JP2016216572A - Support member for organic substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support member for an organic substrate which can reduce foaming and peeling an interface between an organic substrate and a support member while securing good conveying properties of the organic substrate and sufficient peelability from the organic substrate.SOLUTION: There is provided a support member 10 for an organic substrate for temporarily stuck to an organic substrate 12 in manufacture of an electronic device having the organic substrate 12 which has a resin film base material 2 and a resin layer 4 that is provided on one surface side of the resin film base material 2 and contains a thermosetting resin, where when the resin layer 4 has been subjected to a heating treatment on a heating condition that the resin layer is heated sequentially at 130°C for 30 minutes and at 170°C for 60 minutes in a state of being stuck to a resist layer formed from AUS (registered trademark) 308 being a solder resist ink for substrate, a 90° peeling strength with respect to the resist layer of the resin layer 4 after subjected to the heating treatment is 200 N/m or less at 25°C and 2 N/m or more at 175°C.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an organic substrate support member. More specifically, the present invention enables, for example, protecting the back surface of the organic substrate by pasting on the back surface of the organic substrate, or improving the transportability of the thin organic substrate by pasting on the back surface of the organic substrate. The present invention relates to a support member for an organic substrate.

  As electronic devices such as smartphones and tablet PCs become multifunctional, stacked MCPs (Multi Chip Packages) in which semiconductor elements are stacked in multiple stages to increase the capacity have become widespread. With such multi-layer stacking of semiconductor elements, the thickness of the semiconductor device tends to increase, but electronic devices are required to be further downsized, and the thickness of the semiconductor device is rather indispensable. It has become.

  In order to achieve such multi-layer stacking of semiconductor elements and thinning of a semiconductor device, the thinning of the semiconductor element, the thinning of the paste or film adhesive used for mounting the semiconductor element, and the organic for mounting the semiconductor element Thinning the substrate has been studied.

  In recent years, the thickness of a semiconductor element has been reduced to about 30 μm, and the thickness of a paste-like or film-like adhesive used for mounting a semiconductor element has been reduced to about 5 μm. On the other hand, even if the substrate is thin, it is about 100 μm, and the ratio of the thickness of the substrate in the entire semiconductor device is large, and it is an important issue to reduce the thickness of the organic substrate. For example, wiring has been conventionally formed using a core material, but a thin organic substrate having no core has been developed, and mounting of semiconductor elements on these has been studied.

JP 2004-266138 A

  A thin organic substrate having no core has a thickness of less than 70 μm and is easy to bend. Therefore, there is a problem that conveyance is poor and it is difficult to use alone. For this reason, improvement of transportability is indispensable for the development of a semiconductor package using a thin organic substrate having no core. As one of the measures for improving the transportability, the inventor attaches a peelable adhesive film as a support member to the back surface of the thin organic substrate, and after the process such as mounting of the semiconductor element in that state, finally The method of peeling and removing the adhesive film was examined. According to this method, moderate rigidity is imparted to the organic substrate, and better transportability can be obtained. Therefore, it can be expected that manufacturing of an electronic device such as a semiconductor device using a thin organic substrate will be facilitated. .

  However, when the adhesive film is attached to the back surface of the organic substrate as a support member, when a high-temperature and high-pressure process such as formation of a sealing layer is performed, firing may occur between the adhesive film and the organic substrate. In some cases, the adhesive force between the film and the organic substrate cannot withstand the high pressure during the formation of the sealing layer, and the adhesive film peels from the organic substrate. Although foaming and peeling of the adhesive film can be prevented by increasing the adhesion of the adhesive film to the organic substrate, in that case, the peelability at the time of finally peeling the adhesive film from the organic substrate decreases, and adhesion It tends to happen that the film breaks or the resin remains on the back surface of the organic substrate.

  The present invention has been made in view of the above circumstances, and relates to a support member for an organic substrate that is temporarily attached to an organic substrate in the manufacture of an electronic device including the organic substrate. The main object is to reduce foaming and peeling at the interface between the organic substrate and the support member while ensuring sufficient peelability from the organic substrate.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research on the layer structure of the support member, the adjustment of physical properties to be satisfied by each layer, and the selection of the resin to be used. And the present inventors came to find the support member for organic substrates provided with the resin layer which has specific peelability.

  One aspect of the present invention relates to a support member for an organic substrate that is temporarily attached to an organic substrate in the manufacture of an electronic device including the organic substrate. The support member includes a resin film substrate and a resin layer that is provided on one surface side of the resin film substrate and contains a thermosetting resin. Depending on the heating conditions in which the resin layer is affixed to a resist layer formed from AUS (registered trademark) 308, which is a solder resist ink for substrates, in order of 30 minutes at 130 ° C. and 60 minutes at 170 ° C. When the heat treatment is performed, the 90 ° peel strength of the resin layer after the heat treatment with respect to the resist layer may be 200 N / m or less at 25 ° C. and 2 N / m or more at 175 ° C.

  According to the support member, foaming and peeling at the interface between the organic substrate and the support member can be further reduced while ensuring good transportability of the organic substrate and sufficient peelability from the organic substrate. AUS (registered trademark) 308 is an ink widely used by those skilled in the art to form a solder resist on an organic substrate. The peel strength with respect to the resist layer thus formed is regarded as a value representative of the peel strength with respect to a general organic substrate, and the peelability of the resin layer after the heat treatment is specified using this as an index.

  When the resin layer is heat-treated under the above heating conditions, the storage elastic modulus at 175 ° C. of the resin layer after the heat treatment may be 6 MPa or more. As a result, better transportability can be obtained, and further excellent effects can be obtained in terms of suppressing deformation of the resin layer under high temperature and pressure.

  The resin layer includes (A) a release layer having a surface opposite to the resin film substrate of the resin layer as a main surface, and (B) a high elasticity provided between the release layer and the resin film substrate. And an efficiency layer. Here, the high elastic modulus layer has a storage elastic modulus at 175 ° C. of the high elastic modulus layer after the heat treatment when the high elastic modulus layer and the release layer are heat treated under the above heating conditions. It is a layer higher than the storage elastic modulus at 175 ° C. of the release layer after the heat treatment. The resin layer has two layers, a release layer and a high modulus layer, so that the release layer can be provided with appropriate adhesion before the heat treatment and peelability after the heat treatment while the high temperature and high pressure. It is possible to easily suppress the protrusion of the resin from the resin layer.

  The release layer has (a1) a weight average molecular weight of 200000 to 1100000, a glass transition temperature of −50 ° C. to 50 ° C., a high molecular weight component having a crosslinkable functional group, (a2) a release agent, May be contained. Thereby, the moderate adhesiveness of the release layer before heat processing and the peelability from the organic substrate after heat processing can be obtained more easily.

