Laminate

Abstract

A laminate provided with a first member, a film-like adhesive and a second member in this order, the film-like adhesive joining the first member and the second member, the film-like adhesive comprising a thermosetting resin composition containing a filler, the film-like adhesive having a single-layer structure having a first surface and a second surface, the film-like adhesive has not only a region near the first surface but also a region in which the content of the filler decreases from the second surface side toward the first surface side.

Description

Technical Field

[0001] The present invention relates to a laminated body. Background Art

[0002] In recent years, a technology has become known for laminating components such as metal sheets using film-like adhesives to form laminates for heat dissipation or electrical conductivity in electronic devices. Conventional adhesives struggle to bond electronic components and metal sheets with sufficient bonding strength. Therefore, to improve bonding strength, the use of film-like adhesives made from thermosetting adhesive compositions is being studied (for example, see Patent Document 1).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-292908 Summary of the Invention

[0004] However, conventional film adhesives can sometimes cause warping in laminates due to differences in thermal expansion coefficients between components or uneven temperature distribution caused by heat generation. Therefore, an object of the present invention is to provide a laminate that can reduce warping.

[0005] One aspect of the present invention relates to the following [1] to [8].

[0006] [1] A laminate comprising a first member, a film-like adhesive, and a second member in this order, wherein:

[0007] The film adhesive bonds the first component to the second component.

[0008] The film adhesive is composed of a thermosetting resin composition containing a filler and has a single-layer structure having a first surface and a second surface.

[0009] The film adhesive has a region that is near the first surface and a region in which the content of the filler decreases from the second surface side toward the first surface side.

[0010] [2] A laminate comprising a first member, a film-like adhesive, and a second member in this order, wherein:

[0011] The film adhesive bonds the first component to the second component.

[0012] The film adhesive is composed of a thermosetting resin composition containing a filler and has a single-layer structure having a first surface and a second surface.

[0013] When the film adhesive is heated and cured, the thermally cured film adhesive has a region near the first surface and a region where the filler content decreases from the second surface side toward the first surface side.

[0014] [3] A laminate comprising a first member, an adhesive layer, and a second member in this order, wherein:

[0015] The adhesive layer bonds the first component to the second component,

[0016] The adhesive layer is a resin layer formed by curing at least a portion of a thermosetting resin composition containing a filler, and has a single-layer structure having a first surface and a second surface.

[0017] The adhesive layer has a region that is near the first surface and a region where the content of the filler decreases from the second surface side toward the first surface side.

[0018] [4] The laminate according to [1] or [2], wherein

[0019] The ratio of the thickness of the region to the entire thickness of the film adhesive is 25% or less.

[0020] [5] The laminate according to [3], wherein

[0021] The ratio of the thickness of the region to the entire thickness of the adhesive layer is 25% or less.

[0022] [6] The laminate according to any one of [1] to [5], wherein

[0023] The thickness of the region is 2 μm or less.

[0024] [7] The laminate according to any one of [1] to [6], wherein

[0025] The region is located at a position shallower than a position at a depth of 2 μm from the first surface.

[0026] [8] The laminate according to any one of [1] to [7], wherein

[0027] The content of the filler is 3 to 55% by mass based on the total mass of the resin composition.

[0028] [9] The laminate according to any one of [1] to [8], wherein

[0029] The resin composition contains acrylic rubber,

[0030] The content of the acrylic rubber is 50 to 85% by mass based on the total mass of the resin composition.

[0031]

[10] The laminate according to any one of [1] to [9], wherein

[0032] The first component is made of at least one selected from the group consisting of metal, glass, resin and ceramics,

[0033] The second member is made of at least one selected from the group consisting of metal, glass, resin, and ceramics.

[0034] Effects of the Invention

[0035] According to the present invention, a laminated body capable of reducing warping can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a cross-sectional view schematically showing one embodiment of the laminated body according to the present invention.

