Resin film with support, laminate, printed wiring board, and semiconductor package

Abstract

To provide a resin film with a support, which prevents the resin film from being peeled off from the support, and to provide a laminate, a printed wiring board, and a semiconductor package obtained using the resin film with the support.SOLUTION: Provided is a resin film with a support, comprising: a support; and a resin film containing a resin composition disposed on one surface of the support. When analyzed with a surface and interfacial cutting analysis system, the horizontal force, which is measured at a vertical displacement of 15 μm from the surface of the resin film, is equal to or greater than 1.5 times the horizontal force measured at a vertical displacement of 5 μm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a support-attached resin film, a laminate, a printed wiring board, and a semiconductor package. [Background technology]

[0002] In electronic devices and communication devices, such as mobile communication devices such as mobile phones and their base station equipment, network infrastructure devices such as servers and routers, and large computers, the speed and capacity of the signals used are increasing year by year. In particular, it is expected that the amount of information processed will increase dramatically in next-generation communications, such as the fifth-generation mobile communication system (5G). For this reason, there is a need to further miniaturize printed wiring boards used in electronic devices and communication devices, and there is a demand, for example, to use resin films that do not contain aggregates such as glass cloth (see, for example, Patent Document 1) instead of prepregs. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-077847 Summary of the Invention [Problem to be solved by the invention]

[0004] The resin film itself does not contain aggregate and therefore has poor self-supporting properties. Therefore, the resin film is usually transported and handled with a support such as copper foil or polyethylene terephthalate (PET) attached. However, even in the case of a resin film with a support (hereinafter referred to as a resin film with a support), a part of the resin film may peel off from the support during transportation and handling, which reduces the yield.

[0005] In view of the current situation, an object of the present disclosure is to provide a resin film with a support in which the resin film is difficult to peel off from the support, and to provide a laminate, a printed wiring board, and a semiconductor package obtained using the resin film with a support. [Means for solving the problem]

[0006] As a result of investigations conducted by the present inventors to solve the above problems, they have found that the problems can be solved by the present embodiment described below. This embodiment relates to the following [1] to

[13] . [1] A resin film with a support, comprising: a support; and a resin film containing a resin composition provided on one surface of the support; A resin film with a support, wherein when analyzed with a surface and interface physical property analyzer, the horizontal force at a vertical displacement of 15 μm from the surface of the resin film is 1.5 times or more the horizontal force at a vertical displacement of 5 μm. [2] The support-attached resin film according to the above [1], wherein the thickness of the resin film is 20 μm or more. [3] The supported resin film according to the above [1] or [2], wherein the resin composition contains (A) a thermosetting resin. [4] The supported resin film according to the above [3], wherein the component (A) contains an (A1) maleimide resin. [5] The supported resin film according to the above [4], wherein the content of the component (A1) is 40 to 95 mass % based on the total amount of the component (A). [6] The supported resin film according to any one of the above [3] to [5], wherein the component (A) contains (A2) an epoxy resin having two or more oxyalkylene bonds. [7] The resin film with a support described in [6] above, wherein the component (A2) is an epoxy resin obtained by glycidyl etherifying a compound having a structure formed by an addition reaction of an alkylene oxide with a phenolic hydroxyl group of a phenol compound. [8] The supported resin film according to the above [6] or [7], wherein the content of the component (A2) is 5 to 40 mass % based on the total amount of the component (A). [9] The supported resin film according to any one of the above [1] to [8], wherein the resin composition contains (B) an inorganic filler.

[10] The supported resin film according to any one of the above [1] to [9], wherein the support is a plastic film, a metal foil or a release paper.

[11] A laminate comprising a cured product of the resin film in the supported resin film according to any one of [1] to

[10] above, and a metal foil.

[12] A printed wiring board having a cured product of the resin film in the support-attached resin film according to any one of [1] to

[10] above.

[13] A semiconductor package comprising the printed wiring board according to

[12] above and a semiconductor element. Effect of the Invention

[0007] According to the present disclosure, it is possible to provide a resin film with a support in which the resin film is difficult to peel off from the support, and to provide a laminate, a printed wiring board, and a semiconductor package obtained using the resin film with a support. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a simplified schematic diagram of a surface and interface characterization analyzer (SAICAS) used in this embodiment. [Diagram 2] FIG. 2 is a perspective view of a cutting blade of a surface and interface characterization apparatus (SAICAS) used in this embodiment. [Diagram 3] FIG. 2 is a side view of a cutting blade of a surface and interface characterization apparatus (SAICAS) used in this embodiment. [Figure 4] 2 is a photograph showing the appearance of the support-attached resin film obtained in Example 1 after transport. [Diagram 5] 1 is a photograph showing the appearance of the support-attached resin film obtained in Comparative Example 1 after transport. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the numerical ranges described in the present disclosure, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. In addition, the lower and upper limits of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range. In the expression of a numerical range "AA to BB", the numerical values ​​AA and BB at both ends are included in the numerical range as the lower and upper limits, respectively. In the present disclosure, for example, the expression "10 or more" means 10 and a numerical value exceeding 10, and the same applies when the numerical values ​​are different. Also, for example, the expression "10 or less" means 10 and a numerical value less than 10, and the same applies when the numerical values ​​are different.