  The high elastic modulus layer comprises (b1) a high molecular weight component having a weight average molecular weight of 200000 to 1100000 and a glass transition temperature of −50 ° C. to 50 ° C. and having a crosslinkable functional group, and (b2) the heat described above. It may contain a curable resin and (b3) an inorganic filler. Thereby, a storage elastic modulus higher than that of the release layer can be particularly easily imparted to the high elastic modulus layer. In addition, the transportability of the organic substrate can be improved more easily.

  The shear viscosity at 80 ° C. of the release layer and the high elastic modulus layer may be 20000 Pa · s or less. Thereby, the embedding property to the unevenness | corrugation of the organic substrate surface and the adhesiveness to an organic substrate can be improved more.

  The storage elastic modulus at 175 ° C. of the resin film substrate may be 500 MPa or more. Thereby, it becomes difficult to deform | transform a support member under high temperature / high pressure, and the conveyance property of an organic substrate can be improved more.

  According to the present invention, regarding the support member for an organic substrate to be temporarily attached to the organic substrate in the manufacture of an electronic device including the organic substrate, the organic substrate has good transportability and sufficient peelability from the organic substrate. While ensuring, foaming and peeling at the interface between the organic substrate and the support member can be further reduced.

It is sectional drawing which shows one Embodiment of a support member. It is sectional drawing which shows one Embodiment of the manufacturing method of the electronic device which uses a support member.

  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.

  FIG. 1 is a cross-sectional view showing an embodiment of a support member. A support member 10 shown in FIG. 1 includes a resin film substrate 2 and a resin layer 4 provided on one surface side of the resin film substrate 2. The resin layer 4 is a layer that contains a thermosetting resin and has adhesiveness.

  The support member 10 for organic substrates is used because it is temporarily attached to an organic substrate in the manufacture of an electronic device including the organic substrate. FIG. 2 is a cross-sectional view illustrating an embodiment of a method for manufacturing an electronic device using a support member.

  The method according to the embodiment of FIG. 2 includes a step (a) in which the support member 10 is bonded to one surface of the organic substrate 12 so that the resin layer 4 faces the organic substrate 12, and the support member 10 of the organic substrate 12. A step (b) of mounting a plurality of electronic components 14 on the opposite surface, a step (c) of forming a sealing layer 16 for sealing the electronic components 14 mounted on the organic substrate 12; A step (d) of peeling the support member 10 from the organic substrate 12.

  The mounting of the electronic component 14 and the formation of the sealing layer 16 are performed after the laminated body 100 having the organic substrate 12 and the support member 10 bonded to the organic substrate 12 is conveyed or conveyed to a predetermined position. ,It can be carried out. By bonding the support member 10, the organic substrate 12 can be easily transported while maintaining an accurate position and shape.

  The organic substrate 12 is not particularly limited as long as it is a substrate such as a printed wiring board configured so that an electronic component can be mounted. For example, one or more build-up layers and an inner side of the build-up layer A multilayer printed wiring board having a core material provided may be used, or a coreless wiring board having only a buildup layer and / or a rewiring layer and no core material may be used. An ultra-thin organic substrate (particularly a coreless wiring board) tends to be difficult to handle by itself, and sticking a support member to this is particularly useful for ensuring sufficient transportability and the like. . The thickness of the extremely thin organic substrate is, for example, less than 80 μm or less than 70 μm. Although the minimum in particular of the thickness of an organic substrate is not restrict | limited, For example, it is 40 micrometers.

  The support member 10 is bonded to the organic substrate 12 while the support member 10 is heated by a method such as thermal lamination as necessary. The heating temperature is, for example, 60 to 140 ° C.

  As shown in FIG. 2B, a plurality of electronic components 14 are mounted on the surface of the organic substrate 12 opposite to the support member 10. The electronic component 14 is, for example, a semiconductor element. The plurality of electronic components 14 may be mounted on the organic substrate 12 at a time, or may be sequentially mounted while transporting the organic substrate 12. The number of electronic components 14 mounted on the organic substrate 12 may be one.

  As shown in FIG. 2C, the sealing layer 16 is formed on the surface of the organic substrate 12 opposite to the support member 10 so as to cover the electronic component 14. The sealing layer 16 can be formed by a method such as molding with heating and pressurization using various sealing resin materials usually used by those skilled in the art. When forming the sealing layer 16, the laminated body 100 (and sealing resin material) is heated and pressurized on conditions of 160-190 degreeC, 1-4 minutes, and 4-10 MPa, for example. For example, in the case of molding, pressure is applied by a clamping load of a mold for molding.

  After the formation of the sealing layer 16, as shown in FIG. 2D, the support member 10 is peeled from the organic substrate 12, whereby the organic substrate 12 and the electronic component 14 provided on the organic substrate 12. And the electronic device 20 including the sealing layer 16 for sealing the electronic component 14 is obtained.

  In the step of forming the sealing layer 16, the support member 10 is exposed to high temperature and high pressure, so that the support member 10 is not substantially deformed even under high temperature and high pressure, and at the interface between the resin layer 4 and the organic substrate 12. It is desirable that peeling and foaming do not occur. Furthermore, it is also required that the support member 10 is finally easily peeled from the organic substrate.

  In order to satisfy these requirements, a resin layer 4 having a specific peelability after heat treatment is used. In addition, the support member 10 attached to the organic substrate 12 is heat-treated to suppress peeling and foaming at the interface between the resin layer 4 and the organic substrate 12 while maintaining a good peelability of the support member. can do. In the case of this embodiment, the step of heat-treating the support member 10 may be provided between the step of bonding the support member 10 to the organic substrate 12 and the step of forming the sealing layer 16. The support member 10 may be subjected to heat treatment by heating in the step of forming. When the support member 10 is heat-treated by heating different from the step of forming the sealing layer 16, the conditions are, for example, 130 to 140 ° C. for 30 to 40 minutes and 165 to 175 ° C. for 50 to 70 minutes. is there.

