Conductive pillar module precursor for semiconductor manufacturing, conductive pillar module for semiconductor manufacturing, semiconductor or semiconductor precursor, and method for manufacturing same

Abstract

In the prior art, it is not possible to obtain a conductive pillar module for semiconductor manufacturing without using photolithography, which can be used for secondary wiring of a substrate of a flip chip package or for forming a reconfiguration layer (RDL) in a rear chip (RDL-first) package. The invention provides a conductive pillar module precursor for semiconductor manufacturing, a semiconductor or a semiconductor precursor, and a method for manufacturing the same, the conductive pillar module precursor having a structure in which a conductive pillar member is supported by a sheet-shaped cured resin and having sufficient adhesion to a substrate, stress relaxation properties, and durability.

Description

Technical Field

[0001] The invention relates to a conductive column module precursor for semiconductor manufacturing, a conductive column module for semiconductor manufacturing, a semiconductor or a semiconductor precursor and a manufacturing method thereof. Background Art

[0002] In semiconductor manufacturing, flip chip packaging technology that uses solder bumps to connect chips and substrates has been used for about 30 years. In recent years, the miniaturization of semiconductor devices has continued to advance, and the miniaturization of their substrate structures has become increasingly significant, but the use of solder bumps is limited by the pitch. Therefore, in the miniaturization below 100μm, the use of copper pillar wiring can achieve a finer pitch with high I / O (input and output) density.

[0003] Patent Document 1 discloses a method for producing copper pillar wiring using flip chip packaging technology and resist technology.

[0004] However, the method described in Patent Document 1 requires photolithography technology for forming and peeling off a photoresist layer, and has a problem of increasing the production time and the number of steps, resulting in high costs.

[0005] Therefore, it is necessary to shorten the manufacturing process and time and reduce the cost of semiconductor manufacturing by a manufacturing method that is simpler than the conventional technology.

[0006] In addition, the resin used in the conductive column module needs to have good adhesion to metal and a coating that can be sandblasted. In addition, in flip-chip packaging, durability after reflow is required, and in fan-out packaging, which is a manufacturing method for other semiconductors, adaptability to the next process corresponding to the application, such as applicability to the RDL (reconfiguration layer) formation process, is required. Therefore, the resin used in the conductive column module is required to have adhesion to various substrates, stress relaxation, and durability.

[0007] On the other hand, curable silicone compositions can be cured to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water resistance, and transparency, and are therefore used in a wide range of industrial fields. In particular, cured products of curable silicone compositions are generally less likely to change color than other organic materials, and their physical properties are less likely to deteriorate over time, so they are also suitable as sealants for semiconductor devices.

[0008] The present applicant proposed a hot-melt curable granular silicone composition and a reactive silicone composition for molding in Patent Documents 2 and 3. These silicone compositions contain a large amount of inorganic filler to achieve their properties, and have a high melt viscosity.

[0009] When sealing a substrate that has become smaller and smaller with the miniaturization of semiconductor devices in recent years, low viscosity is required for sealing. In addition, as semiconductor devices have become larger in area in recent years, film-shaped or sheet-shaped sealants tend to be preferred as sealants, and the same is true for the resin composition used in the conductive column module. The above-mentioned hot-melt curable granular silicone composition and reactive silicone composition for molding with relatively high melt viscosity are not suitable as sheet-shaped resin compositions used in conductive column modules.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Publication No. 2017-17300

[0013] Patent Document 2: International Publication No. 2016 / 136243

[0014] Patent Document 3: International Publication No. 2019 / 078140 Summary of the invention

[0015] Problems to be solved by the invention

[0016] Therefore, in the prior art, it is impossible to obtain a conductive pillar module for semiconductor manufacturing that does not use photolithography technology and can be used for secondary wiring of a substrate of a flip chip package or for forming a redistribution layer (RDL) in a post-chip (RDLfirst) package.

[0017] The present invention is completed to solve the above-mentioned problems, and its purpose is to provide a conductive column module precursor for semiconductor manufacturing, a conductive column module for semiconductor manufacturing, a semiconductor or a semiconductor precursor and a manufacturing method thereof, wherein the conductive column module precursor for semiconductor manufacturing has sufficient adhesion to the substrate, stress relaxation and durability.

[0018] Solutions for solving problems

[0019] The present inventors have conducted intensive research on the above problems and have achieved the present invention. That is, the object of the present invention is achieved by a conductive column module precursor for semiconductor manufacturing having a structure in which a conductive column member is supported by a sheet-like cured resin.

[0020] Preferably, in the conductive column module precursor for semiconductor manufacturing of the present invention, the sheet-shaped resin cured material is a silicone cured material, and the conductive column component is a conductive column with a short diameter of 50 to 500 μm and a long diameter of 50 to 500 μm.

[0021] Preferably, in the conductive column module precursor for semiconductor manufacturing of the present invention, the sheet-shaped resin cured material is an organic silicon cured material obtained by curing through a hydrosilylation reaction, and the conductive column component is a cylindrical copper column with a diameter of 50 to 500 μm and a height of 50 to 2000 μm.