[0010] Unless otherwise specified, each of the components and materials exemplified in the present disclosure may be used alone or in combination of two or more types. In the present disclosure, when a plurality of substances corresponding to each component are present in the resin composition, the content of each component in the resin composition means the total amount of the plurality of substances present in the resin composition, unless otherwise specified. In this disclosure, "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also considered to be solid content. Additionally, any combination of the descriptions in this disclosure is also included in this embodiment.

[0011] In the present disclosure, the number average molecular weight and the weight average molecular weight are values ​​measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

[0012] [Resin film with support] The support-attached resin film of the present embodiment is as follows. A resin film with a support, the resin film having a support and a resin film containing a resin composition provided on one side of the support, the horizontal force at a vertical displacement of 15 μm from the surface of the resin film being 1.5 times or more the horizontal force at a vertical displacement of 5 μm when analyzed with a surface and interface property analyzer.

[0013] The surface and interfacial property analysis device is sometimes called SAICAS (Surface and Interfacial Cutting Analysis System). SAICAS is a registered trademark. The surface and interfacial property analysis device is a device that cuts a sample (a resin film with a support in this embodiment) at an oblique angle by moving a cutting blade in two axial directions, horizontally and vertically, and can investigate the shear fracture strength in the shear process and the peel strength in the peel process from the horizontal force acting on the cutting blade and the vertical displacement of the cutting blade (see FIG. 1). In this embodiment, the investigation of the shear fracture strength in the shear process is used. The analysis using the surface and interface property analyzer can be started at any desired site on the resin film side of the supported resin film. A commercially available surface and interface property analysis device can be used, and SAICAS (e.g., DN-20, etc.) manufactured by Daipla Wintes Co., Ltd. can be used. Surface and interface property analyzers are generally used to measure solid materials such as paint films, metal deposition films, and plastic materials, but in this embodiment, the surface and interface property analyzer was used to measure a resin film in a B-stage state. Here, in this disclosure, B-stage refers to the B-stage defined in JIS K6900 (1994).

[0014] The cutting blade used in the surface and interface property analysis device is usually one having the shape shown in FIG. 2 and FIG. The width of the cutting edge is not particularly limited, but may be 0.1 to 5 mm, 0.5 to 3 mm, or 1 mm. The rake angle of the cutting edge (see FIG. 3) is not particularly limited, but is preferably 3 to 20 degrees, more preferably 5 to 15 degrees, and further preferably 10 degrees. The clearance angle of the cutting edge (see FIG. 3) is not particularly limited, but is preferably 3 to 20 degrees, more preferably 5 to 15 degrees, and further preferably 10 degrees. The material of the cutting blade is not particularly limited, but examples thereof include sintered alloy and single crystal diamond. In the measurement using a surface and interface physical property analyzer, the temperature of the cut site is not particularly limited, but is preferably 10 to 40°C, more preferably 20 to 30°C, and further preferably 20 to 25°C. In the measurement using the surface and interface physical property analyzer, cutting may be performed while maintaining a constant vertical load (vertical force) or while maintaining a constant speed (vertical speed and horizontal speed). The vertical speed is preferably 0.01 to 1 μm / sec, more preferably 0.05 to 0.5 μm / sec, and even more preferably 0.1 μm / sec. The horizontal speed is preferably 0.5 to 6 μm / sec, more preferably 1 to 4 μm / sec, and even more preferably 2 μm / sec. In the measurement using a surface and interface physical property analyzer, the shear angle is preferably 30 to 60 degrees, more preferably 35 to 55 degrees, and further preferably 40 to 50 degrees.

[0015] In the measurement using a surface and interface property analyzer, the shear fracture strength is calculated by the following formula (1).

[0016]

number

[0017] In formula (1), T is the shear fracture strength (MPa), and F H is the horizontal force (kN), W is the width of the cutting edge (m), d is the vertical displacement (m), and φ is the shear angle (deg).

[0018] When the resin film with a support of this embodiment is analyzed by a surface and interface physical property analyzer, the horizontal force at a vertical displacement of 15 μm from the surface of the resin film is 1.5 times or more the horizontal force at a vertical displacement of 5 μm, so that the resin film is less likely to peel off from the support. It is presumed that the reason for this effect is that shear fracture is less likely to occur in the resin film, and peeling due to shear fracture is suppressed. However, even if this presumption is incorrect, it does not affect the scope of the present disclosure. From the viewpoint of making the resin film difficult to peel off from the support, the horizontal force at a vertical displacement of 15 μm from the resin film surface is preferably 1.7 times or more, more preferably 2.0 times or more, even more preferably 2.2 times or more, and particularly preferably 2.4 times or more than the horizontal force at a vertical displacement of 5 μm. Although not particularly limited, the horizontal force at a vertical displacement of 15 μm from the resin film surface may be 8 times or less, 6 times or less, 5 times or less, 4 times or less, 3.5 times or less, or 3.2 times or less than the horizontal force at a vertical displacement of 5 μm. In other words, the horizontal force at a vertical displacement of 15 μm from the resin film surface may be 1.5 to 8 times the horizontal force at a vertical displacement of 5 μm.

