscosity becomes 20000 Pa · s or lower when heated at 150 ° C. There is little risk of voids remaining.

  The crosslinkable functional group possessed by the high molecular weight component is a functional group capable of forming a crosslinked structure by reaction between the crosslinkable functional groups and / or reaction with the thermosetting component. The high molecular weight component may contain 1 to 10% by mass of a monomer unit having a crosslinkable functional group based on the mass of the high molecular weight component. When the ratio of the monomer unit having a crosslinkable functional group is 1% by mass or more, the film-like pressure-sensitive adhesive easily forms sufficient crosslinks after thermosetting, and a substrate to be ground such as a semiconductor element is sufficiently obtained in the grinding process. It becomes easy to hold. Furthermore, foaming of the film-like pressure-sensitive adhesive can be further suppressed during heating at 200 ° C. when a circuit is formed on the ground element surface. On the other hand, when the ratio is 10% by mass or less, the shear viscosity of the film-like pressure-sensitive adhesive does not easily increase due to a crosslinking reaction, and excessive shear viscosity increase due to heating in the production process of the film-like pressure-sensitive adhesive. It tends to be easier to control. Moreover, deterioration with time of the film-like pressure-sensitive adhesive can be further suppressed. From the same viewpoint, the ratio of the monomer unit having a crosslinkable functional group is preferably 1 to 10% by mass, more preferably 3 to 8% by mass based on the mass of the high molecular weight component.

  It is preferable that content of a high molecular weight component is 25-1200 mass parts with respect to 100 mass parts of thermosetting components. When the content of the high molecular weight component is 25 parts by mass or more with respect to 100 parts by mass of the thermosetting component, it is difficult to cause an excessive decrease in the shear viscosity, and the excessive protrusion of the film-like pressure-sensitive adhesive can be further suppressed. And less likely to contaminate the device. On the other hand, when the content of the high molecular weight component is 1200 parts by mass or less with respect to 100 parts by mass of the thermosetting component, an excessive increase in the shear viscosity is unlikely to occur, and the shear viscosity is 20000 Pa · s when heated at 150 ° C. As a result, it is less likely that voids remain after pressure bonding. In addition, it becomes easier for the film-like pressure-sensitive adhesive to form a sufficient cross-link after curing by heating, and it becomes easier to sufficiently hold a substrate to be ground such as a semiconductor element in the grinding process. Furthermore, foaming of the film-like pressure-sensitive adhesive can be further suppressed during heating at 200 ° C. when a circuit is formed on the ground element surface. From the same viewpoint, the content of the high molecular weight component is preferably 25 to 1200 parts by mass and more preferably 100 to 600 parts by mass with respect to 100 parts by mass of the thermosetting component.

  By adjusting the weight average molecular weight of the high molecular weight component, Tg, the ratio of the monomer having a crosslinkable functional group and the content thereof as described above, the film-like pressure-sensitive adhesive is heated in order of 15 minutes at 130 ° C. and 15 minutes at 170 ° C. When is cured, the elastic modulus at 200 ° C. of the cured film-like pressure-sensitive adhesive can be facilitated by 0.1 MPa or more.

  The high molecular weight component includes, for example, at least one polymer selected from the group consisting of a polyimide resin, a (meth) acrylic resin, and a urethane resin. Among these, (meth) acrylic resins are preferable. In this specification, (meth) acrylic resin means a copolymer containing (meth) acrylic acid ester as a main monomer unit. In the present specification, “(meth) acryl” means “acryl” or “methacryl” corresponding to it.

The crosslinkable functional group possessed by the polymer component can be, for example, at least one functional group selected from the group consisting of epoxy groups and alcoholic or phenolic hydroxyl groups. For example, a (meth) acrylic resin such as a (meth) acrylic copolymer obtained by polymerizing a functional monomer having an epoxy group such as glycidyl (meth) acrylate as a crosslinkable functional group is more preferred.