[0037] Figure 2 It is schematically represented Figure 1 A cross-sectional view of the film adhesive in the laminate shown.

[0038] Figure 3 It is a cross-sectional view schematically showing another embodiment of the film-like adhesive.

[0039] Figure 4 It schematically indicates that Figure 1 sectional view of an example of an adhesive film of the film-like adhesive shown. Detailed description

[0040] The following describes embodiments of the present invention with appropriate reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including steps, etc.) are not required unless otherwise indicated. The sizes of the constituent elements in the various figures are conceptual, and the relative sizes of the constituent elements are not limited to the relationships shown in the various figures.

[0041] The numerical values ​​and their ranges in this specification do not limit the present invention. In this specification, the numerical range expressed by "~" indicates a range that includes the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges recorded in stages in this specification, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. Moreover, in the numerical ranges recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the examples. In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl, (meth)acrylic copolymer, etc.

[0042] <Laminated body>

[0043] Figure 1 1 is a cross-sectional view schematically showing a laminate according to the present embodiment. The laminate 10 shown in the figure includes a first member 11, a film adhesive 1, and a second member 12 in this order. The film adhesive 1 joins the first member 11 and the second member 12 together.

[0044] Film adhesives

[0045] Figure 2 It is schematically represented Figure 1 A cross-sectional view of a film adhesive in the laminate shown. The film adhesive 1 has a single-layer structure, and the single-layer structure is composed of a resin composition having thermosetting properties and containing a filler. The thickness of the film adhesive 1 may be, for example, 50 μm or less, or may be 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. If the thickness of the film adhesive 1 is 50 μm or less, there is a tendency that the ratio of the region where the filler content is reduced relative to the thickness of the film adhesive increases, and thus it is easy to obtain the effect of the present invention. There is no particular restriction on the lower limit of the thickness of the film adhesive 1, and it is, for example, 2 μm or more. If the thickness of the film adhesive 1 is 2 μm or more, there is a tendency that it is easy to maintain adhesion to the component.

[0046] The film adhesive 1 has a region R1 (in the vicinity of the first surface F1) where the filler content decreases from the second surface F2 side toward the first surface F1 side. Figure 2 In the enlarged view shown, the arrows indicate the thickness of the region.) At this time, the film adhesive 1 may be before or after curing.

[0047] Region R1 is composed of a plurality of fillers 1f and resin components. In region R1, the filler content can be reduced continuously or in stages. In the case where the filler content of region R1 near the first surface F1 is relatively low, in other words, near the first surface F1, a region with a relatively high content of the resin component (resin-rich region) is locally formed in the thickness direction, and on the other hand, a continuous expansion can be formed in the surface direction. It can be inferred that region R1 is denser and softer in the surface direction than other regions, so it can relieve stress, thereby reducing the warping of the laminate. The first surface F1 can be the surface on the side of the first component 11 or the surface on the side of the second component 12.

[0048] Region R1 varies depending on the thickness of the film adhesive 1, but is located shallower than a depth of 2 μm from the first surface F1. In other words, "near the first surface F1" in this embodiment refers to a region shallower than a depth of 2 μm from the first surface F1. It suffices to have region R1 near the first surface F1; for example, a region with a high filler content may exist locally on the first surface F1.

[0049] The existence and thickness of region R1 can be confirmed, for example, by measuring the wear rate by making a slurry containing abrasive particles collide with the first surface F1 at high speed, or by measuring it based on a rigid pendulum-type physical property tester. In particular, the method of measuring the wear rate by making a slurry containing abrasive particles collide with each other at high speed can sufficiently reduce the influence of heat on the film adhesive 1. The existence and thickness of region R1 can also be confirmed after the film adhesive 1 is heated and cured. Specifically, a film adhesive after heat curing and a film adhesive near the first surface F1 after heat curing are prepared, the crystallization of ATR is changed, the penetration depth is changed and measured, and thus the composition difference between the two can be grasped. In addition, the existence and thickness of region R1 can also be confirmed by observing the cross section of the laminate 10.