[0019] In addition, the analysis using the surface and interface physical property analyzer is performed three times, and the average value is used to reduce measurement fluctuation. In other words, if the horizontal force at a vertical displacement of 5 μm in the first analysis is X1 and the horizontal force at a vertical displacement of 15 μm is Y1, the horizontal force at a vertical displacement of 5 μm in the second analysis is X2 and the horizontal force at a vertical displacement of 15 μm is Y2, and the horizontal force at a vertical displacement of 5 μm in the third analysis is X3 and the horizontal force at a vertical displacement of 15 μm is Y3, then the horizontal force X at a vertical displacement of 5 μm is (X1+X2+X3) / 3, and the horizontal force Y at a vertical displacement of 15 μm is (Y1+Y2+Y3) / 3, and Y / X is 1.5 or more.

[0020] Furthermore, when the resin film with a support of this embodiment is analyzed by a surface and interface property analyzer, it is preferable that the horizontal force at a vertical displacement of 10 μm from the resin film surface is 1.3 times or more than the horizontal force at a vertical displacement of 5 μm, since the resin film tends to be difficult to peel off from the support. From the same viewpoint, the horizontal force at a vertical displacement of 10 μm from the resin film surface is preferably 1.5 times or more, more preferably 1.7 times or more, than the horizontal force at a vertical displacement of 5 μm. Although not particularly limited, the horizontal force at a vertical displacement of 10 μm from the resin film surface may be 5 times or less, 4 times or less, 3 times or less, 2.5 times or less, 2.3 times or less, or 2.0 times or less than the horizontal force at a vertical displacement of 5 μm. In other words, the horizontal force at a vertical displacement of 10 μm from the resin film surface is preferably 1.3 to 5 times the horizontal force at a vertical displacement of 5 μm.

[0021] (Resin film) The resin film in the support-attached resin film of the present embodiment is a resin film containing a resin composition. The resin composition will be described later. The thickness of the resin film is not particularly limited, but is preferably 20 μm or more, more preferably 30 μm or more, even more preferably 40 μm or more, and even more preferably 50 μm or more; the upper limit is not particularly limited, but is preferably 1,000 μm or less, more preferably 700 μm or less, and even more preferably 500 μm or less, and may be 200 μm or less, 100 μm or less, or 80 μm or less. In other words, the thickness of the resin film may be 20 to 1,000 μm.

[0022] (Support) Examples of the support include a plastic film, a metal foil, a release paper, etc. Among these, a plastic film and a metal foil are preferred, and a metal foil is more preferred. Examples of the plastic film include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate films, polyimide films, etc. Among these, from the viewpoints of economy and ease of handling, polyester films are preferred, and polyethylene terephthalate films are more preferred. Examples of the metal of the metal foil include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements, and copper and aluminum are preferred, and copper is more preferred. In particular, when a copper foil is used as the support, the copper foil can be used as a conductor layer to form a circuit. In this case, the copper foil can be a rolled copper foil, an electrolytic copper foil, or the like. The copper foil can also be a copper foil with a carrier. The support may be one that has been subjected to a surface treatment such as a matte treatment, a corona treatment, etc. Furthermore, the support may be one that has been subjected to a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like. The thickness of the support is not particularly limited, but from the viewpoints of ease of handling and economic efficiency, it is preferably 10 to 150 μm, more preferably 20 to 100 μm, and even more preferably 30 to 70 μm.

[0023] The support of the supported resin film of the present embodiment preferably has an arithmetic mean roughness Ra of the surface on the resin film side of the support of 0.06 to 1.0 μm. When the arithmetic mean roughness Ra is equal to or greater than the lower limit, the cured product of the resin film has excellent adhesion to a conductor. From the same viewpoint as above, the arithmetic mean roughness Ra of the surface of the support on the resin film side is preferably 0.07 to 0.8 μm, more preferably 0.15 to 0.6 μm, and even more preferably 0.2 to 0.6 μm. The arithmetic mean roughness Ra of the support is not particularly limited, but can be measured using a surface roughness measuring device (manufactured by Kosaka Laboratory Co., Ltd., product name "Surfcorder SE3500") under conditions of a cutoff value of 0.8 mm and a measurement length of 8 mm.