[0022] The present invention also relates to a conductive column module for semiconductor manufacturing, which has a structure in which a conductive column component is supported by a sheet-like cured resin material, and the conductive column component is exposed from both sides of the sheet-like cured resin material.

[0023] The present invention also relates to a semiconductor or a semiconductor precursor having the following structure: at least a portion of the conductive column component of the conductive column module for semiconductor manufacturing of the present invention is welded on a substrate, and the conductive column exposed from the surface on the opposite side of the sheet-like resin cured material is bonded to the semiconductor chip directly or via a conductive layer (reconfiguration layer).

[0024] Preferably, the semiconductor or semiconductor precursor of the present invention has a structure in which the gaps among the substrate, the semiconductor chip, and the conductive pillar member are filled with a molded underfill material.

[0025] The present invention also relates to a method for manufacturing a semiconductor or a semiconductor precursor, the method comprising the step of bonding a conductive pillar component exposed from the conductive pillar module precursor for semiconductor manufacturing of the present invention to a semiconductor chip or a substrate.

[0026] The present invention also relates to a method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention, the manufacturing method comprising the following steps (I) to (IV):

[0027] Step (I): a step of disposing a conductive column component on a molded component;

[0028] Step (II): a step of disposing at least one curable resin composition and an optional release liner on the conductive column member;

[0029] Step (III): a step of curing the curable resin composition into a sheet form by one or more curing mechanisms selected from heating and high-energy ray irradiation; and

[0030] Step (IV): a step of separating the conductive pillar module precursor for semiconductor manufacturing from the molded part after removing any of the release liners.

[0031] Preferably, the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is characterized in that the curable resin composition used in step (II) is a sheet of a curable resin composition having heat-melting properties, and is a step in which the sheet of the curable resin composition is arranged on the conductive column component and then the sheet of the curable resin composition is heated and melted, thereby at least a portion of the conductive column is supported inside the sheet of the curable resin composition.

[0032] Preferably, the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is characterized in that the curable resin composition used in step (II) is a hydrosilylation reaction curable silicone sheet having heat-melting properties, and the step is as follows: after the hydrosilylation reaction curable silicone sheet is arranged on the conductive column component, the hydrosilylation reaction curable silicone sheet is heated and melted, thereby at least a portion of the conductive column component is supported inside the sheet of the curable resin composition, and

[0033] Step (III) is a step of curing the hydrosilylation reaction-curable silicone sheet into a sheet form by one or more curing mechanisms selected from heating and high-energy ray irradiation.

[0034] Preferably, the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention further comprises the following step after the above-mentioned step (IV): after bonding any exposed conductive column component to a semiconductor chip or substrate, the conductive column is exposed on both sides of the sheet-like resin cured material by shaving off at least one side of the sheet-like resin cured material.

[0035] The present invention also relates to a method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention, the manufacturing method comprising the following steps (I') to (V'):

[0036] Step (I'): a step of disposing a conductive column component on a first molding component;

[0037] Step (II'): a step of disposing a second molding component on the conductive column component;

[0038] Step (III'): a step of filling the gap between the conductive column member, the first molding member, and the second molding member with a curable resin composition;

[0039] Step (IV'): a step of curing the curable resin composition into a sheet by one or more curing mechanisms selected from heating and high-energy ray irradiation; and

[0040] Step (V'): a step of separating the first molding member and the second molding member from the conductive pillar module precursor for semiconductor manufacturing.

[0041] The present invention also relates to a method for manufacturing a semiconductor or a semiconductor precursor, the method comprising the following steps (L1) to (L5):

[0042] Step (L1): a step of closely attaching the conductive pillar module precursor for semiconductor manufacturing of the present invention to a carrier member;

[0043] Step (L2): a step of bonding the conductive pillar member on one side of the conductive pillar module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a semiconductor chip;

[0044] Step (L3): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin;

[0045] Step (L4): a step of soldering the conductive column member exposed in step (L3) to a substrate; and

[0046] Process (L5): A process of filling the gaps between the substrate, the semiconductor chip, and the conductive pillar members with a molded underfill material.

[0047] The present invention also relates to a method for manufacturing a semiconductor or a semiconductor precursor, the method comprising the following steps (L1') to (L5'):

[0048] Step (L1'): a step of making the conductive column module precursor for semiconductor manufacturing of the present invention adhere closely to a carrier member;

[0049] Step (L2'): a step of bonding the conductive column component on one side of the conductive column module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a substrate by welding;

[0050] Step (L3'): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin;

[0051] Step (L4'): a step of bonding the conductive pillars exposed in step (L3') directly or via a conductive layer (reconfiguration layer) to a semiconductor chip; and

[0052] Step (L5'): a step of filling the gaps between the substrate, the semiconductor chip, and the conductive pillars with a molded underfill material.