  Examples of the (meth) acrylic resin include a (meth) acrylic acid ester copolymer having an epoxy group, a (meth) acrylic rubber having an epoxy group, and the like, and a (meth) acrylic rubber having an epoxy group is preferable. Epoxy group-containing (meth) acrylic rubber is mainly composed of (meth) acrylic acid ester, and is mainly a copolymer of butyl (meth) acrylate and acrylonitrile, ethyl (meth) acrylate and acrylonitrile, A rubber having an epoxy group made of such a copolymer is preferable.

<(A3) (Meth) acrylic monomer>
The film-like pressure-sensitive adhesive may contain a (meth) acrylic monomer. As the (meth) acrylic monomer, any of monofunctional, bifunctional, or trifunctional or higher polyfunctional ones can be used, and there is no particular limitation, and ordinary ones can be used.

  As monofunctional (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (Meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl ( Acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro- 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, Aliphatic (meth) acrylates such as mono (2- (meth) acryloyloxyethyl) succinate; cyclopentyl (meth) acrylate , Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate , Alicyclic (meth) acrylates such as mono (2- (meth) acryloyloxyethyl) hexahydrophthalate; phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) ) Acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphth Toxiethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl ( Aromatic (meth) acrylates such as meth) acrylate; 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethylhexahydrophthalimide, 2- ( Data) acrylate heterocyclic such as acryloyloxyethyl -N- carbazole (meth) acrylate, etc. These caprolactone modified products thereof.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol di (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopent Glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated 2- Aliphatic (meth) acrylates such as methyl-1,3-propanediol di (meth) acrylate; cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, propoxylated cyclohexanedimethanol (meth) acrylate, Et Silylated propoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated propoxylation Tricyclodecane dimethanol (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated Fats such as hydrogenated bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di (meth) acrylate Cyclic (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, propoxy Bisphenol F di (meth) acrylate, ethoxylated propoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) ) Acrylate, ethoxylated fluorene type di (meth) acrylate, propoxylated fluorene type di (meth) acrylate, ethoxylated propoxylated fluorene type di (meth) acrylate Aromatic (meth) acrylates such as acrylates; heterocyclic (meth) acrylates such as ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate These modified caprolactones; aliphatic (meth) acrylates such as neopentyl glycol type epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F Type alicyclic (meth) acrylate such as epoxy (meth) acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy ( Data) acrylate, bisphenol AF type epoxy (meth) acrylates, and aromatic epoxy (meth) acrylates such as fluorene epoxy (meth) acrylate.

  Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxylated tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (me ) Aliphatic (meth) acrylates such as acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate; ethoxylated isocyanuric acid tri (meth) acrylate, propoxylated Heterocyclic (meth) acrylates such as isocyanuric acid tri (meth) acrylate and ethoxylated propoxylated isocyanuric acid tri (meth) acrylate; these caprolactone modified products; phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meta) ) Aromatic epoxy (meth) acrylates such as acrylate. These compounds can be used individually or in combination of 2 or more types, and also can be used in combination with other polymerizable compounds.

  The (meth) acrylic monomer content is preferably 25 to 1200 parts by mass and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the thermosetting component. When the content of the (meth) acrylic monomer is within the above range, it becomes easier to achieve low peeling after light irradiation.

<(A4) Photoradical polymerization initiator>
The film-like pressure-sensitive adhesive may contain a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it initiates polymerization of the (meth) acrylic monomer by irradiation with actinic rays such as ultraviolet rays and visible rays.