  Specifically, the resin layer 4 is attached to a resist layer formed from AUS (registered trademark) 308, which is a solder resist ink for substrates, in the order of 30 minutes at 130 ° C. and 60 minutes at 170 ° C. When the heat treatment is performed under the heating conditions, the 90 ° peel strength of the resin layer 4 after the heat treatment with respect to the resist layer is 200 N / m or less at 25 ° C. and 2 N / m or more at 175 ° C. Also good. When the 90 ° peel strength at 175 ° C. is 2 N / m or more, peeling of the resin layer 4 from the organic substrate 12 in a high-temperature and high-pressure process such as formation of a sealing layer can be suppressed. Moreover, the favorable peelability from the organic substrate of the resin layer 4 after heat processing can be acquired because the 90 degree peel strength in 25 degreeC is 200 N / m or less. From the same viewpoint, the 90 ° peel strength of the resin layer 4 after the heat treatment with respect to the resist layer may be 150 N / m or less, or 50 N / m or less at 25 ° C. The lower limit of the 90 ° peel strength at 25 ° C. is not particularly limited, but may be, for example, 10 N / m. The upper limit of the 90 ° C. peel strength at 175 ° C. is not particularly limited, but may be, for example, 40 N / m.

  The storage elastic modulus at 175 ° C. of the resin layer 4 after being heat-treated under the same heating conditions as described above may be 6 MPa or more. Since the storage elastic modulus at 175 ° C. of the resin layer after the heat treatment is 6 MPa or more, the protrusion of the resin from the end of the support member under high temperature and high pressure can be effectively suppressed. The upper limit of the storage elastic modulus is not particularly limited, but is, for example, 20 MPa.

  The thickness of the resin layer 4 may be, for example, 10 to 80 μm or 20 to 60 μm.

  An example of the form of the support member 10 and the resin layer 4 having the above characteristics will be described below.

  The resin layer 4 of the support member 10 according to the present embodiment includes a release layer 6 having a surface opposite to the resin film substrate 2 as a main surface, and between the release layer 6 and the resin film substrate 2. And a high elastic modulus layer 8 having a higher storage elastic modulus than the release layer 6.

  The release layer 6 is a layer that exhibits appropriate peelability from the organic substrate 12 after the heat treatment. The high elastic modulus layer 8 is heat-treated when the high elastic modulus layer 8 and the release layer 6 are heat-treated under the heating conditions of heating at 130 ° C. for 30 minutes and 170 ° C. for 60 minutes in this order. The storage elastic modulus at 175 ° C. of the increased elastic modulus layer 8 after heating is higher than the storage elastic modulus at 175 ° C. of the release layer 6 after the heat treatment.

  The release layer 6 is configured to have an appropriate peelability after the heat treatment while having an appropriate adhesion to the organic substrate before the heat treatment. Although the surface of the organic substrate 12 is often uneven, the release layer 6 has adequate adhesion so that the unevenness can be sufficiently embedded when bonded to the organic substrate 12. If the unevenness on the surface of the organic substrate is insufficient, foaming may occur due to a thermal history during the subsequent process, which may cause a problem that the semiconductor element cannot be mounted accurately.

  By providing appropriate adhesion to the release layer 6, it is possible to satisfactorily bury the irregularities on the surface of the organic substrate. In this case, the resin layer 4 is deformed under high pressure, and the end of the support member 10 is There is a possibility that the resin protrudes from the portion. In the case of this embodiment, since the high elastic modulus layer 8 is provided on the inner side of the release layer 6, even if the release layer 6 has a certain degree of fluidity, The protrusion can be effectively suppressed.

  Adhesiveness of the resin layer 4 to the organic substrate 12 and embedding in the irregularities on the surface of the organic substrate 12 can be achieved, for example, by managing the shear viscosity of the release layer 6 before the heat treatment. From such a viewpoint, the shear viscosity at 80 ° C. of the release layer 6 before the heat treatment may be 20000 Pa · s or less, 18000 Pa · s or less, or 16000 Pa · s or less. The lower limit of the shear viscosity is not particularly limited, but may be, for example, 2000 Pa · s. Such a reduction in viscosity can be achieved, for example, by adjusting the amount of fluid components such as a release agent, a thermosetting resin, and a curing agent.

  In order to more effectively prevent deformation of the resin layer 4 under high temperature and high pressure, the thickness of the release layer 6 can be reduced. In that case, not only the shear viscosity of the release layer 6 but also the shear viscosity of the high elastic modulus layer may be set within the above numerical range.

  The above shear viscosity is a film-like test piece formed from a release layer or a high elastic modulus layer with a temperature increase rate of 10 ° C./min while applying 5% strain using a viscoelasticity measuring device. It means a measured value at 80 ° C. when the shear viscosity is measured. As the viscoelasticity measuring device, for example, ARES (manufactured by Rheometric Scientific) is used.

  The storage elastic modulus at 175 ° C. of the high elastic modulus layer 8 after the heat treatment may be 7 MPa or more, or 8 MPa or more. Thereby, the resin layer 4 becomes difficult to deform under high temperature and high pressure, and the protrusion of the resin can be particularly effectively suppressed. Moreover, since the rigidity of the whole support member 10 increases, it is advantageous also in terms of transportability that the high elastic modulus layer 8 has a high storage elastic modulus.

  When the elastic modulus of the resin layer 4 is increased, it is expected that the deformation under high temperature and high pressure is reduced, but in this case, the adhesion and fluidity of the resin layer 4 tend to decrease. However, by providing the resin film substrate 2 in addition to the resin layer 4, high resistance to high temperature and high pressure conditions can be easily imparted to the support member 10 while ensuring appropriate adhesion and fluidity of the resin layer 4. be able to. Since the composite storage elastic modulus of the laminate composed of a plurality of layers is the sum of the product of the thickness of each layer and the storage elastic modulus, the support member is provided by providing not only the resin layer 4 but also the resin film substrate 2. The composite storage elastic modulus of the entire 10 can be designed high. As a result, deformation under high temperature and high pressure can be effectively suppressed, and good transportability can be easily obtained. Furthermore, as a result of providing the resin film base material, the necessity of increasing the elasticity of the release layer and the high modulus layer is relatively reduced, so that the likelihood of material design in these layers can be expanded. .

  From the above viewpoint, the storage elastic modulus at 175 ° C. of the resin film substrate 2 may be 500 MPa or more, 600 MPa or more, or 650 MPa or more. Further, the storage elastic modulus at 175 ° C. of the resin film substrate 2 may be 10,000 MPa or less, 9000 MPa or less, or 8000 MPa or less. As the resin film substrate 2, a thermoplastic resin film whose storage elastic modulus at 175 ° C. does not substantially change before and after the heat treatment can be selected. Examples of the thermoplastic resin film used as the resin film substrate include a polyimide film and a polyethylene naphthalate film (PEN film).

  From the viewpoint of suppressing the protrusion of the resin under high temperature and high pressure, the thickness of the release layer 6 may be smaller than the thickness of the high elastic modulus layer 8. Specifically, the thickness of the release layer 6 may be 0.5 to 50 μm, 3 to 40 μm, or 5 to 30 μm. By thinning the release layer 6 having a relatively low elastic modulus, it is possible to particularly effectively suppress the resin from protruding from the end of the support member under high temperature and high pressure.