[0050] To further reduce warping of the laminate, the thickness of region R1 can be 0.1 μm or greater, 0.3 μm or greater, 0.5 μm or greater, 0.8 μm or greater, or 1 μm or greater. To further enhance the mechanical strength of the laminate, the thickness of region R1 can be 2 μm or less, 1.5 μm or less, or 1 μm or less. The thickness of region R1 can be adjusted by adjusting the wind speed and drying temperature during formation of the film adhesive 1.

[0051] From the perspective of further reducing warping of the laminate, the ratio of the thickness of region R1 to the overall thickness of the film adhesive 1 may be 3% or more, 4% or more, or 5% or more. From the perspective of further improving the mechanical strength of the laminate, the ratio of the thickness of region R1 to the overall thickness of the film adhesive 1 may be 25% or less, 20% or less, or 15% or less.

[0052] like Figure 3 As shown, the film adhesive may form a region R2 similar to the region R1 near the second surface F2. Figure 3 The film adhesive 1A shown further has a region R2 near the second surface F2, in which the filler content decreases as it moves from the first surface F1 side toward the second surface F2 side. It has the same structure as the film adhesive 1 except that the region R2 is located at a position shallower than a position 2 μm deep from the second surface F2. In other words, "near the second surface F2" refers to a region shallower than a position 2 μm deep from the second surface F2. It is sufficient for the region R2 to exist near the second surface F2. For example, a region with a high filler content may exist locally on the second surface F2. The thickness of the region R2 can be effectively adjusted by adjusting the wind speed and drying temperature when the film adhesive 1 is formed. Furthermore, it can be adjusted by changing the support film with which the film adhesive 1 contacts during drying. The thickness of the region R2 and the ratio of the thickness of the region R2 to the overall thickness of the film adhesive 1 can be within the same range as that of the region R1 described above.

[0053] From the perspective of further reducing warping of the laminate, the total thickness of regions R1 and R2 may be 0.1 μm or greater, 0.3 μm or greater, 0.5 μm or greater, 0.8 μm or greater, 1 μm or greater, 1.2 μm or greater, or 1.4 μm or greater. From the perspective of further improving the mechanical strength of the laminate, the total thickness of regions R1 and R2 may be 4 μm or less, 3 μm or less, 2 μm or less, or 1.5 μm or less.

[0054] From the perspective of further reducing warping of the laminate, the ratio of the total thickness of the regions R1 and R2 to the overall thickness of the film adhesive 1 may be 6% or more, 7% or more, or 8% or more. From the perspective of further improving the mechanical strength of the laminate, the ratio of the total thickness of the regions R1 and R2 to the overall thickness of the film adhesive 1 may be 45% or less, 40% or less, or 35% or less.

[0055] The film adhesive 1 is composed of an adhesive composition containing (A) a thermosetting resin component and (B) a filler. The film adhesive 1 can be in a semi-cured (B-stage) or cured (C-stage) state. In one embodiment, the (A) thermosetting resin component can include (A1) a thermosetting resin, (A2) a curing agent, and (A3) an elastomer.

[0056] When the film-like adhesive 1 is in a solidified (C stage) state, at least a portion of the film-like adhesive 1 is solidified, or all of the film-like adhesive 1 is solidified. When the film-like adhesive 1 is in a solidified (C stage) state, the laminate comprises a first component, an adhesive layer, and a second component in sequence. That is, another embodiment of the present invention is a laminate comprising a first component, an adhesive layer, and a second component in sequence, wherein the adhesive layer joins the first component to the second component, the adhesive layer is a resin layer solidified from at least a portion of a thermosetting resin composition containing a filler, and is a single-layer structure having a first surface and a second surface, the adhesive layer having both an area near the first surface and an area in which the content of the filler decreases as it moves from the second surface side toward the first surface side. In addition, in the adhesive layer, since the film-like adhesive is a solidified material, the film-like adhesive can be replaced with an adhesive in the description of the structure of the adhesive layer described above.