[0053] Effects of the Invention

[0054] The conductive pillar module precursor for semiconductor manufacturing or the conductive pillar module for semiconductor manufacturing of the present invention has the following characteristics: it can be used for secondary wiring of a substrate of a flip chip package, or for forming a redistribution layer (RDL) in a post-chip (RDL-first) package, and has excellent adhesion to the substrate, stress relaxation, and durability. In addition, a semiconductor or semiconductor precursor using the conductive pillar module can be provided.

[0055] According to the method for manufacturing a conductive pillar module precursor for semiconductor manufacturing, or the method for manufacturing a semiconductor or a semiconductor precursor of the present invention, a manufacturing method can be provided which does not use photolithography technology and reduces the number of steps and time. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is one embodiment of the conductive column module precursor for semiconductor manufacturing of the present invention.

[0057] Figure 2 This is one embodiment of the conductive column module for semiconductor manufacturing of the present invention.

[0058] Figure 3 This is one embodiment of the semiconductor or semiconductor precursor of the present invention.

[0059] Figure 4 This is one embodiment of the semiconductor or semiconductor precursor of the present invention.

[0060] Figure 5 This is one embodiment of a method for producing a conductive column module precursor for semiconductor manufacturing according to the present invention.

[0061] Figure 6 This is one embodiment of a conductive column module precursor manufactured by the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention.

[0062] Figure 7 This is one embodiment of a method for producing a conductive column module precursor for semiconductor manufacturing according to the present invention.

[0063] Figure 8 This is one embodiment of a method for manufacturing the semiconductor or semiconductor precursor of the present invention by using flip chip packaging.

[0064] Fig. 9 This is one embodiment of a method for manufacturing a semiconductor or semiconductor precursor of the present invention by chip-last packaging using an RDL (reconfiguration layer).

[0065] Fig.10 This is a diagram showing the overall configuration of a curable silicone sheet production apparatus used in Examples (including the overall structure of a sheet-forming portion).

[0066] Fig.11The graph shows the results of checking the warping of the structure or the movement of the conductive pillars after placing the structure obtained in the example in an oven set at 250° C. for 30 seconds. DETAILED DESCRIPTION

[0067] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

[0068] In the present invention, atmospheric pressure refers to the atmospheric pressure in an environment such as a laboratory or factory where the curable silicone composition of the present invention is operated. It is not limited to a specific pressure and generally refers to an atmospheric pressure in the range of -100 hPa to +100 hPa relative to 1 atmosphere (1013.25 hPa), and particularly refers to 1 atmosphere (1013.25 hPa).

[0069] In this specification, room temperature refers to the temperature of the environment where the personnel who process the conductive pillar module precursor for semiconductor manufacturing of the present invention are located. Room temperature generally refers to 0-40°C, particularly 15-30°C, and especially 18-25°C.

[0070] [Conductive pillar module precursor for semiconductor manufacturing]

[0071] The conductive column module precursor for semiconductor manufacturing of the present invention is first described in detail below. The conductive column module precursor for semiconductor manufacturing of the present invention is characterized by having a structure in which a conductive column member is supported by a sheet-like cured resin.

[0072] exist Figure 1 In the figure, an embodiment of the conductive column module precursor (A) for semiconductor manufacturing of the present invention is shown. The conductive column module precursor for semiconductor manufacturing of the present invention has the following structure: a plurality of conductive column components (2) are supported on a sheet-like resin cured material (1'). The supported structure refers to a structure in which the conductive column components (2) are exposed from at least one surface of the sheet-like resin cured material (1').

[0073] The sheet-shaped cured resin may be a cured product of a curable silicone composition.

[0074] A curable silicone composition, characterized in that it contains:

[0075] (A) 100 parts by mass of an organopolysiloxane resin comprising the following components (A1) and (A2) in a mass ratio of 20:80 to 90:10, wherein the mass reduction rate when exposed to 200° C. for one hour is 2.0% by mass or less;

[0076] (A1) has a curing reactive functional group containing a carbon-carbon double bond in the molecule and contains 20 mol % or more of SiO4 / 2 The siloxane unit shown alone does not have a heat-fusible, solid organopolysiloxane resin at 25°C;

[0077] (A2) does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol % or more of SiO 4 / 2 The siloxane unit shown alone does not have a heat-fusible, solid organopolysiloxane resin at 25°C;

[0078] (B) 10 to 100 parts by weight of a linear or branched organopolysiloxane having at least two curing reactive functional groups containing carbon-carbon double bonds in the molecule and being liquid or plastic at 25° C.;

[0079] (C) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule: the number of silicon-bonded hydrogen atoms per silicon-bonded alkenyl group contained in the entire composition is 0.5 to 20.0; and the composition as a whole has hot melt properties.

[0080] In the present invention, unless otherwise specified, "having hot melt properties" means that the softening point of the composition is between 50 and 200°C, the composition has a melt viscosity of 1 to 500 Pa·s at 100°C, and has the property of being able to flow. Therefore, in this specification, a curable silicone composition having hot melt properties is also referred to as a curable hot melt silicone composition.