  The thickness of the high elastic modulus layer 8 may be 5 to 200 μm, 5 to 150 μm, or 10 to 100 μm from the viewpoint of suppressing the protrusion of the resin under high temperature and high pressure and maintaining the transportability.

  The thickness of the resin film substrate can be 12.5 to 200 μm. In order to suppress the deformation of the support member under high pressure and particularly remarkably increase the transportability of the organic substrate, the thickness of the resin film substrate may be 17.5 to 150 μm, or 20 to 100 μm.

Hereinafter, materials that can be used to form each layer having the above-described characteristics will be described.
(A) Release layer The release layer may contain (a1) a high molecular weight component which is a polymer having a crosslinkable functional group, and (a2) a release agent. By the combination of the high molecular weight component and the release agent, a release layer having adhesion (shear viscosity) before heat treatment and peelability after heat treatment as described above can be easily formed.

  The weight average molecular weight of the high molecular weight component is 200000 to 1100000, 400000 to 1000000, or 600000 to 950,000 in order to provide the release layer with appropriate fluidity before heat treatment and moderate peelability after heat treatment. There may be. From the same viewpoint, the glass transition temperature (Tg) of the high molecular weight component may be −50 ° C. to 50 ° C., −45 to 30 ° C., or −40 to 10 ° C. By using a high molecular weight component having a weight average molecular weight and / or Tg within these ranges, it is particularly effective that the release layer that has become excessively soft stretches and peeling of the resin layer from the organic substrate becomes difficult. Can be suppressed. In addition, particularly excellent effects are easily obtained from the viewpoint of adhesion and embedding to the surface of the organic substrate including irregularities.

  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).

  The crosslinkable functional group of the high molecular weight component in the release layer has a cross-linked structure by reaction between the crosslinkable functional groups and / or reaction between the crosslinkable functional group and a thermosetting resin or a curing agent described below. It is a functional group that can be formed. Due to the reaction of the crosslinkable functional group accompanying the heat treatment, the adhesiveness and peelability of the release layer change. 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, a release layer having a good bulk strength is easily formed, and it is possible to suppress the difficulty in peeling due to the extension of the release layer during peeling. . When this ratio is 10% by mass or less, an appropriate peel strength is easily obtained when the crosslinking reaction proceeds by heat treatment. From the same viewpoint, the ratio of the monomer unit having a crosslinkable functional group may be 2 to 9% by mass based on the mass of the high molecular weight component.

  The high molecular weight component in the release layer 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, a (meth) acrylic resin can be particularly selected. 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 of the high molecular weight component in the release layer can be, for example, at least one functional group selected from the group consisting of an epoxy group, an alcoholic or phenolic hydroxyl group, and a carboxy group.

  For example, the (meth) acrylic resin having a crosslinkable functional group includes a monomer unit derived from a functional monomer such as (meth) acrylic acid glycidyl having an epoxy group and (meth) acrylic acid having a carboxy group. The (meth) acrylic resin having a crosslinkable functional group is, for example, a (meth) acrylic acid ester copolymer having an epoxy group, a (meth) acrylic rubber having an epoxy group, or a (meth) acrylic acid ester having a carboxy group. It may be at least one selected from the group consisting of a polymer and a (meth) acrylic rubber having a carboxy group. Among these, you may select the (meth) acrylic rubber which has an epoxy group or a carboxy group.

  30-85 mass%, 40-80 mass%, or 45-75 mass% may be sufficient as content of the high molecular weight component in a mold release layer with respect to the mass of a mold release layer. Thereby, the mold release layer which has the above adhesiveness (shear viscosity) before heat processing and the peelability after heat processing as mentioned above can be formed still more easily.

  With the release agent, the peelability of the release layer after the heat treatment can be controlled. In order to form a release layer (resin layer) having a predetermined 90 ° peel strength with respect to the resist layer as described above, the content of the release agent is 25 to 100 masses per 100 mass parts of the high molecular weight component. Part. When the content of the release agent is less than 25 parts by mass, the 90 ° peel strength at 25 ° C. with respect to the resist layer of the resin layer after the heat treatment tends to easily exceed 200 N / m. When the content of the release agent exceeds 100 parts by mass, the 90 ° peel strength at 175 ° C. of the resin layer after the heat treatment tends to be less than 2 N / m. From the same viewpoint, the content of the release agent may be 25 to 90 parts by mass or 25 to 80 parts by mass with respect to 100 parts by mass of the high molecular weight component.

  The manufacturing process of an electronic device generally includes heating at about 175 ° C. for the formation of a sealing layer and the like. From the viewpoint of realizing heat resistance against heat history at 175 ° C., the 5% weight reduction temperature of the release agent may be 175 ° C. or higher.

  The release agent may contain at least one selected from, for example, a silicone compound, a fluorine-containing compound, and a higher fatty acid. A silicone compound can be used from the viewpoint that it is inexpensive and has good peelability and is rich in variety. From the viewpoint of suppressing the generation of residues after peeling, one or more types of silicone compounds having a phenyl group, silicone compounds having a crosslinkable functional group, and silicone compounds having a functional group capable of interacting with a hydroxy group are separated. A mold can be selected. Silicone compounds having a phenyl group or a crosslinkable functional group have good compatibility with other components such as high molecular weight components. As a crosslinkable functional group which a silicone compound has, an epoxy group, a carboxy group, and a hydroxy group are mentioned, for example. Examples of the functional group capable of interacting with a hydroxy group include a hydroxy group, an amino group, a polyether group, and a urethane group. The hydroxy group is formed, for example, by reaction of an epoxy resin used as a thermosetting resin described later.

  Examples of commercially available silicone compounds that can be used as a release agent include SH3773M and SH550 manufactured by Toray Dow Corning Co., Ltd., KF105 and X-22-4741 manufactured by Shin-Etsu Chemical Co., Ltd., TA manufactured by Hitachi Chemical Polymer Co., Ltd. Series etc. are mentioned.

  The release layer may further contain (a3) a thermosetting resin as required. When the release layer contains a thermosetting resin, the shear viscosity of the release layer before the heat treatment can be designed to be lower, and the embedding property of the unevenness on the surface of the organic substrate can be improved. Further, since the thermosetting resin is a component that contributes to adhesiveness, it is also effective for controlling the adhesion to the organic substrate.

  In the present specification, the thermosetting resin means a low molecular compound having two or more crosslinkable functional groups that form a crosslinked structure by heating, self-polymerization, and / or reaction with a curing agent, and the molecular weight thereof is Usually, it is 8000 or less. The high modulus layer can also contain a thermosetting resin, but the release layer can contain the same or different thermosetting resin as the high modulus layer.