[0057] (A1) Ingredients: Thermosetting resin

[0058] From the viewpoint of adhesion, (A1) component can be epoxy resin.Epoxy resin can be used without particular limitation as long as it is a resin having an epoxy group in the molecule.As epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, containing triazine skeleton epoxy resin, containing fluorene skeleton epoxy resin, trisphenol methane type epoxy resin, biphenyl type epoxy resin, xylene type epoxy resin, biphenyl aralkyl (biphenyl aralkyl) type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols, diglycidyl ether compounds of the polycyclic aromatics such as anthracene can be listed.They can be used alone or in combination of two or more. Among them, from the viewpoint of film viscosity, flexibility, etc., the component (A1) may be a cresol novolac epoxy resin, a phenol novolac epoxy resin, a bisphenol F epoxy resin, or a bisphenol A epoxy resin.

[0059] The epoxy equivalent of the epoxy resin is not particularly limited and may be 90 to 300 g / eq or 110 to 290 g / eq. If the epoxy equivalent of the epoxy resin is within this range, the bulk strength of the film adhesive tends to be maintained while ensuring fluidity.

[0060] (A2) Component: Curing agent

[0061] (A2) component can be the phenolic resin that can become the curing agent of epoxy resin.As long as phenolic resin has phenolic hydroxyl group in molecule, then can use without particular restriction.As phenolic resin, for example can list phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxy naphthalene and formaldehyde etc. with aldehyde group compound condensation or co-condensation and novolac type phenolic resin obtained under acidic catalyst, by phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalene diol, phenol novolac, phenol and / or naphthols and dimethoxy-p-xylene or bis(methoxymethyl) biphenyl synthesis phenol aralkyl resin, naphthol aralkyl resin etc..They can be used alone 1 kind or also can be used in combination of 2 or more. The phenolic resin may be a phenol novolac type phenolic resin or a naphthol aralkyl resin.

[0062] The hydroxyl equivalent weight of the phenolic resin may be 70 g / eq or greater, or 70 to 300 g / eq. A hydroxyl equivalent weight of 70 g / eq or greater tends to further improve the storage modulus of the film, while a hydroxyl equivalent weight of 300 g / eq or less can prevent problems caused by foaming, degassing, and the like.

[0063] From the perspective of curability, the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenolic resin (epoxy equivalent of the epoxy resin / hydroxyl equivalent of the phenolic resin) can be 0.30 / 0.70 to 0.70 / 0.30, 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45. When this equivalent ratio is 0.30 / 0.70 or higher, there is a tendency to obtain more sufficient curability. When this equivalent ratio is 0.70 / 0.30 or lower, it is possible to prevent the viscosity from becoming too high, and more sufficient fluidity can be obtained.

[0064] The total content of components (A1) and (A2) can be 5 to 50 parts by mass, 10 to 40 parts by mass, or 15 to 30 parts by mass relative to 100 parts by mass of the total mass of component (A). If the total content of components (A1) and (A2) is 5 parts by mass or more, the elastic modulus tends to increase due to crosslinking. If the total content of components (A1) and (A2) is 50 parts by mass or less, the film handling properties tend to be maintained.

[0065] (A3) Ingredient: Elastomer

[0066] Component (A3) may be an acrylic rubber having as its main component a structural unit derived from a (meth)acrylate ester. The content of the structural unit derived from a (meth)acrylate ester in component (A3) may be, for example, 70% by mass or greater, 80% by mass or greater, or 90% by mass or greater, based on the total amount of the structural units. The acrylic rubber may contain structural units derived from a (meth)acrylate ester having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, or a carboxyl group.