[0024] The supported resin film of this embodiment is suitable as a supported resin film for forming an insulating layer of a printed wiring board such as a multilayer printed wiring board, or as a supported resin film for sealing a semiconductor in a semiconductor package.

[0025] <Method of manufacturing a resin film with a support> The method for producing the resin film with the support of the present embodiment is not particularly limited. For example, the resin film with the support of the present embodiment can be produced by applying a resin composition containing an organic solvent [hereinafter, the resin composition containing an organic solvent may be referred to as a "resin varnish"] to the support and then drying by heating.

[0026] As a coating device for coating the resin varnish, a coating device known to those skilled in the art can be used, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc. These coating devices may be appropriately selected depending on the thickness of the resin film to be formed. The drying conditions after the resin varnish is applied may be appropriately determined depending on the content, boiling point, etc. of the organic solvent, and are not particularly limited. For example, in the case of a resin varnish containing 40 to 60 mass % of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited, but from the viewpoints of productivity and appropriately bringing the resin composition into a B-stage, it is preferably 50 to 200°C, more preferably 80 to 150°C, and even more preferably 100 to 130°C. In addition, in the case of the above-mentioned resin varnish, the drying time is not particularly limited, but from the viewpoints of productivity and appropriately bringing the resin composition into a B-stage, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0027] (Resin composition) Next, the resin composition for forming the resin film will be described. The resin composition preferably contains a thermosetting resin (A). Here, in the present disclosure, the thermosetting resin (A) may be abbreviated to component (A), and other components may be abbreviated in the same manner.

[0028] <(A) Thermosetting resin> (A) Examples of thermosetting resins include epoxy resins, phenolic resins, maleimide resins, modified polyphenylene ether resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. The modified polyphenylene ether resin is preferably a polyphenylene ether resin having an ethylenically unsaturated bond-containing group at its terminal, more preferably a polyphenylene ether resin having an ethylenically unsaturated bond-containing group at both terminals. Examples of the ethylenically unsaturated bond-containing group include unsaturated aliphatic hydrocarbon groups such as vinyl groups, allyl groups, 1-methylallyl groups, isopropenyl groups, 2-butenyl groups, 3-butenyl groups, and styryl groups; and groups containing a heteroatom and an ethylenically unsaturated bond, such as maleimide groups and (meth)acryloyl groups. The (A) thermosetting resin may be used alone or in combination of two or more kinds.

[0029] (Maleimide resin) From the viewpoint of heat resistance and toughness, the (A) thermosetting resin preferably contains (A1) a maleimide resin. The (A1) component more preferably contains one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins, and more preferably is at least one selected from the group consisting of maleimide resins having two or more N-substituted maleimide groups and derivatives thereof. In the maleimide resin and its derivatives having two or more N-substituted maleimide groups, the nitrogen atoms of the multiple N-substituted maleimide groups are preferably bonded to each other via an organic group, which may include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, or a combination thereof, each of which may contain a heteroatom.

[0030] The maleimide resin having one or more N-substituted maleimide groups is not particularly limited, and examples thereof include aromatic maleimides having one N-substituted maleimide group bonded to an aromatic ring, such as N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, and N-benzylmaleimide; bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl aromatic bismaleimides having preferably two N-substituted maleimide groups bonded to an aromatic ring, such as 1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and indane ring-containing bismaleimide; aromatic polymaleimides having preferably three or more N-substituted maleimide groups bonded to an aromatic ring, such as polyphenylmethane maleimide and biphenyl aralkyl maleimide; and aliphatic maleimides such as N-dodecylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and pyrophosphate binder type long-chain alkyl bismaleimide. Among these, from the viewpoints of compatibility with other resins, heat resistance, low thermal expansion, and toughness, aromatic bismaleimides preferably having two N-substituted maleimide groups bonded to an aromatic ring are more preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is even more preferred.

[0031] Examples of the derivatives of maleimide resins include addition reaction products of maleimide resins having one or more (preferably two or more) N-substituted maleimide groups with amine compounds such as monoamine compounds and diamine compounds (hereinafter, these may be referred to as "modified maleimide compounds"). Examples of the monoamine compounds include monoamine compounds having an acidic substituent, such as o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Examples of the diamine compound include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4,4'-diaminodiphenyl)propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4' -diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, siloxane diamine, and the like. Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and siloxane diamine are preferred, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and siloxane diamine are more preferred. The monoamine compound and the diamine compound may each be used alone or in combination of two or more kinds. The component (A1) preferably contains an addition reaction product between a maleimide resin having two or more N-substituted maleimide groups and an amine compound, more preferably contains an addition reaction product between a maleimide resin having two or more N-substituted maleimide groups and a diamine compound, and even more preferably contains an addition reaction product between a maleimide resin having two or more N-substituted maleimide groups and a diamine compound including a siloxane diamine.