  Examples of the radical photopolymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4 [4- (2-hydroxy Α-hydroxy ketones such as 2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyethoxy) ethyl oxyphenylacetate, oxy 2- (2-oxo-2-phenylacetoxyethoxy) ethyl phenylacetate, etc. Glyoxyester; 2-benzyl-2-dimethylamino-1- (4-morpholin-4-ylphenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-ylphenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropan-1-one, etc. Α-aminoketone of 1,2-octanedione, 1- [4- (phenylthio), 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl], oxime esters such as 1- (O-acetyloxime); bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimeth) Cybenzoyl) -2,4,4-trimethylpentylphosphine oxide, phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 2,4,5-triarylimidazole dimers such as 2,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N, N ′ , N′-tetramethyl-4,4′-diaminobenzophenone, N, N, N ′, N′-tetraethyl Benzophenone compounds such as 4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2 , 3-Benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4 -Quinone compounds such as naphthoquinone and 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin, Benzoin compounds such as ethylbenzoin; benzyl compounds such as benzyldimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis (9,9′-acridinylheptane): N-phenylglycine, coumarin and the like It is done. A radical photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types. Furthermore, the radical photopolymerization initiator can be used in combination with an appropriate sensitizer.

  It is preferable that content of radical photopolymerization initiator is 0.05-10 mass parts with respect to 100 mass parts of thermosetting components. When the content of the photo radical polymerization initiator is within the above range, it becomes easier to obtain sufficient (meth) acryl monomer reactivity by sufficient light irradiation. From the same viewpoint, the content of the radical photopolymerization initiator is preferably 0.05 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the thermosetting component. More preferred.

<(A5) Sulfur compound>
The film-like pressure-sensitive adhesive may contain a sulfur compound containing at least one of a thiol compound or a thioether compound. The thiol compound or thioter compound is not particularly limited as long as it is a compound having at least one thiol group (—SH) and / or thioether group (—S—) in the molecule, and usual compounds can be used.

  As the thiol compound or thioether compound, for example, dihexylthiodipropionate, dinonylthiodipropionate, didecylthiodipropionate, diundecylthiodipropionate, didodecylthiodipropionate, ditridecylthiodipropionate, Ditetradecylthiodipropionate, dipentadecylthiodipropionate, hexadecylthiodipropionate, diheptadecylthiodipropionate, dioctadecylthiodipropionate, dihexylthiodibutyrate, dinonylthiodibutyrate, di Decylthiodibutyrate, diundecylthiodibutyrate, didodecylthiodibutyrate, ditridecylthiodibutyrate, ditetradecylthiodibutyrate, dipentadecylthiodibutyrate, hexadecyl Ojibuchireto and di heptadecyl thio dibutyrate and the like.

  Examples of commercially available thiol compounds or thioether compounds include IRGANOX 1726 manufactured by BASF Corporation and SUMILIZER TP-D manufactured by Sumitomo Chemical Co., Ltd.

  It is preferable that it is 0.05-10.0 mass parts with respect to 100 mass parts of thermosetting components, and, as for content of a sulfur compound, it is more preferable that it is 1.0-5.0 mass parts. When the content of the sulfur compound is 0.05 parts by mass or more, the thermal reaction of the (meth) acrylic monomer during heating at 200 ° C. is further suppressed, and the (meth) acrylic monomer is more irradiated by light irradiation after heating at 200 ° C. Can be reacted. On the other hand, when the amount is 10.0 parts by mass or more, the reaction of the (meth) acrylic monomer in the light irradiation after heating at 200 ° C. tends to be suppressed, so the content of the sulfur compound is 10.0 parts by mass or less. Is preferred.

  A sulfur compound can be used individually by 1 type or in combination of 2 or more types.

<(A6) Release agent>
The film-like pressure-sensitive adhesive may further contain a release agent. The 5% weight reduction temperature of the release agent may be 200 ° C. or higher from the viewpoint of realizing heat resistance at 200 ° C.

  The release agent content is such that the 30 ° peel strength of glass adhesive after irradiation with light is 50 N / m or less, and the substrate to be ground can be easily peeled off from the support without prior application of the release component. In addition, from the viewpoint of suppressing residue generation after peeling, the amount may be 8 to 430 parts by mass with respect to 100 parts by mass of the thermosetting component. When it is 8 parts by mass or more, sufficient peelability is obtained and the peel strength tends to be suppressed, and when it is 430 parts by mass or less, (a1) a thermosetting component and (a2) a high molecular weight component. There is a tendency that the compatibility with respect to increases and the film is easily molded. From the same viewpoint, the content of the release agent is preferably 8 to 430 parts by mass and more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the thermosetting component.