[0081] That is, the curable hot-melt silicone composition is a silicone composition that can be thermally cured by a hydrosilylation reaction, the main components of the composition are component (A) and component (B), and further contain: an organohydrogenpolysiloxane (component (C)) as a crosslinking agent, wherein component (A) is composed of the following (A1) and (A2) in a mass ratio of (A1):(A2)=20:80-90:10, 35:65-90:10, 50:50-90:10: (A1) has a mass reduction rate of 2.0% or less when exposed to 200°C for one hour, has a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of all siloxane units composed of SiO 4 / 2The siloxane units shown (hereinafter referred to as "Q units") are organic polysiloxane resins that are solid at 25°C and do not have heat-fusibility alone; (A2) an organic polysiloxane resin that has a mass reduction rate of 2.0 mass% or less when exposed to 200°C for one hour, does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of the Q units of all siloxane units, which are not heat-fusible alone and are solid at 25°C; and a linear or branched organic polysiloxane containing a carbon-carbon double bond that is liquid or plastic at 25°C (component (B)). In addition, a hydrosilylation reaction retarder, i.e., a so-called curing retarder, can be arbitrarily selected and used in the curable hot-melt silicone composition, but in this case, it is preferred to use a curing retarder having a boiling point of 200°C or more, particularly a boiling point of 200°C or more at 1 atmosphere (1013.25 hPa). Furthermore, the curable hot-melt silicone composition may also be added with other additives known in the art within the scope of the present invention that can maintain the target properties.

[0082] [Thermal Melt Properties and Structure of Curable Silicone Composition]

[0083] The curable silicone composition is characterized in that the composition as a whole has hot melt properties and can flow under heating conditions. In particular, the curable silicone composition preferably has a softening point of 50°C or above and a melt viscosity at 150°C (preferably, a melt viscosity of less than 200 Pa·s as measured by a high-temperature flow tester described later). It should be noted that in the present invention, as long as the composition as a whole has hot melt properties, the individual components constituting the composition (especially component (A)) do not have hot melt properties.

[0084] [Ingredients (A)]

[0085] In order to minimize the surface tackiness (surface viscosity) of the cured product formed by curing the present composition and to suppress changes in the elastic modulus of the cured product at high temperatures, the mass reduction rate of component (A) after exposure to 200°C for one hour needs to be 2.0 mass% or less.

[0086] The curable silicone composition comprises the following composition as component (A) in a mass ratio of 20:80 to 90:10, 35:65 to 90:10, and 50:50 to 90:10: an organopolysiloxane resin having a curing reactive functional group containing a carbon-carbon double bond, containing 20 mol% or more of the Q unit of the total siloxane unit, which does not exhibit hot melting properties alone, and is solid at 25°C; and an organopolysiloxane resin having no curing reactive functional group containing a carbon-carbon double bond, containing 20 mol% or more of the Q unit of the total siloxane unit, which does not exhibit hot melting properties alone, and is solid at 25°C. The organopolysiloxane resin may also include R3SiO1 / 2 、R2SiO 2 / 2 、RSiO 3 / 2 (R each independently represents a monovalent organic group, in particular a monovalent hydrocarbon group having 1 to 10 carbon atoms) or a siloxane unit composed of R 2 O 1 / 2 (R 2 The organopolysiloxane resin may be a branched siloxane unit having a large amount of other branched siloxane units (e.g., RSiO) or a branched siloxane unit having a large amount of other branched siloxane units (e.g., RSiO 3 / 2 ), sometimes the technical effect of the present invention cannot be achieved.

[0087] Such an organopolysiloxane resin (A) is an organopolysiloxane resin mixture containing the following components at a mass ratio of 20:80 to 90:10, 35:65 to 90:10, or 50:50 to 90:10 (component (A1):component (A2)):

[0088] (A1) an organopolysiloxane resin having a curing reactive functional group containing a carbon-carbon double bond in the molecule, containing 20 mol % or more of Q units based on all siloxane units, which alone has no thermal meltability and is solid at 25° C.; and

[0089] (A2) An organopolysiloxane resin which does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule and contains 20 mol% or more of Q units in all siloxane units. It is not hot-meltable alone and is solid at 25°C. Here, curing reactivity means that it can undergo a hydrosilylation reaction with the organohydrogensiloxane of component (C), thereby curing the entire composition, and refers to a curing reactive functional group containing a carbon-carbon double bond in the molecule such as an alkenyl group or an acryloxy group.

[0090] The component (A) does not exhibit hot melt properties alone, but can be used in combination with the component (B) described below within a predetermined range of quantitative ratio to impart hot melt properties to the entire composition.

[0091] [Organopolysiloxane resin having curing reactive functional group (A1)]

[0092] The component (A1) is one of the main components of the present composition and is an organopolysiloxane resin containing 20 mol% or more of Q units, not having heat-fusibility alone, and having a curing reactive functional group containing a carbon-carbon double bond in the molecule.

[0093] The component (A1) needs to have a curing reactive group containing a carbon-carbon double bond in the molecule. Such a curing reactive group is a hydrosilylation-reactive functional group, which can form a cured product by a hydrosilylation crosslinking reaction with the component (C). Such a curing reactive group can be particularly an alkenyl group, for example, an alkenyl group having 2 to 10 carbon atoms such as vinyl and hexenyl can be listed.