[0032] The weight average molecular weight of the component (A1) is not particularly limited, but from the standpoint of handleability and moldability, it is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0033] (Content of component (A1) in component (A)) The content of the (A1) component is not particularly limited, but is preferably 40 to 95 mass%, more preferably 50 to 95 mass%, and even more preferably 70 to 90 mass% based on the total amount of the (A) component. When the content of the (A1) component is equal to or more than the lower limit, compatibility with other resins, heat resistance, low thermal expansion, and mechanical properties tend to be good, and the effects of the present embodiment tend to be easily achieved. When the content of the (A1) component is equal to or less than the upper limit, it becomes easier to include other (A) components such as the (A2) component described below.

[0034] (Epoxy resin) Although a known epoxy resin can be used as the epoxy resin, it is preferable that the epoxy resin (A2) has two or more oxyalkylene bonds. In other words, the (A) component preferably contains the (A2) epoxy resin having two or more oxyalkylene bonds. When the (A) component contains the (A2) component, the resin film tends to be more difficult to peel off from the support. In addition, the present inventors have attempted to impart flexibility to the resin film by using, instead of the (A2) component, a rubber component such as an acrylic rubber, a phenoxy resin, or a styrene-based thermoplastic elastomer, or a low-molecular-weight epoxy resin such as a liquid epoxy resin (excluding epoxy resins having two or more oxyalkylene bonds), in order to obtain the same results as those of the (A2) component, but in this case, the effect obtained when the (A2) component is used was not manifested or was extremely small (for example, see Comparative Example 1). The number-average molecular weight of the low-molecular-weight epoxy resin is 1,000 or less, and may be 150 to 1,000 or 200 to 800. In addition, in the present disclosure, "liquid" means that the viscosity calculated by the following measurement method is 100,000 mPa·s or less. <Method of measuring viscosity> Equipment: E-type viscometer Cone rotor: 1°34'×R24 Temperature: 25℃ Sample volume: 1.0mL Rotation speed: 20 rpm

[0035] The component (A2) may be used alone or in combination of two or more kinds. The alkylene group constituting the oxyalkylene bond in the component (A2) preferably has 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably 2 or 3 carbon atoms, from the viewpoint of making the resin film difficult to peel off from the support. The alkylene group may or may not have a substituent. When the alkylene group has a substituent, the number of carbon atoms of the substituent is included in the number of carbon atoms of the alkylene group. The oxyalkylene bond is represented, for example, by the following general formula (A2-1).

[0036] [ka] (R a1 is an alkylene group having 2 to 5 carbon atoms.

[0037] R a1 Examples of the alkylene group having 2 to 5 carbon atoms represented by include an ethylene group, a propylene group, a butylene group, and a pentylene group. In the present disclosure, the alkylene group also includes an alkylidene group. Among these, an ethylene group and a propylene group are preferred from the viewpoint of making it difficult for the resin film to peel off from the support. From the same viewpoint, the oxyalkylene bond is preferably a bond represented by the following formula (A2-2) or the following formula (A2-3).

[0038] [ka]

[0039] The bond represented by the general formula (A2-2) can be formed by a ring-opening addition reaction of ethylene oxide, and the bond represented by the general formula (A2-3) can be formed by a ring-opening addition reaction of propylene oxide.

[0040] The number of oxyalkylene bonds contained in the component (A2) is 2 or more, preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 6, from the viewpoint of making the resin film difficult to peel off from the support.

[0041] The number of epoxy groups contained in the component (A2) is preferably 2 or more, more preferably 2 to 5, even more preferably 2 or 3, and particularly preferably 2, from the viewpoint of making the resin film difficult to peel off from the support.

[0042] From the viewpoint of making the resin film difficult to peel off from the support, the component (A2) is preferably an epoxy resin obtained by glycidyl etherifying a compound having a structure formed by addition reaction of an alkylene oxide (preferably ethylene oxide or propylene oxide) with a phenolic hydroxyl group of a phenol compound. As the phenol compound, for example, a bisphenol compound such as bisphenol A, bisphenol F, or bisphenol S is preferable, and bisphenol A is more preferable.

[0043] From the viewpoint of making it easier to suppress warping of the resin-coated metal foil, the component (A2) is preferably a compound represented by the following general formula (A2-4). [ka] (In the formula, R a1 is R in the general formula (A2-1). a1 is the same as R a2 and R a3 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a1 is a single bond, or a divalent organic group represented by an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, or a keto group. a1 and n a2 Each of m independently represents an integer of 0 to 4. a1 and m a2 Each independently is a number from 1 to 10. a1 and Y a2 each independently represents a group containing an epoxy group.

[0044] R in the above general formula (A2-4) a1 A preferred embodiment of the formula (A2-1) is a1 This is the same as the preferred embodiment of In the above general formula (A2-4), m a1 and m a2 are each independently a number from 1 to 10, preferably a number from 1 to 6, and more preferably a number from 1 to 3.