  From the viewpoint of realizing heat resistance at 175 ° C., the 5% weight reduction temperature of the thermosetting resin may be 175 ° C. or higher.

  The thermosetting resin in the release layer may contain at least one of an epoxy resin or a (meth) acryl monomer, for example.

  Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin (for example, EXA830-CRP manufactured by DIC Corporation) and bisphenol E type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. It may be at least one selected from a novolac type epoxy resin such as a type epoxy resin (for example, YDCN-700-10 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). These have good heat resistance.

  Examples of the (meth) acrylic monomer include polyfunctional aliphatic (meth) acrylates such as dipentaerythritol hexaacrylate (for example, A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) and urethane acrylates (for example, Shin-Nakamura Chemical Industry). At least one compound can be selected from the UA series manufactured by KK.

  The release layer may further contain a thermosetting resin curing agent. The curing agent is a compound that reacts with the thermosetting resin to form a crosslinked structure with the thermosetting resin. For example, an epoxy resin and a phenol resin as its curing agent can be combined. Examples of commercially available phenol resins 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. It is done.

  The release layer may contain a curing accelerator that functions as a catalyst for the curing reaction of the thermosetting resin from the viewpoint of realizing smooth curing of the thermosetting resin. In the case of a curing reaction of an epoxy resin and a phenol resin, a compound such as an amine compound or an imidazole compound can be used as a curing accelerator. Since excessive addition of the curing accelerator may impair the storage stability of the support member, the content of the curing accelerator is 0.01 to 3.0 mass with respect to 100 parts by mass of the high molecular weight component. Part.

  When the thermosetting resin contains a (meth) acrylic monomer, the release layer may further contain a radical polymerization initiator such as an organic peroxide or an organic azo compound. The content of the radical polymerization initiator may be, for example, 5 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer.

  The content of the thermosetting resin or the total content of the thermosetting resin and the curing agent may be 30 parts by mass or less with respect to 100 parts by mass of the high molecular weight component. By these content being 30 mass parts or less, the adhesiveness with respect to the organic substrate of the mold release layer before heat processing can be easily controlled to an appropriate range.

  The release layer may further contain an inorganic filler. The inorganic filler can contribute to the control of adhesion to the resist layer formed from the AUS308 of the release layer after the heat treatment, and the resin can contribute to the suppression of headings. Moreover, film formation can be facilitated by appropriately controlling the viscosity of the coating liquid for forming the release layer using an inorganic filler. The content of the inorganic filler in the release layer may be 10 parts by mass or less with respect to 100 parts by mass of the high molecular weight component. When the content of the inorganic filler is 10 parts by mass or less, it is possible to obtain good moldability of the release layer without excessively increasing the shear viscosity of the release layer before heat treatment and the adhesion to the resist layer. Can be obtained.

  The inorganic filler in the release layer may be at least one kind of particles selected from silica and alumina, for example. The maximum particle size of the inorganic filler may be equal to or less than the film thickness of the release layer. A component having a particle size exceeding the thickness of the release layer may be previously removed from the inorganic filler.

(B) High elastic modulus layer The high elastic modulus layer may contain (b1) a high molecular weight component having a crosslinkable functional group, (b2) a thermosetting resin, and (b3) an inorganic filler. Good. The high elastic modulus layer containing these combinations has a relatively high storage elastic modulus after heat treatment based on the crosslinking reaction of the high molecular weight component and the thermosetting resin, the blending of the inorganic filler, and the like. That is, the high elastic modulus layer in which the storage elastic modulus at 175 ° C. of the high elastic modulus layer after the heat treatment is higher than the storage elastic modulus at 175 ° C. of the release layer after the heat treatment. Can be easily formed. The high molecular weight component and the thermosetting resin in the high elastic modulus layer may be the same as or different from the high molecular weight component and the thermosetting resin in the release layer, respectively.

  The weight average molecular weight of the high molecular weight component in the high elastic modulus layer may be 200000 to 1100000. When the weight average molecular weight of the high molecular weight component is 200,000 or more, sufficient bulk strength can be expressed in the resin layer after the heat treatment, and excessive resin deformation and protrusion at high temperature and high pressure can be suppressed. When the weight average molecular weight of the high molecular weight component is 1100000 or less, the shear viscosity at 80 ° C. of the high elastic modulus layer before the heat treatment can be stably 20000 Pa · s or less. From the same viewpoint, the weight average molecular weight of the high molecular weight component may be 200000 to 1000000, 200000 to 950,000, or 200000 to 900000.

  The glass transition temperature (Tg) of the high molecular weight component in the high elastic modulus layer may be -50 to 50 ° C. When the Tg of the high molecular weight component is −50 ° C. or higher, the high elastic modulus layer is prevented from being excessively soft at room temperature, and good handleability is easily obtained. When the Tg of the high molecular weight component is 50 ° C. or less, the shear viscosity at 80 ° C. of the high elastic modulus layer before the heat treatment can be stably reduced to 20000 Pa · s or less. From the same viewpoint, the Tg of the high molecular weight component may be -30 to 40 ° C, or -20 to 30 ° C.

  The high molecular weight component in the high elastic modulus layer may contain a monomer unit having a crosslinkable functional group. The ratio of the monomer units may be 1 to 10% by mass 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, a high elastic modulus layer having good bulk strength is easily formed, and the high elastic modulus layer is elongated at the time of peeling, so that peeling becomes difficult. This can be suppressed. When this ratio is 10% by mass or less, an excessive increase in the shear viscosity of the high elastic modulus layer due to a crosslinking reaction during storage can be suppressed. From the same viewpoint, the ratio of the monomer unit having a crosslinkable functional group may be 2 to 9% by mass based on the mass of the high molecular weight component.

  The high molecular weight component in the high elastic modulus layer and the crosslinkable functional group thereof can be selected, for example, in the same manner as described for the high molecular weight component in the release layer. From the viewpoint that rapid reactivity with the thermosetting resin or its curing agent can be obtained, (meth) acrylic rubber having an epoxy group can be used.

  As the thermosetting resin of the high elastic modulus layer, the same resin as described above with respect to the thermosetting resin in the release layer can be selected.

  Specific examples of the epoxy resin that can be included as a thermosetting resin in the high elastic modulus layer include bisphenol A type epoxy resin, bisphenol F type epoxy resin (for example, EXA830-CRP manufactured by DIC Corporation), and bisphenol E type epoxy. Bifunctional epoxy resins such as resins, phenol novolac type epoxy resins and cresol novolak type epoxy resins (for example, YDCN-700-10 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and epoxy resins having a naphthalene skeleton (For example, NC-7000L manufactured by Nippon Kayaku Co., Ltd.).