  The mold release agent may contain, for example, at least one selected from silicone compounds and fluorine compounds. From the viewpoint of suppressing the generation of residues after peeling, the silicone compound should be selected from at least one selected from a silicone compound having a crosslinkable functional group and a silicone compound having a functional group capable of interacting with a hydroxy group. Can do. Examples of commercially available silicone compounds that can be used as a release agent include SH3773M and L-7001 manufactured by Toray Dow Corning Co., Ltd., KF105 and X-22-4741 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

<(A7) Curing accelerator>
The film-like pressure-sensitive adhesive may further contain a curing accelerator that functions as a catalyst for the curing reaction of the thermosetting component. If the reactivity of the curing accelerator is too high, excessive curing may proceed in the heat drying process for producing the film-like pressure-sensitive adhesive, which may cause an increase in shear viscosity before curing. May occur. Moreover, there is a tendency that deterioration with time is likely to be caused. On the other hand, if the reactivity of the curing accelerator is too low, not only the curing of the film-like pressure-sensitive adhesive is delayed and the curing time becomes long, but also the degree of crosslinking after heat curing is insufficient, and the substrate to be ground It may be difficult to securely fix to the support. From these viewpoints, an imidazole compound can be selected as the curing accelerator. Examples of the imidazole compound include 1-cyanoethyl-2-phenylimidazole and 2-phenylimidazole.

  The content of the curing accelerator is preferably 0.05 to 3.0 parts by mass and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the thermosetting component. When the content of the curing accelerator is 0.05 parts by mass or more, curing by heating sufficiently proceeds and the substrate to be ground tends to be reliably fixed to the support. Furthermore, since it is 0.05 mass part or more, a heat treatment for a long time is not required for hardening, and the heat-curing of a film adhesive can be implemented in a short time. On the other hand, when the content of the curing accelerator is 3.0 parts by mass or less, there is little possibility that the shear viscosity will increase due to heating during the production process of the film-like pressure-sensitive adhesive, and deterioration over time can be further suppressed. .

<(A8) Inorganic filler>
The film-like pressure-sensitive adhesive may further contain an inorganic filler. By containing the inorganic filler, the elastic modulus of the film-like pressure-sensitive adhesive can be easily controlled. It is preferable that content of the said inorganic filler is 70 mass parts or less with respect to 100 mass parts of thermosetting components. By making content of an inorganic filler into 70 mass parts or less, the excessive raise of the shear viscosity of a film adhesive can be suppressed.

  The inorganic filler may be at least one particle selected from, for example, titanium oxide, alumina, and silica. Alumina or silica can be selected from the viewpoint of a wide selection range of particle diameter and shape. In general, silica is cheaper.

  Examples of the shape of the inorganic filler include a spherical shape and an indefinite shape, but are not particularly limited thereto. The particle size of the inorganic filler is usually smaller than the film thickness of the film adhesive. In consideration of the film-forming property of the film adhesive, the particle size of the inorganic filler may be 5 μm or less. Although the minimum in particular of the particle size of an inorganic filler is not restrict | limited, For example, 0.01 micrometer may be sufficient. The particle diameter of the inorganic filler means the major axis diameter of the particles.

  Examples of commercially available inorganic fillers include SC2050-HLG, SC1030-HLG and YA050C-HHG manufactured by Admatechs Co., Ltd., and R972 manufactured by Nippon Aerosil Co., Ltd.

  The film-like pressure-sensitive adhesive may further contain other additives as long as the effects of the present invention are not impaired. Examples of additives include phenothiazine, hindered phenol polymerization inhibitors, nitroso polymerization inhibitors, general polymerization inhibitors such as aromatic amine antioxidants, and antioxidants.