[0045] R in the above general formula (A2-4) a2 and R a3 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc.; an alkenyl group having 2 to 5 carbon atoms; an alkynyl group having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the above general formula (A2-4), n a1 and n a2 each independently represents an integer of 0 to 4. n a1 or n a2 If is an integer equal to or greater than 2, multiple R a1 R a2 They may be the same or different from each other.

[0046] Y in the above general formula (A2-4) a1 and Y a2 An example of the group containing an epoxy group represented by the formula (I) is a glycidyl group.

[0047] (Content of component (A2) in component (A)) The content of the (A2) component is not particularly limited, but is preferably 5 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 30 mass%, based on the total amount of the (A) component. When the content of the (A2) component is equal to or more than the lower limit, the resin film tends to be more difficult to peel off from the support, and the effect of the present embodiment tends to be more pronounced.

[0048] Examples of the epoxy resin other than the component (A2) include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; alicyclic epoxy resins such as dicyclopentadiene type epoxy resins; aliphatic chain epoxy resins; novolac type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, phenol aralkyl novolac type epoxy resins, and biphenyl aralkyl novolac type epoxy resins; stilbene type epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthol novolac type epoxy resins and naphthol aralkyl type epoxy resins; biphenyl type epoxy resins; xylylene type epoxy resins; dihydroanthracene type epoxy resins, etc. Among these, the epoxy resin other than the component (A2) is preferably a novolac type epoxy resin, and more preferably a biphenyl aralkyl novolac type epoxy resin or a phenol novolac type epoxy resin. The epoxy resin may be any of a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, and a glycidyl ester type epoxy resin, with a glycidyl ether type epoxy resin being preferred. The epoxy resins other than the component (A2) are epoxy resins that do not have two or more oxyalkylene bonds.

[0049] ((A) Thermosetting resin content) In the resin composition, the content of the (A) component (however, when two or more types of (A) components are contained, the content is the total content thereof) is not particularly limited, but is preferably 5 to 60 mass %, more preferably 10 to 55 mass %, even more preferably 15 to 50 mass %, and particularly preferably 20 to 40 mass %, based on the total solid content in the resin composition of this embodiment. When the content of the (A) component is equal to or greater than the lower limit, the heat resistance, moldability, processability, and adhesion to the conductor tend to be improved. When the content of the (A) thermosetting resin is equal to or less than the upper limit, the dielectric properties (dielectric constant and dielectric loss tangent) tend to be improved.

[0050] <(B) Inorganic filler> The resin composition preferably further contains an inorganic filler as component (B). By containing component (B), the resin composition tends to easily obtain excellent low thermal expansion, heat resistance, and flame retardancy. As component (B), one type may be used alone, or two or more types may be used in combination. Examples of the (B) component include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), molybdic acid compounds such as zinc molybdate, talc, aluminum borate, silicon carbide, etc. Among these, from the viewpoints of low thermal expansion, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred. Examples of silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water, etc. Dry method silica further includes crushed silica, fumed silica, fused silica, etc. From the standpoint of improving dispersibility and adhesion to the organic component, the component (B) may be surface-treated with a surface treatment agent such as a silane coupling agent.

[0051] The average particle size of component (B) is not particularly limited, but from the viewpoint of dispersibility and fine wiring ability of component (B), it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm. In the present disclosure, the average particle size refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%. The average particle size of component (B) can be measured using a particle size distribution measuring device using a laser diffraction scattering method. The shape of component (B) may be spherical, crushed, etc., with spherical being preferred.

[0052] ((B) Inorganic filler content) When the resin composition contains the (B) component, the content of the (B) component is not particularly limited, but is preferably 20 to 95 mass %, more preferably 40 to 85 mass %, and even more preferably 50 to 75 mass %, based on the total solid content of the resin composition. When the content of component (B) is equal to or greater than the lower limit, the low thermal expansion, heat resistance, and flame retardancy tend to be improved. When the content of component (B) is equal to or less than the upper limit, the moldability and adhesion to the conductor tend to be improved.

[0053] <(C) Curing accelerator> The resin composition preferably further contains a curing accelerator as component (C). By containing component (C), the resin composition has improved curability, and as a result, excellent heat resistance and adhesion to the conductor tend to be easily obtained. The component (C) may be used alone or in combination of two or more.

[0054] Examples of the (C) component include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organometallic salts, acid catalysts, organic peroxides, etc. In the present disclosure, imidazole-based curing accelerators are not classified as amine-based curing accelerators. Examples of the amine-based curing accelerator include amine compounds having primary to tertiary amines, such as triethylamine, pyridine, tributylamine, dicyandiamide, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; and quaternary ammonium compounds. Examples of the imidazole-based curing accelerator include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole). Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine; and quaternary phosphonium compounds such as an addition product of p-benzoquinone and tri-n-butylphosphine. The organic metal salts include carboxylates of manganese, cobalt, zinc, etc. The acid catalyst includes p-toluenesulfonic acid and the like. Examples of organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-di(t-butylperoxy)diisopropylbenzene. Among these, from the viewpoint of obtaining heat resistance, adhesion to a conductor, elastic modulus, and glass transition temperature, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferred, and phosphorus-based curing accelerators are more preferred.