  The high elastic modulus layer may further contain a curing agent of a thermosetting resin. For example, an epoxy resin and a phenol resin as its curing agent can be combined. Examples of commercially available phenol resins 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. It is done.

  The thermosetting resin (for example, epoxy resin) and / or the curing agent (for example, phenol resin) may include a component that is liquid at room temperature (25 ° C.) and has a softening point or a melting point of 85 ° C. or lower. Of the total content of 100 parts by mass of the thermosetting resin and the curing agent, the ratio of components having a liquid state at room temperature (25 ° C.) and a softening point or melting point of 85 ° C. or less may be 50 parts by mass or more. It may be 85 parts by mass or less. Thereby, the shear viscosity in 80 degreeC of the high elastic modulus layer before heat processing can be easily made into 20000 Pa.s or less. Moreover, the bulk strength of the high elastic modulus layer after the heat treatment can be improved, and deformation of the resin layer under high temperature and high pressure can be particularly remarkably suppressed.

  Even if the content of the thermosetting resin or the total content of the thermosetting resin and the curing agent in the high elastic modulus layer is 50 to 300 parts by mass with respect to 100 parts by mass of the high molecular weight component. Good. Thereby, the shear viscosity in 80 degreeC of the high elastic modulus layer before heat processing can be easily made into 20000 Pa.s or less. Moreover, the bulk strength of the high elastic modulus layer after the heat treatment can be improved, and deformation of the resin layer under high temperature and high pressure can be particularly remarkably suppressed. The excessively low viscosity of the varnish used for forming the high elastic modulus layer because the content of the thermosetting resin or the total content of the thermosetting resin and the curing agent is 300 parts by mass or less. The film formation can be suppressed and good film formability can be obtained. Furthermore, it is possible to prevent the high elastic modulus layer from becoming excessively soft at room temperature and to obtain good handleability. From the same viewpoint, the content of the thermosetting resin or the total content of the thermosetting resin and the curing agent may be 80 to 280 parts by mass or 100 to 260 parts by mass.

  The high elastic modulus layer may contain a curing accelerator that functions as a catalyst for the curing reaction of the thermosetting resin from the viewpoint of realizing smooth curing of the thermosetting resin. If the reactivity of the curing accelerator is too high, excessive curing proceeds in the heat drying for forming the high elastic modulus layer, which may cause an increase in shear viscosity before the heat treatment. Also, there is a tendency that deterioration with time is likely to be prominently caused. If the reactivity of the curing accelerator is too low, not only the curing of the high elastic modulus layer by heat treatment is delayed and the curing time becomes long, but also the degree of crosslinking after the heat treatment is insufficient, In some cases, deformation and protrusion of the resin layer are likely to occur. From these viewpoints, an imidazole compound having an imidazole ring can be selected as the curing accelerator. Examples of the imidazole compound include 1-cyanoethyl-2-phenylimidazole and 2-phenylimidazole.

  Excessive addition of the curing accelerator may cause excessive curing in heat drying for forming the high elastic modulus layer, which may cause an increase in shear viscosity before the heat treatment. Further, there is a tendency that deterioration with time is likely to be prominently caused. From such a viewpoint, the content of the curing accelerator in the high elastic modulus layer is 0.01 to 2.0 parts by mass, 0.1 to 1.5 parts by mass, or 100 parts by mass of the high molecular weight component. 0.2-1.0 mass part may be sufficient.

  When the high elastic modulus layer contains an inorganic filler, the viscosity of the varnish used for forming the high elastic modulus layer can be appropriately controlled to facilitate film formation. Moreover, the protrusion of the resin under high temperature and high pressure can be further suppressed. The content of the inorganic filler in the high elastic modulus layer may be 4 to 25 parts by mass with respect to 100 parts by mass of the high molecular weight component. When the content of the inorganic filler is 25 parts by mass or less, the shear viscosity at 80 ° C. of the high elastic modulus layer before the heat treatment can be easily suppressed to an appropriate range. From the same viewpoint, the content of the inorganic filler may be 4 to 22 parts by mass or 4 to 19 parts by mass with respect to 100 parts by mass of the high molecular weight component.

  The inorganic filler includes, for example, at least one kind of particles selected from the group consisting of 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 high elastic modulus layer. Considering the film formability of the high modulus layer, etc., 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. Among them, R972 manufactured by Nippon Aerosil Co., Ltd., which can be expected to have a small particle size and better film formability, can be selected.

Manufacturing method of support member The support member according to the present embodiment includes, for example, forming a release layer and a high elastic modulus layer, and forming a release layer, a high elastic modulus layer, and a resin film substrate. It can manufacture by the method of laminating | stacking in order.

  The release layer and the high elastic modulus layer are prepared by, for example, applying a varnish prepared by mixing and kneading the above-described composition containing each component in an organic solvent to a film for film formation, and then applying the organic solvent from the applied varnish. It can form by the method of removing. The film for film formation is usually removed when the support member is produced.

  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, for example, by heating at 60 to 200 ° C. for 0.1 to 90 minutes.

  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 film for film-forming, 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, a methylpentene film is mentioned.

  The preferred embodiment of the support member according to the present invention has been described above. However, the present invention is not necessarily limited to the above-described embodiment, and modifications may be made as appropriate without departing from the spirit of the present 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 support member>
(Examples 1-16 and Comparative Examples 1-5)
A composition composed of various raw materials having the product names and composition ratios (unit: parts by mass) shown in Tables 1 to 3 and a cyclohexanone are stirred and mixed to form a release layer-forming varnish and a highly elastic layer. The varnish was obtained. In order to increase the stirring efficiency, components other than acrylic rubber were first stirred and mixed, and finally acrylic rubber was added and stirred until each component became uniform.

  Next, each varnish obtained was filtered through a 100 mesh filter and vacuum degassed. The varnish after vacuum defoaming was applied on a polyethylene terephthalate (PET) film having a thickness of 38 μm subjected to a mold release treatment as a film for film formation. The applied varnish was dried by two-step heating at 90 ° C. for 5 minutes followed by 140 ° C. for 5 minutes. Thus, a 10 μm thick release layer and a 40 μm thick elastic modulus layer formed on the PET film were obtained.

  Next, the release layer and the high elastic modulus layer were respectively peeled from the PET film, and the release layer and the high elastic modulus layer were bonded together by heat laminating at 80 ° C. to obtain a resin layer. Subsequently, the resin film base material was bonded to the surface of the resin layer on the high elastic modulus layer side by heat lamination at 80 ° C. to obtain a support member having the resin film base material and the resin layer. The support member of each example had moderate rigidity and good transportability.