[0067] The glass transition temperature (Tg) of the (A3) component can be -50 to 50°C or -30 to 30°C. If the Tg of the (A3) component is -50°C or above, there is a tendency to prevent the softness of the adhesive from becoming too high. As a result, the film adhesive is easily cut during wafer cutting, and burrs can be prevented. If the Tg of the (A3) component is 50°C or below, there is a tendency to suppress the reduction in the softness of the adhesive. As a result, when the film adhesive is attached to the wafer, there is a tendency to easily fill the pores. In addition, debris during cutting caused by a reduction in the adhesion of the wafer can be prevented. Here, the glass transition temperature (Tg) refers to a value measured using a DSC (differential scanning calorimeter) (for example, Thermo Plus 2, manufactured by Rigaku Corporation).

[0068] The weight average molecular weight (Mw) of component (A3) may be 100,000 to 3,000,000 or 200,000 to 2,000,000. If the Mw of component (A3) is within such a range, film formation, film strength, flexibility, viscosity, etc. can be appropriately controlled, and reflowability is excellent, which can improve embedding properties. Here, Mw refers to a value measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.

[0069] As a commercial item of (A3) component, SG-P3 improved product and SG-80H (both are manufactured by Nagase ChemteX Corporation) are mentioned, for example.

[0070] The content of component (A3) can be 50 to 95 parts by mass, 60 to 90 parts by mass, or 70 to 85 parts by mass relative to 100 parts by mass of the total mass of component (A). When component (A3) is an acrylic rubber, the content of the acrylic rubber can be, for example, 50 to 85% by mass, 55 to 80% by mass, or 60 to 80% by mass, based on the total mass of the adhesive composition. When this content is 50% by mass or greater, the formation of region R1 is facilitated. On the other hand, when it is 85% by mass or less, the workability during the manufacture of the film adhesive 1 is easily maintained.

[0071] In another embodiment, the thermosetting resin component (A) may comprise an elastomer having crosslinkable functional groups such as epoxy groups, alcoholic or phenolic hydroxyl groups, or carboxyl groups, and a curing agent capable of reacting with the crosslinkable functional groups. Examples of combinations of an elastomer having crosslinkable functional groups and a curing agent capable of reacting with the crosslinkable functional groups include combinations of epoxy-containing acrylic rubber and phenolic resin.

[0072] (B) ingredient: filler

[0073] (B) component can be any one of an inorganic filler and an organic filler. As an inorganic filler, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, silicon dioxide, etc. can be mentioned. They can be used alone or in combination of two or more. Among them, from the viewpoint of adjusting the melt viscosity, (B) component can be silicon dioxide. As organic fillers, carbon, rubber-based fillers, silicone-based microparticles, polyamide microparticles, polyimide microparticles, etc. can be listed. The shape of (B) component is not particularly limited and can be spherical.

[0074] From the viewpoint of fluidity, the average particle size of the component (B) may be 0.01 to 1 μm, 0.01 to 0.8 μm, or 0.03 to 0.5 μm. Here, the average particle size refers to a value calculated from the BET specific surface area.

[0075] The content of component (B) can be 0.1 to 50 parts by mass, 0.1 to 30 parts by mass, or 0.1 to 20 parts by mass relative to 100 parts by mass of the total mass of component (A). The content of component (B) can be, for example, 3 to 55% by mass, 5 to 50% by mass, or 7 to 40% by mass, based on the total mass of the adhesive composition. A content of 3% by mass or greater can achieve the effect of maintaining the mechanical strength of the film adhesive 1, while a content of 55% by mass or less can achieve the effect of maintaining the good appearance of the film adhesive 1.

[0076] The film-like adhesive (adhesive composition) may further contain (C) a coupling agent, (D) a curing accelerator, and the like.

[0077] (C) Component: Coupling agent

[0078] (C) component can be a silane coupling agent. Examples of the silane coupling agent include γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane. These can be used alone or in combination of two or more.