[0094] Component (A1) is an organopolysiloxane resin which is not hot-melting alone and is solid in the absence of a solvent. Here, not hot-melting means that the organopolysiloxane resin as component (A1) does not exhibit heating and melting behavior at 200°C or below, specifically, does not have a softening point and melt viscosity at 200°C or below. In order to make component (A1) exhibit such physical properties, the functional group in the organopolysiloxane resin is a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially a functional group selected from an alkyl group having 1 to 10 carbon atoms such as a methyl group, and substantially does not contain an aryl group such as a phenyl group, for example, the proportion of the aryl group in the total silicon-bonded organic group is 5 mol% or less, or 2 mol% or less, and preferably does not contain any aryl group. In the case where component (A1) contains a large amount of aryl groups such as phenyl groups as organic groups, the component sometimes exhibits hot-melting properties alone, and sometimes reduces the effect of reinforcing the cured product from the Q unit.

[0095] Preferably, the functional group bonded to the silicon atom of the organopolysiloxane resin of component (A1) is a group selected from alkenyl groups such as methyl and vinyl, 70 mol% to 99 mol% of all organic groups bonded to the silicon atom may be methyl, and the other organic groups bonded to the silicon atom may be alkenyl groups such as vinyl. Within the scope involved, component (A1) is not hot-melt alone, and is useful as a component with particularly excellent coloring resistance at high temperatures of the cured product obtained from the curable silicone composition. It should be noted that the organopolysiloxane resin of component (A1) may also contain a small amount of hydroxyl or alkoxy groups.

[0096] Component (A1) is an organopolysiloxane resin that is solid in a solvent-free state. Preferably, component (A1) is:

[0097] (A1-1) an organopolysiloxane resin represented by the following average unit formula:

[0098] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R2 O 1 / 2 ) e

[0099] (In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 1 to 12 mol% are alkenyl groups; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0.20≤d≤0.65, 0≤e≤0.05, wherein 0.20≤c+d, and a+b+c+d=1)

[0100] The organopolysiloxane resin shown alone does not have thermal melting properties and is solid at 25°C.

[0101] In the above average unit formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, for example, alkyl groups such as methyl, alkenyl groups such as vinyl, and aryl groups such as phenyl. 1 1 to 12 mol% are alkenyl groups, and all R 1 2 to 10 mol% of the alkenyl group is particularly preferably vinyl. When the content of the alkenyl group is less than the lower limit of the above range, the mechanical strength (hardness, etc.) of the obtained cured product sometimes becomes insufficient. On the other hand, if the content of the alkenyl group is below the upper limit of the above range, the composition containing this component can achieve good hot melt performance as a whole composition.

[0102] In the above formula, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 The alkyl group of R 2 The group R 2 O 1 / 2 This corresponds to the hydroxyl group or alkoxy group of the organopolysiloxane resin of the component (A).

[0103] In the above formula, a represents the general formula: R 1 3SiO 1 / 2 The ratio of the siloxane units in the composition is 0.1≤a≤0.60 and 0.15≤a≤0.55. If a is greater than the lower limit of the above range, the composition containing the present component can achieve good hot melt performance as a whole composition. On the other hand, if a is less than the upper limit of the above range, the mechanical strength (hardness, elongation, etc.) of the cured product obtained by curing the curable silicone composition does not become too low.

[0104] In the above formula, b represents the general formula: R 1 2SiO 2 / 2 b satisfies 0≤b≤0.70 and 0≤b≤0.60. If b is below the upper limit of the above range, the composition containing this component can achieve good hot melt performance as a whole composition and can obtain a composition with less stickiness at room temperature.

[0105] In the above formula, c represents the general formula: R 3 SiO 3 / 2 c satisfies 0≤c≤0.80 and 0≤c≤0.75. If c is below the upper limit of the above range, the composition containing this component can achieve good hot melt performance as a whole composition, and a composition with little stickiness, low viscosity or no viscosity at room temperature can be obtained. In the present invention, c can be 0, and preferably.

[0106] In the above formula, d is a number representing the ratio of Q units, and can be 0.20≤d≤0.65, 0.25≤d≤0.65. If d is within the above numerical range, the composition containing this component can achieve good hot melt performance as a whole composition, and the cured product obtained by curing the composition is hard and has sufficient flexibility for practical use.

[0107] In the above formula, e represents the general formula: R 2 O 1 / 2 The number of the proportion of units, which refers to a hydroxyl or alkoxy group bonded to a silicon atom that may be contained in the organopolysiloxane resin. e satisfies 0≤e≤0.05, preferably 0≤e≤0.03. If e is below the upper limit of the range, a material that achieves good hot melt properties as a composition as a whole can be obtained. It should be noted that in the above formula, the total of a, b, c and d, which are the sum of each siloxane unit, is equal to 1.