<Method for producing film adhesive>
The film-like pressure-sensitive adhesive is obtained by, for example, applying a varnish prepared by mixing and kneading the above-described composition containing each component in an organic solvent on a base film, and removing the organic solvent from the applied varnish. Can be formed.

  Said mixing and kneading | mixing can be performed with a normal stirrer, a raking machine, a three roll, a ball mill, or the combination of these dispersers. The removal of the organic solvent is not particularly limited as long as the organic solvent is sufficiently volatilized, but can be performed by heating at 60 to 200 ° C. for 0.1 to 90 minutes, for example.

  The organic solvent for producing the varnish is not particularly limited as long as each component can be uniformly dissolved, kneaded or dispersed, and a normal one can be used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, dimethylacetamide, N methylpyrrolidone, toluene, and xylene. An organic solvent can be selected from methyl ethyl ketone and cyclohexanone because the drying speed is high and the price is low.

  There is no restriction | limiting in particular as a base film, For example, a polyester film, a polypropylene film (OPP film etc.), a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, and a methylpentene film are mentioned.

  The thickness of the film-like pressure-sensitive adhesive is preferably equal to or less than the unevenness on the surface of the semiconductor element, preferably 5 to 130 μm, from the viewpoint of sufficiently embedding the unevenness on the surface of the semiconductor element.

<Manufacturing method of thinned substrate to be ground>
An example of a method for manufacturing a substrate to be ground such as a thinned silicon mirror wafer according to this embodiment will be described below. (B) A film-like pressure-sensitive adhesive is affixed on a support at 60 to 120 ° C. by roll lamination. For example, a glass plate or a silicon mirror wafer is used as the support. Next, (c) the substrate to be ground is (80) 150-150 ° C./0.01-0.2 MPa / 1-5 min, 1-15 mbar using a vacuum bonding apparatus on the film-like adhesive. Vacuum bonding is performed to obtain a laminate. (C) The non-circuit surface of the substrate to be ground in the obtained laminate is ground to a desired thickness, and then (a) the film-like pressure-sensitive adhesive and (b) the support are removed to support (b) Collect body. Next, after grinding (c) the film-like pressure-sensitive adhesive remaining on the substrate to be ground was peeled and removed under room temperature to 80 ° C. heating conditions (c) the substrate to be ground Can be obtained.

  As mentioned above, although (a) film-like adhesive which concerns on this invention, its manufacturing method, and (c) the manufacturing method of the to-be-ground base material reduced in thickness was demonstrated, this invention is not necessarily the embodiment mentioned above. However, the present invention is not limited to this, and changes may be made as appropriate without departing from the spirit of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Production of film adhesive>
(Examples 1-10 and Comparative Examples 1-3)
(A1) epoxy resin and phenolic resin as thermosetting components, and (a6) silicone compound as mold release agent, as necessary (a8) of the product names and composition ratios (unit: parts by mass) shown in Table 1 or Table 2 ) The composition composed of inorganic filler and cyclohexanone were stirred and mixed. (A2) Acrylic rubber as a high molecular weight component and (a3) (meth) acrylic monomer are added and stirred. (A4) Photoradical polymerization initiator, (a5) Sulfur compound and (a7) Curing accelerator And stirred until each component became uniform to obtain a varnish for forming a film-like pressure-sensitive adhesive.

  Next, the obtained varnish was filtered through a 100-mesh filter and vacuum degassed. The varnish after vacuum defoaming was applied onto a polyethylene terephthalate (PET) film having a thickness of 38 μm as a base film. The applied varnish was heated and dried in two stages at 90 ° C. for 5 minutes and then at 140 ° C. for 5 minutes. Thus, a film-like pressure-sensitive adhesive having a thickness of 40 μm formed on the PET film was obtained.