[0079] (D) Component: Curing Accelerator

[0080] (D) component is not particularly limited, and commonly used components can be used. As (D) component, for example, imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. can be mentioned. They can be used alone or in combination of two or more. Among them, from the viewpoint of reactivity, (D) component can be imidazoles and derivatives thereof. As imidazoles, for example, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, etc. can be mentioned. They can be used alone or in combination of two or more.

[0081] The film adhesive 1 may further contain other components. Examples of such other components include leveling agents, pigments, ion trapping agents, and antioxidants. The content of component (C), component (D), and other components may be 0 to 30 parts by mass relative to 100 parts by mass of the total mass of component (A).

[0082] The film-like adhesive 1 can be formed by applying an adhesive composition to a support film. When a varnish of the adhesive composition (adhesive varnish) is used, the film-like adhesive 1 can be obtained by mixing component (A) and component (B), and other components as needed, in a solvent, mixing or kneading the mixture to prepare the adhesive varnish, applying the adhesive varnish to the support film 5, and removing the solvent by drying. Figure 4 The adhesive sheet 100 shown is composed of a support film 5 and a film-like adhesive 1 provided on the surface of the support film 5 .

[0083] When forming a film adhesive 1 from a coating of adhesive varnish, wind is applied to the surface of the coating to remove the solvent through drying, thereby forming a region R1 near the first surface F1. The wind speed flowing parallel to the upper surface of the coating is, for example, 3 to 20 m / s. A speed of 3 m / s or higher promotes the drying of component (A) on the surface of the coating to which the wind is applied, facilitating the formation of a region R1 having a sufficient thickness near the first surface F1 of the film adhesive 1. A speed of 20 m / s or lower facilitates the maintenance of the coating surface's appearance.

[0084] The drying temperature of the adhesive varnish is, for example, 25 to 150° C., or 50 to 145° C. A drying temperature of 50° C. or higher facilitates maintaining productivity, while a drying temperature of 150° C. or lower facilitates suppressing appearance defects.

[0085] The support film 5 is not particularly limited as long as it can withstand the aforementioned heat drying. Examples include polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyethylene naphthalate film, and polymethylpentene film. The support film 5 may be a multilayer film composed of two or more materials, or may be surface-treated with a release agent such as a silicone or silica-based release agent. The thickness of the support film 5 may be, for example, 10 to 200 μm or 20 to 170 μm.

[0086] Mixing or kneading uses general stirrer, crusher, three-roll mill, ball mill and other dispersion machines, and can suitably combine them to carry out.As long as the solvent for preparing adhesive varnish can dissolve, knead or disperse each component evenly, then there is no restriction, can use conventionally known solvent.As such solvent, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, toluene, xylene etc. can be enumerated.From the viewpoint that drying speed is fast, price is cheap, solvent can be methyl ethyl ketone, cyclohexanone etc.As the method for adhesive varnish being coated on support film, can use conventionally known method, for example, can enumerate blade coating method, roller coating method, spray coating method, gravure coating method, rod coating method and curtain coating method etc.

[0087] The surface tension of the adhesive varnish is, for example, 27 to 44 mN / m, 28 to 40 mN / m, or 28 to 38 mN / m. This value within the above range facilitates the production of a film with a good appearance and maintains ease of production workability. The surface tension of the adhesive varnish refers to the value measured by the hanging drop method under windless conditions at room temperature of 22 to 28°C and a humidity of 40 to 60%. The surface tension of the adhesive varnish can be adjusted, for example, by adding a leveling agent to the adhesive varnish.

[0088] <First Part, Second Part>

[0089] Examples of materials constituting the first member 11 and the second member 12 include metal, glass, resin, and ceramic. Specifically, the first member 11 may be composed of at least one selected from the group consisting of metal, glass, resin, and ceramic, and the second member 12 may be composed of at least one selected from the group consisting of metal, glass, resin, and ceramic.