  The detail of each material in Tables 1-3 is shown below.

<Resin layer>
1. High molecular weight component having a crosslinkable functional group HTR-860P-3CSP (sample name, Teikoku Chemical Industry Co., Ltd., acrylic rubber having epoxy group, weight average molecular weight: 800,000, 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. )
HTR-280 (sample name, Teikoku Chemical Industry Co., Ltd., acrylic rubber having carboxyl group, weight average molecular weight: 900,000, ratio of monomer unit having carboxyl group: 8% by mass, Tg: -37 ° C.)
HTR prototype 91 (sample name, manufactured by Teikoku Chemical Industry Co., Ltd., acrylic rubber having epoxy group, weight average molecular weight: 800000, ratio of monomer unit having glycidyl group: 8% by mass, Tg: 18 ° C.)

2. Release agent TA31-209E (trade name, manufactured by Hitachi Chemical Co., Ltd., silicone-modified aminoalkyd resin, 5% weight reduction temperature: 233 ° C.)
・ SH3773M (trade name, manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil, 5% weight reduction temperature: 215 ° C.)
-SH550 (trade name, manufactured by Toray Dow Corning Co., Ltd., phenyl-modified silicone oil, 5% weight loss temperature: 329 ° C)

3. Thermosetting resin epoxy resin / EXA830-CRP (trade name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 155-163, liquid at room temperature, 5% weight loss temperature: 254 ° C.).
YDCN-700-10 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent: 210, softening point: 80 ° C., 5% weight loss temperature: 310 ° C.)
NC-7000L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 230, softening point: 88 ° C., 5% weight loss temperature: 330 ° C.)

(Meth) acrylic monomer / UA-160TM (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., urethane acrylate)
・ UA-4200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., urethane acrylate)

4). Curing agent for epoxy resin, Millex XLC-LL (trade name, manufactured by Mitsui Chemicals, phenol resin, hydroxyl group equivalent: 175, softening point: 77 ° C, 5% weight loss temperature: 380 ° C or higher)

5. Radical polymerization initiator, perbutyl D (trade name, manufactured by NOF Corporation, di-t-butyl peroxide)

6). Epoxy resin curing accelerator, Curesol 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl-2-phenylimidazole)

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

<Resin film substrate>
Polyethylene naphthalate (PEN) film Q81-38 (trade name, manufactured by Teijin DuPont Films, Inc., thickness: 38 μm, storage elastic modulus at 175 ° C .: 740 MPa)
Q83-50 (trade name, manufactured by Teijin DuPont Films, Inc., thickness: 50 μm, 175 ° C. storage elastic modulus: 730 MPa).
Q65-125 (trade name, manufactured by Teijin Ltd., thickness: 125 μm, storage elastic modulus at 175 ° C .: 750 MPa)

Polyimide film / 25SGA (trade name, manufactured by Ube Industries, Ltd., thickness: 25 μm, storage elastic modulus at 175 ° C .: 7100 MPa)

Polyethylene terephthalate (PET) film G2-50 (trade name, manufactured by Teijin DuPont Films, Inc., thickness: 50 μm, storage elastic modulus at 175 ° C .: 430 MPa)

<Evaluation of various physical properties>
Shear viscosity of release layer and higher elastic modulus layer, peel strength of resin layer, storage elastic modulus of resin layer and higher elastic modulus layer, embeddability of step on substrate surface, resin protrusion and resin film base during molding Evaluation of material thickness change, foaming / peeling during process, and tape peelability. Each evaluation method is as follows. The evaluation results are shown in Tables 4-6.

1. Shear viscosity of release layer and high elastic modulus layer before heat treatment The release layer or high elastic modulus layer formed on the PET film as the film for film formation was peeled from the PET film. A plurality of release layers or high elastic modulus layers were laminated by roll lamination at 80 ° C. to obtain a release layer laminate having a thickness of 160 μm and a high elastic modulus layer laminate. By punching them out to 10 mm square in the thickness direction, a test piece having a square main surface of 10 mm square and thickness of 160 μm was obtained. 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 test piece of a release layer or a high elastic modulus layer was set therein. Then, the shear viscosity was measured while applying a strain of 5% and increasing the temperature from 35 ° C. to 150 ° C. at a rate of temperature increase of 20 ° C./min. (Pa · s) was recorded.

2. Peel strength of resin layer An evaluation substrate (50 mm × 150 mm) having a resist layer formed on the entire surface from AUS308 (product name, manufactured by Taiyo Ink Manufacturing Co., Ltd.), which is a solder resist ink for a substrate, was prepared. A support member was attached to the resist layer of the evaluation substrate by heat lamination at 80 ° C. so that the release layer of the resin layer was on the resist layer side. Next, the bonded evaluation substrate and support member were heat-treated in an oven at 130 ° C. for 30 minutes and at 170 ° C. for 60 minutes in order, thereby obtaining a specimen for peel strength measurement. This test body has a configuration corresponding to the laminated body 100 of the support member 10 and the organic substrate 12 (evaluation substrate) shown in FIG. However, no electronic component is provided on the evaluation substrate of the test body. The test specimen was cut to a width of 10 mm, the test specimen was placed on a hot plate set at 25 ° C. or 175 ° C., and a peel test at a peel angle of 90 ° was performed at a peel speed of 50 mm / sec using a peel tester. . The peel strength at that time was recorded as the peel strength at 25 ° C. or 175 ° C.

3. Storage Elasticity Resin Layer A resin layer composed of a release layer having a thickness of 10 μm and a high elastic modulus layer having a thickness of 40 μm is cut into a width of 4 mm and a length of 30 mm, 60 minutes at 170 ° C. for 30 minutes in a 130 ° C. oven. A test piece for measurement was obtained by heat treatment under the sequential heating conditions for minutes. The obtained test piece was set in a dynamic viscoelastic device (product name: Rheogel-E4000, manufactured by UMB), a tensile load was applied, and the storage elastic modulus was measured at a frequency of 10 Hz and a heating rate of 3 ° C./min. The measured value at 175 ° C. was recorded.

High elastic modulus layer The high elastic modulus layer was peeled from the PET film. A plurality of high elastic modulus layers after peeling were laminated by roll lamination at 80 ° C. to obtain a laminate of high elastic modulus layers having a thickness of 160 μm. With respect to the obtained laminate, the same heat treatment as that for the resin layer and the measurement of the storage elastic modulus were performed. The measured storage modulus at 175 ° C. was recorded.