Details of each material in Table 1 and Table 2 are shown below.
1. Thermosetting component (epoxy resin)
EXA830-CRP (trade name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 155-163, liquid at room temperature)
YDCN-700-10 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent: 210, softening point: 75-85 ° C.)
(Phenolic resin)
Millex XLC-LL (trade name, manufactured by Mitsui Chemicals, phenol resin, hydroxyl equivalent: 175, softening point: 77 ° C.)
GPH103 (trade name, manufactured by Nippon Kayaku Co., Ltd., phenol resin, hydroxyl group equivalent: 230, softening point: 99-106 ° C.)

2. High molecular weight component having a crosslinkable functional group / acrylic rubber HTR-860P-3CSP (sample name, Teikoku Chemical Sangyo Co., Ltd., acrylic rubber having epoxy group, weight average molecular weight: 800000, ratio of monomer unit having glycidyl group: 3 mass%, Tg: -7 ° C)
HTR-860P-30B-CHN (sample name, manufactured by Teikoku Chemical Industry Co., Ltd., acrylic rubber having an epoxy group, weight average molecular weight: 230000, ratio of monomer unit having a glycidyl group: 8% by mass, Tg: −7 ° C. )

3. (Meth) acrylic monomer A-DPH (sample name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)
A-9300 (sample name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)

4). Photoradical polymerization initiator Irgacure 369 (sample name, manufactured by BASF Corporation, 2-pentyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1)

5. Sulfur compound, IRGANOX 1726 (sample name, manufactured by BASF Corporation, 2,4-bis (dodecylthiomethyl) -6-methylphenol)
SUMILIZER TP-D (sample name, manufactured by Sumitomo Chemical Co., Ltd., bis [3- (dodecylthio) propionic acid] 2,2-bis [{3- (dodecylthio) -1-oxopropyloxy} methyl] -1,3 -Propanediyl)

6). Release agent (silicone compound)
TA31-209E (trade name, manufactured by Hitachi Chemical Co., Ltd., silicone-modified aminoalkyd resin, 5% weight loss temperature: 233 ° C.)
・ SH3773M (trade name, manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil, 5% weight reduction temperature: 215 ° C.)

7). Curing accelerator, Curesol 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl-2-phenylimidazole)

8). Inorganic filler R972 (trade name, manufactured by Nippon Aerosil Co., Ltd., surface treatment: dimethylsilane-treated silica, average particle size: 0.016 μm)

[Presence or absence of UV irradiation]
The film-like pressure-sensitive adhesives of Examples 1 to 10 and Comparative Examples 1 to 3 were subjected to UV irradiation of 1000 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Moreover, the case where UV irradiation was not performed to the film-like adhesive produced similarly to Example 1 was made into the reference example 1. FIG.

<Evaluation of various physical properties>
About the obtained film-like pressure-sensitive adhesive, shear viscosity, elastic modulus at 200 ° C. after curing, 30 ° peel strength from glass, presence / absence of voids in laminate, peelability in debonding apparatus, and heat resistance at 200 ° C. Was evaluated.

[Shear viscosity]
After peeling off and removing the base film from the film-like pressure-sensitive adhesive, four film-like pressure-sensitive adhesives were laminated by roll lamination at 80 ° C. to obtain a laminate having a thickness of 160 μm. This was punched into a 10 mm square in the thickness direction to obtain a test piece having a square main surface of 10 mm square and a thickness of 160 μm. A circular aluminum plate jig having a diameter of 8 mm was attached to a dynamic viscoelastic device ARES (manufactured by Rheometric Scientific), and a film-like adhesive test piece was set there. Thereafter, the shear viscosity was measured while raising the temperature from 35 ° C. to 150 ° C. at a rate of temperature increase of 20 ° C./min while applying 5% strain, and the temperature at which the shear viscosity value was 20000 Pa · s was recorded.