[0055] ((C) Content of hardening accelerator) When the resin composition contains the (C) component, the content of the (C) component is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) thermosetting resin. When the content of component (C) is equal to or greater than the lower limit, the curing acceleration effect tends to be good, and when the content of component (C) is equal to or less than the upper limit, the storage stability tends to be good.

[0056] <Other ingredients> The resin composition may further contain, as necessary, one or more optional components selected from the group consisting of resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, and other additives. Each of the optional components may be used alone or in combination of two or more. When the resin composition contains the optional components, their contents are not particularly limited, and may be, relative to 100 parts by mass of component (A), 0.01 parts by mass or more, 0.1 parts by mass or more, 0.5 parts by mass or more, or 30 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less. Furthermore, the resin composition of the present embodiment may not contain the optional components, depending on the desired performance.

[0057] <Organic solvent> From the viewpoint of facilitating handling and production of a resin film, the resin composition may be a varnish-like resin composition containing an organic solvent. Examples of the organic solvent include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethylsulfoxide; and ester-based solvents such as γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

[0058] When the resin composition contains an organic solvent, its content is not particularly limited, but the solid content of the resin composition is preferably 30 to 90 mass%, more preferably 40 to 80 mass%, and even more preferably 50 to 70 mass%. If the content of the organic solvent is within the above range, the resin composition becomes easy to handle, and the production of a resin film having a desired thickness tends to be even easier.

[0059] [Laminate] The laminate of the present embodiment is a laminate having a metal foil and a cured product of the resin film in the supported resin film of the present embodiment. The laminate of this embodiment can be produced, for example, by peeling the support from one sheet of the supported resin film of this embodiment, and then arranging a metal foil on one or both sides, or by peeling the support from a laminate obtained by stacking two or more sheets of the supported resin film of this embodiment, and then arranging a metal foil on one or both sides, and then molding under heat and pressure. When the support is a metal foil, the process of peeling the support and then arranging the metal foil can be omitted. In the laminate of this embodiment, the resin film is C-staged. The metal of the metal foil is as described above regarding the metal foil as the support. The method for carrying out the hot-press molding is not particularly limited, but may be, for example, under conditions of 100 to 300° C., 0.2 to 10 MPa, and 0.1 to 5 hours. In addition, the hot-press molding may be carried out by using a vacuum press or the like to maintain a vacuum state for 0.5 to 5 hours.

[0060] [Printed wiring board] The printed wiring board of the present embodiment is a printed wiring board having a cured resin film in a resin film with a support. The printed wiring board of this embodiment can be manufactured by performing a circuit formation process such as drilling, metal plating, and etching of metal foil by a known method using one or more selected from the group consisting of the resin film with support of this embodiment and the laminate of this embodiment. In addition, a multilayer printed wiring board can also be manufactured by performing a multilayer adhesive process as necessary. In the printed wiring board of this embodiment, the resin film of this embodiment is C-staged.

[0061] [Semiconductor package] The semiconductor package of the present embodiment is a semiconductor package having the printed wiring board of the present embodiment and a semiconductor element. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board of the present embodiment. EXAMPLES

[0062] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0063] (Method of measuring weight average molecular weight (Mw)) The weight average molecular weight was calculated by gel permeation chromatography (GPC) from a calibration curve using standard polystyrene. The calibration curve was approximated by a third order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) (manufactured by Tosoh Corporation, product name). The measurement conditions for GPC are shown below. [GPC measurement conditions] Equipment: High-speed GPC equipment HLC-8320GPC Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation] Column: Guard column: TSK Guardcolumn SuperHZ-L + Column: TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all product names manufactured by Tosoh Corporation) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10mg / 5mL Injection volume: 25μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0064] (Analysis method using Surface and Interface Properties Analysis System (SAICAS)) The resin film with support produced in each example was analyzed using the equipment and cutting conditions below. The horizontal force at a vertical displacement of 5 μm from the surface of the resin film, the horizontal force at a vertical displacement of 10 μm from the surface of the resin film, and the horizontal force at a vertical displacement of 15 μm from the surface of the resin film were measured three times and the average value was calculated. (Device) "SAICAS DN-20" (manufactured by Daipla Wintes Co., Ltd.) (Cutting conditions) Cutting edge width: 1mm Cutting edge rake angle (see Figure 3): 10 degrees Cutting edge clearance angle (see Figure 3): 10 degrees Shear angle: 45 degrees Cutting edge material: Single crystal diamond Temperature of cutting area: 25℃ Horizontal speed: 2μm / sec

[0065] Production Example 1: Production of maleimide resin derivative (component (A1)) In a 5L reaction vessel equipped with a thermometer, a stirrer, and a water content meter with a reflux condenser, capable of heating and cooling, 100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 5.6 parts by mass of a silicone compound (primary amino group equivalent weight 750g / mol) having primary amino groups at both ends, 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were added and reacted for 2 hours under reflux. This was concentrated at the reflux temperature for 3 hours to produce a solution of maleimide resin derivative (I) (weight average molecular weight: about 2,700) with a solid content concentration of 65% by mass.