[0108] Component (A1) is an organopolysiloxane resin having the above characteristics, but since it is solid at room temperature, it can be used in a state of being dissolved in a solvent or solvent mixture selected from the group consisting of aromatic hydrocarbons such as toluene, xylene and mesitylene; ethers such as tetrahydrofuran and dipropyl ether; organosilicones such as hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, etc., in order to physically mix with component (B) described later. The solvent used here can be efficiently removed in the process described later.

[0109] [Ingredient (A2)]

[0110] Component (A2) is one of the main ingredients of the present composition. It is an organopolysiloxane resin that does not have hot melt properties alone, does not contain a curing reactive functional group, and is solid at 25°C. It is a component used to achieve hot melt properties as a whole of the curable silicone composition and excellent stress relaxation properties of the cured product obtained by curing the curable silicone composition by using it in combination with the above-mentioned components (A1) and component (B) within a prescribed amount range.

[0111] Component (A2) is an organopolysiloxane resin which is not heat-fusible on its own and is solid in the absence of a solvent. The behavior of component (A2) when not heat-fusible and preferably not containing an aromatic group such as a phenyl group are the same as those of component (A1).

[0112] Component (A2) has the following characteristics: similar to component (A1), it is solid at 25°C, and is an organopolysiloxane resin containing 20 mol% or more of Q units in all siloxane units, but does not have a curing reactive functional group containing at least one carbon-carbon double bond in the molecule. That is, component (A2) is characterized in that it does not contain alkenyl groups such as vinyl as functional groups in the organopolysiloxane resin. The groups possessed by the organopolysiloxane resin as component (A2) can include monovalent hydrocarbon groups having 1 to 10 carbon atoms, especially alkyl groups having 1 to 10 carbon atoms such as methyl, and the organopolysiloxane resin does not substantially contain aryl groups such as phenyl, for example, the proportion of aryl groups in all organic groups bonded to silicon is 5 mol% or less, and can be 2 mol% or less, and preferably contains no aryl groups at all.

[0113] Preferably, the functional group bonded to the silicon atom in component (A2) is an alkyl group having 1 to 10 carbon atoms, such as a methyl group, and 70 to 100 mol% of the organic groups bonded to all silicon atoms may be methyl groups. Within the scope involved, component (A2) may not exhibit heat-fusibility alone and may be composed of SiO 4 / 2 The component containing the siloxane unit is a component that has a particularly excellent reinforcing effect on the cured product. It should be noted that the organopolysiloxane resin of the component (A2) may also contain a small amount of hydroxyl groups or alkoxy groups.

[0114] Component (A2) does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, so it itself does not form a cured product even when combined with the organohydrogen polysiloxane of component (C), but has the effect of improving the hot melt properties of the curable silicone composition as a whole, or reinforcing the cured product obtained by curing the curable silicone composition. In addition, if necessary, by using it in combination with component (A1) having a curing reactive functional group, the heat melting characteristics of the obtained curable silicone composition and the physical properties of the composition after curing can be adjusted.

[0115] The component (A2) is an organopolysiloxane resin which is solid at 25°C in the absence of a solvent, and is characterized in that it contains 20 mol% or more of Q units as branched siloxane units, based on all siloxane units, in the molecule. Preferably, in the organopolysiloxane of the component (A2), the Q units account for 40 mol% or more, 50 mol% or more, and particularly in the range of 50 to 65 mol% of all siloxane units.

[0116] Preferably, component (A2) has the following average unit formula:

[0117] (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j

[0118] (In the formula, each R 3 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms and not containing a carbon-carbon double bond; 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; f, g, h, i and j are numbers satisfying the following: 0.35≤f≤0.55, 0≤g≤0.20, 0≤h≤0.20, 0.45≤i≤0.65, 0≤j≤0.05 and f+g+h+i=1)

[0119] The organopolysiloxane resin shown alone does not have thermal meltability.

[0120] In the above average unit formula, each R 3 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms and not containing a carbon-carbon double bond, for example, a group selected from the group consisting of alkyl groups such as methyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 3 70 mol% or more of the alkyl groups are alkyl groups having 1 to 10 carbon atoms, such as methyl groups, and methyl groups are particularly preferred from the viewpoint of industrial production and the technical effects of the invention. 3 Preferably, the phenyl group or the like is substantially free of aryl groups. When a large amount of phenyl groups or the like are contained, the component (A2) itself becomes hot-melt, and the technical effects of the present invention may not be achieved, and the coloring resistance of the cured product obtained by curing the curable silicone composition at high temperature may deteriorate.

[0121] In the above formula, R 2As above, but R 2 In the case of an alkyl group, a methyl group can be exemplified.

[0122] In the above formula, f represents the general formula: R 3 3SiO 1 / 2 f satisfies 0.35≤f≤0.55 and 0.40≤f≤0.50. If f is above the lower limit of the above range, the curable silicone composition containing this component can achieve good hot melt performance as a whole composition. On the other hand, if f is below the upper limit of the above range, the mechanical strength (hardness, etc.) of the obtained cured product will not become too low.