[Elastic modulus at 200 ° C. after curing]
After peeling off and removing the base film from the film-like pressure-sensitive adhesive, it was cut into a 4 mm width and a length of 30 mm and heated in an oven at 130 ° C. for 15 minutes and then at 170 ° C. for 15 minutes to obtain a test piece. The obtained test piece is set in a dynamic viscoelastic device (product name: Rhegel-E4000, manufactured by UMB), a tensile load is applied, and the elastic modulus is measured at a frequency of 10 Hz and a heating rate of 3 ° C./min. The measured value at 200 ° C. was recorded.

[30 ° peel strength from glass]
The film adhesive was roll laminated at 80 ° C. on a glass (product name: MICRO SLIDE GLASS, Matsunami Glass Industrial Co., Ltd.) surface, and then the substrate film was peeled from the film adhesive. Next, the laminated film-like pressure-sensitive adhesive and glass were used in an oven (product name: Inert Oven DN4101, manufactured by Yamato Scientific Co., Ltd.) in a nitrogen atmosphere at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200. Heated in the order of 30 minutes at ° C. Next, an adhesive tape (PP tape # 400, product number 204H, manufactured by Oji Tac Co., Ltd.) was attached to the film adhesive as a support tape, and then cut into a width of 10 mm to obtain a test specimen for measuring peel strength. Using the obtained specimen, a peel test was performed at a speed of 300 mm / s with a peel tester set so that the peel angle (the angle formed inside the folded film adhesive) was 30 °, The peel strength at that time was recorded as the peel strength before UV irradiation. Thereafter, UV irradiation of 1000 mJ / cm ² was performed from the glass surface using a UV irradiation machine (product name: UV-330 HQP-2 type exposure machine, manufactured by Oak Manufacturing Co., Ltd.), and the same peel test was performed. The peel strength at that time was recorded as the peel strength after UV irradiation. In the peel test, no residue of the film-like adhesive remained on the glass after the film-like adhesive of each Example was peeled off.

[Presence or absence of voids in the laminate]
A film-like pressure-sensitive adhesive was attached to a silicon mirror wafer as a support by roll lamination at 80 ° C. to obtain a support having a film-like pressure-sensitive adhesive. Next, the base film on the film-like adhesive is peeled off, and then the base material to be ground (silicon mirror wafer, thickness 770 μm) is 120 ° C./0.1 MPa / 5 min with a vacuum bonding apparatus (SUSS MicroTech, LF12), A laminate was obtained by vacuum pressure bonding at 5 mbar. The obtained laminate was inspected with an ultrasonic imaging apparatus SAT (manufactured by Hitachi Construction Machinery Co., Ltd., FS200II) to confirm the presence or absence of voids. The evaluation criteria for the presence or absence of voids are as follows.
A: The void ratio is less than 5%.
B: Void ratio is 5% or more.

[Peelability with debonding equipment]
A film-like pressure-sensitive adhesive was attached to glass as a support by roll lamination at 80 ° C. to obtain a support having a film-like pressure-sensitive adhesive. Next, the base film on the film-like adhesive is peeled off, and then the base material to be ground (silicon mirror wafer, thickness 770 μm) is 120 ° C./0.1 MPa / 5 min with a vacuum bonding apparatus (SUSS MicroTech, LF12), A laminate was obtained by vacuum pressure bonding at 5 mbar. The obtained laminate is heated in a nitrogen atmosphere at 130 ° C. for 30 minutes and 170 ° C. for 30 minutes in order to cure the film-like pressure-sensitive adhesive, and then grinded with a grinder (manufactured by Disco, DGP8761HC). The material was ground to 50 μm. Next, after heating at 200 ° C. for 30 minutes in a nitrogen atmosphere, using a UV irradiator from the glass surface, the substrate was irradiated with 1000 mJ / cm ² of UV, and then a dicing tape (Furukawa Electric) on the substrate to be ground. UC-353EP-110 manufactured by Co., Ltd. was pasted, and debonding evaluation was performed using a debonding apparatus (manufactured by SUSS MicroTech, DB12T). A sample that could be separated without damage to the support and the substrate to be ground was designated as A, and a sample that could not be separated or was damaged was designated as B.