[0066] Example 1, Comparative Example 1 (1. Preparation of Resin Composition) A resin composition having a solid content concentration of 50 mass % was prepared by blending each component shown in Table 1 together with methyl isobutyl ketone in the amounts shown in Table 1, and then stirring and mixing while heating at 25° C. In Table 1, the unit of the blending amount of each component is parts by mass, and in the case of a solution or dispersion, it means parts by mass converted into solid content. (2. Production of Resin Film with Support) The resin composition obtained in each example was applied to the M side (matte side) of a 18 μm-thick low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-VLP-18") in a thickness such that the thickness of the resin film after drying would be 60 μm. The resin composition was then heated and dried at 105° C. for 5 minutes to bring it into a B-stage state, thereby producing a resin film with a support. The obtained resin film with a support was analyzed using a surface and interface physical property analyzer according to the above-mentioned method. The results are shown in Table 1. The obtained resin film with a support was cut into a size of 250 mm x 250 mm, and the appearance after being carried by hand is shown in Figure 4 (Example 1) and Figure 5 (Comparative Example 1).

[0067] [Table 1]

[0068] The details of each component shown in Table 1 are as follows. [Component (A)] (A1) Maleimide resin: Derivative of the maleimide resin (I) produced in Production Example 1 (A2) Epoxy resin having two or more oxyalkylene bonds: Propylene oxide-modified bisphenol A diglycidyl ether: A compound represented by the following formula (A2-5): [ka] (In the formula, m 1 and m 2 is a number between 1 and 2.) Other epoxy resins: Phenol novolac type epoxy resins (liquid epoxy resins, not containing oxyalkylene bonds)

[0069] [(B) Component] Inorganic filler: spherical silica, average particle size 0.5μm

[0070] [(C) component] Curing accelerator: p-benzoquinone and tri-n-butylphosphine adduct (phosphorus-based curing accelerator)

[0071] As can be seen from Table 1, in Example 1, where the horizontal force at a vertical displacement of 15 μm from the resin film surface was 1.5 times or more that at a vertical displacement of 5 μm in the analysis by the surface and interface physical property analyzer, the resin film of the supported resin film did not peel off after transportation. Also, no cracks occurred in the resin film. On the other hand, in Comparative Example 1, where the horizontal force at a vertical displacement of 15 μm from the resin film surface was less than 1.5 times that at a vertical displacement of 5 μm in the analysis using a surface and interface physical property analyzer, the resin film peeled off from the supported resin film after transport, even though the resin film contained a liquid epoxy resin to improve flexibility. Also, as can be seen from Figure 5, cracks occurred in the resin film in Comparative Example 1.

Claims

1. A resin film with a support, the resin film having a support and a resin film containing a resin composition provided on one surface of the support, A resin film with a support, wherein when analyzed with a surface and interface physical property analyzer, the horizontal force at a vertical displacement of 15 μm from the surface of the resin film is 1.5 times or more larger than the horizontal force at a vertical displacement of 5 μm.

2. The support-attached resin film according to claim 1 , wherein the resin film has a thickness of 20 μm or more.

3. The supported resin film according to claim 1 , wherein the resin composition contains (A) a thermosetting resin.

4. The support-attached resin film according to claim 3 , wherein the component (A) comprises a maleimide resin (A1).

5. 5. The supported resin film according to claim 4, wherein the content of the component (A1) is 40 to 95% by mass based on the total amount of the component (A).

6. 4. The supported resin film according to claim 3, wherein the component (A) comprises (A2) an epoxy resin having two or more oxyalkylene bonds.

7. The resin film with a support according to claim 6, wherein the component (A2) is an epoxy resin obtained by glycidyl etherifying a compound having a structure formed by an addition reaction of an alkylene oxide with a phenolic hydroxyl group of a phenol compound.

8. 7. The supported resin film according to claim 6, wherein the content of the component (A2) is 5 to 40% by mass based on the total amount of the component (A).

9. The supported resin film according to claim 1 , wherein the resin composition contains (B) an inorganic filler.

10. The supported resin film according to claim 1 , wherein the support is a plastic film, a metal foil or a release paper.

11. A laminate comprising the cured resin film in the supported resin film according to claim 1 and a metal foil.

12. A printed wiring board comprising the cured resin film in the support-attached resin film according to claim 1.

13. A semiconductor package comprising the printed wiring board according to claim 12 and a semiconductor element.

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