[0090] Examples of metals include iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum. These metals may also be alloys. Examples of resins include glass epoxy resins, phenolic resins, melamine resins, cyanate resins, and bismaleimide resins. Examples of ceramics include aluminum oxide, zirconium oxide, silicon carbide, silicon nitride, silicon carbide, silicon nitride, ferrite, and boron nitride.

[0091] The first member 11 and the second member 12 may be made of the same material or different materials. If the hardness of the first member 11 differs from the hardness of the second member 12, the first surface F1 of the film adhesive 1 may be the surface on the harder member side to reduce warping of the laminate 10. In this specification, "hardness" refers to the Mohs hardness.

[0092] The shapes of the first member 11 and the second member 12 are not particularly limited, and may be, for example, film-shaped. When the first member 11 and the second member 12 are film-shaped, the thickness of each of the first member 11 and the second member 12 may be independently 20 to 2500 μm. Example

[0093] Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0094] (Examples 1 to 3)

[0095] [Production of film adhesive]

[0096] <Preparation of adhesive varnish>

[0097] The acrylic rubber solution shown in Table 1 was used as the adhesive varnish. The numerical values ​​related to the composition shown in Table 1 refer to parts by mass of the solid content of the acrylic rubber solution.

[0098] (A1) Epoxy resin

[0099] N-500P-10 (product name, manufactured by DIC Corporation, o-cresol novolac-type epoxy resin, epoxy equivalent: 203 g / eq)

[0100] (A2) Curing agent (phenolic resin)

[0101] MEH-7800M (product name, manufactured by Meiwa Chemical Industry Co., Ltd., phenol novolac-type phenolic resin, hydroxyl equivalent: 175 g / eq, softening point: 61-90°C)

[0102] SG-P3 Improved Product 1 (product name, manufactured by Nagase ChemteX Corporation)

[0103] (B) Inorganic fillers

[0104] R972 (product name, manufactured by NIPPON AEROSIL CO., LTD., silica particles, average particle size: 0.016 μm)

[0105] (C) Coupling agent

[0106] Z-6119 (product name, manufactured by Dow Toray Co., Ltd., 3-ureidopropyltriethoxysilane)

[0107] A-189 (product name, manufactured by Nippon Unicar Company Limited, γ-mercaptopropyltrimethoxysilane)

[0108] (D) Curing accelerator

[0109] 2PZ-CN (product name, manufactured by SHIKOKU CHEMICALS CORPORATION, 1-cyanoethyl-2-phenylimidazole)

[0110] <Production of film adhesive>

[0111] The adhesive varnish of the composition shown in Table 1 was filtered through a 100-mesh filter and vacuum degassed. The surface tension (hanging drop method) of the obtained adhesive varnish was 36 mN / m. A polyethylene terephthalate (PET) film having a thickness of 38 μm and subjected to demolding treatment was prepared as a substrate film, and the adhesive varnish after vacuum degassed was applied to the PET film. The amount of adhesive varnish applied was adjusted so that the thickness after drying became 10 μm. A wind having a flow rate of 3 m / s or more was circulated in parallel with the upper surface of the applied adhesive varnish, and dried at the temperature shown in Table 1, thereby obtaining a film-like adhesive in a B-stage state.

[0112] [Thickness of the area]