[Heat resistance at 200 ° C]
A silicon mirror wafer (6 inches) having a thickness of 625 μm was cut into 30 mm square pieces by blade dicing. A film-like adhesive was roll-laminated at 80 ° C. on the surface of the silicon mirror wafer that had been cut into pieces. Next, after peeling and removing the base film on the film-like adhesive, a slide glass having a thickness of 0.1 to 0.2 mm and a size of about 18 mm square is roll-laminated at 80 ° C. on the film-like adhesive. A laminated product in which a film adhesive was sandwiched between a silicon wafer and a slide glass was produced. The obtained laminate was heated in a nitrogen atmosphere at 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 30 minutes to obtain a test specimen.

The obtained specimen was observed from the slide glass surface, and the image was analyzed with software such as Photoshop (registered trademark), and the heat resistance at 200 ° C. was evaluated from the ratio of voids in the total area of the film-like pressure-sensitive adhesive. The evaluation criteria are as follows.
A: The void ratio is less than 5%.
B: Void ratio is 5% or more.

  Tables 3 and 4 show the evaluation results. As is apparent from these results, the film peel strength of the adhesive on the glass satisfies both the requirements of 100 N / m or more after curing and 50 N / m or less after UV irradiation, so that there is no application of a release component. It can be easily peeled off and sufficient heat resistance to withstand a high temperature of about 200 ° C. can be obtained.

Claims (9)

A film-like pressure-sensitive adhesive containing a thermosetting component,
The film adhesive is cured by heating in order of 130 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 30 minutes, and then 1000 mJ / cm ² of light is applied to the glass plate. When irradiated, the 30 ° peel strength of the film-like adhesive with respect to the glass plate is
After the film-like pressure-sensitive adhesive is cured, before being irradiated with light, at 100 N / m or more,
The film-like pressure-sensitive adhesive is 50 N / m or less after being irradiated with light.
Film adhesive. (A1) the thermosetting component containing at least one of epoxy resin or phenol resin;
(A2) a high molecular weight component having a weight average molecular weight of 150,000 to 1,000,000 and a glass transition temperature of −50 ° C. to 50 ° C. and having a crosslinkable functional group;
(A3) a (meth) acrylic monomer;
(A4) a radical photopolymerization initiator;
(A5) a sulfur compound containing at least one of a thiol compound or a thioether compound;
The film adhesive of Claim 1 containing this.   (A6) The film adhesive of Claim 1 or 2 which further contains a mold release agent.   When the film-like pressure-sensitive adhesive is cured by sequential heating at 130 ° C. for 15 minutes and 170 ° C. for 15 minutes, the elastic modulus at 200 ° C. of the film-like pressure-sensitive adhesive after being cured is 0.1 MPa or more. The film adhesive as described in any one of Claims 1-3 which is.   The temperature at which the shear viscosity becomes 20000 Pa · s or less when the shear viscosity of the film-like pressure-sensitive adhesive is measured while raising the temperature from 35 ° C is 40 ° C to 150 ° C. The film-like pressure-sensitive adhesive according to item. (A) The film-like pressure-sensitive adhesive according to any one of claims 1 to 5, (b) a support, and (c) a substrate to be ground.
The laminate in which the film-like pressure-sensitive adhesive is laminated on the substrate to be ground, and the substrate to be ground is fixed to the support via the film-like pressure-sensitive adhesive.   The laminate according to claim 6, wherein the support is a glass plate or a silicon mirror wafer.   The laminate according to claim 6 or 7, wherein the ground substrate is a silicon mirror wafer. Grinding the substrate to be ground provided in the laminate according to any one of claims 6 to 8,
Separating the ground substrate to be ground from the support so that the film adhesive remains on either the ground substrate or the support; and
Peeling the film adhesive from the substrate to be ground or the support;
A method for producing a ground substrate.