[0123] In the above formula, g represents the general formula: R 3 2SiO 2 / 2 g satisfies 0≤g≤0.20 and 0≤g≤0.10. If g is below the upper limit of the range, the curable silicone composition containing this component can achieve good hot melt performance as a whole composition and can obtain a composition with less stickiness at room temperature. In the present invention, g can be 0.

[0124] In the above formula, h represents the general formula: R 3 SiO 3 / 2 h satisfies 0≤h≤0.20 and 0≤h≤0.10. If h is below the upper limit of the range, the curable silicone composition containing this component can achieve good hot melt performance as a whole composition and can obtain a composition with less stickiness at room temperature. In the present invention, h can be 0.

[0125] In the above formula, i is a number representing the ratio of Q units, and can be 0.45≤i≤0.65, 0.50≤i≤0.65. When i is within this numerical range, the curable silicone composition containing this component can achieve good hot melt performance as a whole composition, the mechanical strength of the cured product obtained by curing the curable silicone composition is excellent, and the composition as a whole can be non-sticky and have good workability.

[0126] In the above formula, j represents the general formula: R 2 O 1 / 2 The ratio of the units is the number of hydroxyl or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. j satisfies 0≤j≤0.05 and 0≤j≤0.03. If j is below the upper limit of the above range, good hot melt performance can be achieved as a whole for the curable silicone composition. It should be noted that in the above formula, the total of f, g, h and i, which are the sum of the siloxane units, is equal to 1.

[0127] Component (A2) is an organopolysiloxane resin having the above characteristics, and its handling properties are the same as those of the above component (A1). That is, component (A2) is solid at room temperature (e.g., 25°C), and thus, like component (A1), it can be used in a state of being dissolved in the above solvent or solvent mixture in order to be mixed with component (B), and then the solvent can be removed to prepare a curable silicone composition.

[0128] [Removal of volatile low molecular weight components in component (A)]

[0129] Regarding the components (A1) and (A2), volatile low molecular weight components are generated in the respective production steps. Specifically, the volatile low molecular weight components are M4Q structures, wherein the M units (R 3 3SiO 1 / 2 ) and Q unit (SiO 4 / 2 ) is polymerized, it appears as a by-product. This structure has the effect of significantly reducing the hardness of the cured product obtained from the curable silicone composition. The organopolysiloxane resins of components (A1) and (A2) are produced by polymerization reaction of raw material monomers in the presence of an organic solvent with high compatibility with them, and the organic solvent is removed by reduced pressure drying, etc., thereby obtaining a solid organopolysiloxane resin, but the M4Q structure has high compatibility with the organopolysiloxane resin and is difficult to remove under drying conditions such as removing the organic solvent. It is known that the M4Q structure can be removed by exposing the organopolysiloxane resin containing it to a temperature of 200°C or above for a short time, but after the curable silicone composition containing the M4Q structure is integrally molded with a substrate such as a semiconductor, if the M4Q structure is removed by exposing it to high temperature, the volume of the cured product produced by the curable silicone composition may be reduced and the hardness may be significantly increased, and the size of the molded product may change, causing warping, etc. Furthermore, the present M4Q structure also has the effect of imparting adhesion to the obtained cured product, and therefore essentially has the effect of increasing the surface viscosity of the cured product. When the cured product is used as a sealant for protecting a substrate, especially a sealant for the purpose of single-sided protection, it is sometimes necessary to reduce the surface viscosity as much as possible, and the presence of the M4Q structure becomes a problem. In addition, when a large amount of the present M4Q structure remains in the composition or the cured product, it sometimes causes a significant increase in hardness and a significant change in the elastic modulus in the adhesive layer or sealing layer for the purpose of double-sided bonding. Therefore, in order to apply the curable silicone composition to the purpose of lamination with a substrate such as a semiconductor, it is preferred to remove the M4Q structure from the organopolysiloxane resin as far as possible before the raw materials are prepared before the curable silicone composition is laminated with the substrate to cure the curable silicone composition.

[0130] Examples of methods for removing the M4Q structure from the organopolysiloxane resin include a method of removing the M4Q structure by drying the obtained organopolysiloxane resin particles in an oven or the like in the production process of the organopolysiloxane resin; and a method of removing the M4Q structure together with the organic solvent using a twin-screw kneader described later.

[0131] More specifically, component (A1) and component (A2) are produced in the presence of an organic solvent, and volatile components such as M4Q structures appear as by-products during the production process. The volatile components can be removed by treating the obtained organopolysiloxane resin as a crude raw material at a high temperature of about 200°C for a short time. Therefore, the organic solvent and volatile components such as M4Q structures can be removed from components (A1) and (A2) at the same time by using a twin-screw kneader set at a temperature of 200°C or above. From the viewpoint of efficiently producing a curable hot-melt silicone composition, it is preferred to perform the following process: add component (B) described later to component (A2) dissolved in an organic solvent or a mixture of component (A1) and component (A2), mix them in a liquid state, feed the mixed substance to a twin-screw extruder set at 200°C or above, and remove volatile components such as M4Q structures together with the organic solvent. A hot-melt mixture of the component (A) and the component (B) can be obtained by this method, and this mixture can be used for kneading with the remaining components constituting the curable silicone composition in the step described later.