[0113] The film adhesive was heated at 170°C for 3 hours to cure. The cured film adhesive was then fixed to the sample stage of an atomic force microscope (SPM400, manufactured by Hitachi High-Tech Corporation). A cantilever (manufactured by Hitachi High-Tech Corporation, product name SI-DF-40, made of Si, with a spring constant of 40 N / m and a tip curvature radius of 8 nm) was placed on the cantilever holder and pushed into the film adhesive from the surface F1 (or F2) within the working range of a scanner set in the thickness direction of the film adhesive to obtain a force curve. The amount of push was set to be greater than the thickness of region R1 (or R2) and less than the working range of the scanner. Based on the force curve of the area where the cantilever was pushed into the sample, Hertz contact theory was used to convert it into a curve representing the relationship between the elastic modulus and the distance from the surface F1 (or F2) (the depth of the cantilever's push). At this time, the cantilever's spring constant was calibrated to monitor its condition and confirm that no significant wear or deterioration was found. The distance from surface F1 (or F2) at which the obtained curve reaches saturation is read as the thickness of region R1 (or R2). This measurement is repeated 20 times, and after eliminating obvious abnormalities, the average value of the combined thickness of regions R1 and R2 is calculated. The average value of the combined thickness of regions R1 and R2 is shown in Table 1 as the region thickness.

[0114] [Changes in warpage]

[0115] On a glass epoxy resin substrate (74mm×80mm×105μm), 40 semiconductor chips (4mm×12mm×30μm) were attached via the film adhesive prepared in each embodiment at 120°C, 0.1MPa, and 1 second to obtain a laminate. Then, the laminate was heated in a heating furnace. The heating of the laminate was carried out as follows: after heating from 25°C to 90°C over 5 minutes, it was kept at 90°C for 5 minutes, after heating from 90°C to 140°C over 2 minutes, it was kept at 140°C for 35 minutes, and then cooled from 140°C to 80°C over 10 minutes. The warping amount of the laminate before and after heating in the heating furnace was measured using the shadow moiré method, and the change in the warping amount was measured. The measurement results are shown in Table 1.

[0116] Table 1

[0117]

[0118] Explanation of symbols

[0119] 1, 1A - film adhesive, 5 - support film, 10 - laminate, 11 - first component, 12 - second component, F1 - first surface, F2 - second surface, R1, R2 - regions.

Claims

1. A laminate comprising a first member, a film-like adhesive, and a second member in this order, wherein: The film adhesive bonds the first component to the second component. The film adhesive is composed of a thermosetting resin composition containing a filler and has a single-layer structure having a first surface and a second surface. The film adhesive has a region that is near the first surface and a region in which the content of the filler decreases from the second surface side toward the first surface side.

2. A laminate comprising a first member, a film-like adhesive, and a second member in this order, wherein: The film adhesive bonds the first component to the second component. The film adhesive is composed of a thermosetting resin composition containing a filler and has a single-layer structure having a first surface and a second surface. When the film adhesive is heated and cured, the thermally cured film adhesive has a region near the first surface and a region where the filler content decreases from the second surface side toward the first surface side.

3. A laminate comprising a first member, an adhesive layer, and a second member in this order, wherein: The adhesive layer bonds the first component to the second component, The adhesive layer is a resin layer formed by curing at least a portion of a thermosetting resin composition containing a filler, and has a single-layer structure having a first surface and a second surface. The adhesive layer has a region that is near the first surface and a region where the content of the filler decreases from the second surface side toward the first surface side.

4. The laminate according to claim 1 or 2, wherein The ratio of the thickness of the region to the entire thickness of the film adhesive is 25% or less.

5. The laminate according to claim 3, wherein The ratio of the thickness of the region to the entire thickness of the adhesive layer is 25% or less.

6. The laminate according to any one of claims 1 to 3, wherein The thickness of the region is 2 μm or less.

7. The laminate according to any one of claims 1 to 3, wherein The region is located at a position shallower than a position at a depth of 2 μm from the first surface.

8. The laminate according to any one of claims 1 to 3, wherein The content of the filler is 3 to 55% by mass based on the total mass of the resin composition.

9. The laminate according to any one of claims 1 to 3, wherein The resin composition contains acrylic rubber, The content of the acrylic rubber is 50 to 85% by mass based on the total mass of the resin composition.

10. The laminate according to any one of claims 1 to 3, wherein The first component is made of at least one selected from the group consisting of metal, glass, resin and ceramics, The second member is made of at least one selected from the group consisting of metal, glass, resin, and ceramics.

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