Resin Film Base A test piece having a width of 4 mm and a length of 30 mm was cut out from the resin film base. The test piece was set in a dynamic viscoelastic device (product name: manufactured by Rheogel-E4000 Co., Ltd. UMB), a tensile load was applied, the storage elastic modulus was measured at a frequency of 10 Hz, and a temperature increase rate of 3 ° C./min. The measured value at ° C was recorded.

4). Embedment of step on the substrate surface A resist layer formed from AUS308 (product name, manufactured by Taiyo Ink Manufacturing Co., Ltd.), which is a solder resist ink for substrates, is formed on the entire surface, and a step of 6 μm is formed on the surface of the resist layer. An evaluation substrate (50 mm × 150 mm) was prepared. The support member was attached to the resist layer of the evaluation substrate by heat lamination at 80 ° C. with the resin layer facing the resist layer. Subsequently, the interface part of the resin layer (release layer) and the evaluation substrate was observed with a microscope from the resin film substrate side to confirm the presence or absence of voids. The evaluation criteria for the step embeddability are as follows.
A: There are 20 or less voids of 100 μm or more.
B: More than 20 voids of 100 μm or more.

5. Resin protrusion during molding and change in thickness of resin film substrate A test body, which is a laminate of an evaluation substrate and a support member, was prepared in the same manner as in “2. Peel strength of resin layer”. Using a mold sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name “CEL-9750ZHF10), on the surface opposite to the support member of the evaluation substrate, the conditions of 175 ° C., 6.7 MPa, 90 seconds The sealing layer was formed by molding, and then the amount of resin protruding from the end of the evaluation substrate was confirmed.The degree of resin protrusion was evaluated according to the following criteria.
A: The amount of protrusion is 200 μm or less.
B: The amount of protrusion exceeds 200 μm.
Moreover, the cross section of the test body after sealing was grind | polished, and the thickness of the resin film base material was measured. The thickness after sealing was compared with the thickness of the resin film substrate used as the raw material, and the amount of change in the resin film substrate thickness was determined. The evaluation criteria regarding thickness change are as follows.
A: The thickness change amount is 10% or less.
B: The thickness change amount exceeds 10%.

6). Foaming / peeling during the process A sealing layer was formed on the evaluation substrate in the same manner as in “5. Resin protrusion during molding and change in thickness of resin film substrate”. The test body before and after sealing was observed from the resin film substrate side, and the area of the portion where foaming or peeling occurred was confirmed. The evaluation criteria for foaming and peeling are as follows.
A: The total area of foaming and peeling is 3% or less of the entire substrate.
B: The total area of foaming and peeling exceeds 3% of the whole substrate.

7). Peelability The substrate for evaluation was sealed in the same manner as in “5. Resin protrusion during molding and change in thickness of resin film substrate”. Thereafter, the support member was peeled off at 25 ° C. from the evaluation substrate. The support member was broken with the peeling, and the presence or absence of a resin residue on the evaluation substrate was visually confirmed. The evaluation criteria for tape peelability are as follows.
A: There is no breakage of the support member, and there is no resin residue on the substrate.
B: Breakage of the support member or resin residue on the substrate is observed.

  Evaluation results are shown in Tables 4-6. As is clear from these results, the peeling strength of the resin layer from the organic substrate after the heat treatment satisfies both requirements of 200 N / m or less at 25 ° C. and 2 N / m or more at 175 ° C. While securing sufficient peelability, foaming and peeling at the interface between the organic substrate and the support member during the manufacturing process of the electronic device can be reduced.

  In addition, the support members of Examples 1 to 14 in which the shear viscosity at 80 ° C. of the high elastic modulus layer before the heat treatment was 20000 Pa · s or less were particularly excellent in terms of step embedding. The support members of Examples 1 to 13 and 15 in which the storage elastic modulus at 175 ° C. of the resin layer after the heat treatment is 6 MPa or more, and the storage elastic modulus at 175 ° C. of the high elastic modulus layer after the heat treatment are 8 MPa or more. The resin was particularly excellent in terms of protrusion at high temperature and high pressure during molding.

  DESCRIPTION OF SYMBOLS 2 ... Resin film base material, 4 ... Resin layer, 6 ... Release layer, 8 ... High elastic modulus layer, 10 ... Support member, 12 ... Organic substrate, 14 ... Electronic component, 16 ... Sealing layer, 20 ... Electronics Apparatus, 100: a laminate of an organic substrate and a support member.

Claims (7)

A support member for an organic substrate for being temporarily attached to the organic substrate in the manufacture of an electronic device including the organic substrate,
The support member has a resin film base and a resin layer containing a thermosetting resin provided on one surface side of the resin film base,
Heating conditions in which the resin layer is heated in order of 30 minutes at 130 ° C. and 60 minutes at 170 ° C. in a state where the resin layer is attached to a resist layer formed from AUS (registered trademark) 308, which is a solder resist ink for substrates. A support member having a 90 ° peel strength with respect to the resist layer of the resin layer after the heat treatment is 200 N / m or less at 25 ° C. and 2 N / m or more at 175 ° C. when heat-treated.   The support member according to claim 1, wherein when the resin layer is heat-treated under the heating condition, a storage elastic modulus at 175 ° C of the resin layer after the heat treatment is 6 MPa or more. The resin layer is
(A) a release layer having a surface opposite to the resin film substrate of the resin layer as a main surface;
(B) including a high elastic modulus layer provided between the release layer and the resin film substrate;
The storage modulus at 175 ° C. of the high modulus layer after the heat treatment when the high modulus layer and the release layer are heat-treated under the heating conditions. The support member according to claim 1, wherein the support member is a layer having a storage elastic modulus at 175 ° C. higher than that of the release layer after the heat treatment. The release layer is
(A1) a high molecular weight component having a weight average molecular weight of 200000 to 1100000 and a glass transition temperature of −50 ° C. to 50 ° C. and having a crosslinkable functional group;
The support member according to claim 3, comprising (a2) a release agent. The high elastic modulus layer is
(B1) a high molecular weight component having a weight average molecular weight of 200000 to 1100000 and a glass transition temperature of −50 ° C. to 50 ° C. and having a crosslinkable functional group;
(B2) the thermosetting resin;
The support member according to claim 3 or 4, comprising (b3) an inorganic filler.   The support member as described in any one of Claims 3-5 whose shear viscosity in 80 degreeC of the said mold release layer and the said high elastic modulus layer is 20000 Pa * s or less.   The support member as described in any one of Claims 1-6 whose storage elastic modulus in 175 degreeC of the said resin film base material is 500 Mpa or more.

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