[0132] [Mass Ratio of Component (A1) to Component (A2) in Component (A)]

[0133] In order to make the present composition as a whole hot melt, component (A2) or a mixture of component (A1) and component (A2) needs to be mixed with component (B) at a predetermined ratio described later, but the ratio of component (A1) to component (A2) can be in the range of 20:80 to 90:10, or in the range of 35:65 to 90:10, or 50:50 to 90:10. Component (A2) itself does not have a curing reactive functional group and therefore does not have curing properties, but by using component (A2) in combination with component (A1) in the present composition, the storage modulus, loss modulus, and tanδ calculated from the ratio of the cured product obtained by curing the present curable composition can be adjusted to some extent, thereby achieving the preferred elastic modulus, softness, and stress relaxation of the cured product. In addition, even in the absence of component (A1), by combining component (A2) with component (B), a curable hot melt silicone composition with desired properties can be prepared.

[0134] [Ingredient (B)]

[0135] Component (B) is one of the main ingredients of the curable silicone composition, and is a straight-chain or branched organopolysiloxane that is liquid or plastic at 25°C and has at least two curing reactive functional groups containing carbon-carbon double bonds in the molecule. Such a curing reactive chain organopolysiloxane can exhibit hot melt properties as the entire composition by mixing with the solid organopolysiloxane resin of component (A).

[0136] Component (B) needs to have a curing reactive functional group containing a carbon-carbon double bond in the molecule. Such a curing reactive functional group has hydrosilylation reactivity and forms a cured product through a crosslinking reaction with other components. Such a curing reactive functional group can be exemplified by an alkenyl group that is the same as the functional group possessed by component (A1), particularly a vinyl group or a hexenyl group.

[0137] Component (B) is a straight-chain or branched organopolysiloxane that is liquid or plastic at 25°C (room temperature), and can exhibit hot-melt properties as a whole composition by mixing with component (A) that is solid at room temperature. The chemical structure of the organopolysiloxane of component (B) can be straight-chain or can be a siloxane unit with a small number of branches (for example, represented by the general formula: R 4 SiO 3 / 2 The T unit (R 4 independently a monovalent hydrocarbon group having 1 to 10 carbon atoms) or a SiO 4 / 2 The Q unit shown in FIG. 1 ) is a branched organopolysiloxane, but preferably,

[0138] (B1) has the following structural formula:

[0139] R 4 3SiO(SiR 4 2O 2 / 2 ) k S i 4 3

[0140] (In the formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein R 4 At least two of the groups are alkenyl groups, and k is a number from 20 to 5,000)

[0141] Preferably, the straight-chain diorganopolysiloxane has an alkenyl group at each end of the molecular chain, and particularly preferably has a vinyl group.

[0142] In the above formula, each R 4are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, for example, groups selected from the group consisting of alkyl groups such as methyl, alkenyl groups such as vinyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 4 is an alkenyl group, especially a vinyl group. 4 It may be a functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, such as a methyl group, and an alkenyl group, such as a vinyl group and a hexenyl group. 4 In one molecule, at least two are alkenyl groups, and the remaining R 4 It should be noted that, from the perspective of the technical effect of the invention, R 4 It is preferred that the phenyl group or other aromatic groups are substantially not contained. When a large amount of phenyl group or other aromatic groups are contained, the coloring resistance of the cured product obtained from the curable silicone composition at high temperature may deteriorate. It is particularly preferred that the molecular chain has one vinyl group or other olefinic group at each end, and the remaining R 4 It may be methyl.

[0143] In the above formula, k is a number of 20 to 5,000, 30 to 3,000, or 45 to 800. If k is greater than or equal to the lower limit of the above range, a curable silicone composition with less stickiness at room temperature can be obtained. On the other hand, if k is less than or equal to the upper limit of the above range, good hot melt performance can be achieved as a whole for the curable silicone composition.

[0144] Here, in order to exhibit hot melt properties as the composition as a whole, the content of the linear or branched organopolysiloxane component (B) is in the range of 10 to 100 parts by mass, or may be in the range of 10 to 70 parts by mass, or 15 to 50 parts by mass, relative to 100 parts by mass of the component (A) as the organopolysiloxane resin. If the content of the component (B) is within the above range, the obtained curable silicone composition can exhibit good hot melt properties, increase the mechanical strength of the cured product obtained by curing the curable silicone composition, and reduce the stickiness of the obtained curable silicone composition at room temperature, thereby improving the workability of the composition.

[0145] [Ingredient (C)]

[0146] Component (C) is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, which is capable of crosslinking with the carbon-carbon double bonds contained in the above-mentioned components (A) and (B) in the presence of a catalyst for a hydrosilylation reaction, and is a component for curing the composition.

[0147] The structure of the organohydrogen polysiloxane used as a crosslinking agent is not particularly limited and may be linear, branched, cyclic or resinous. That is, component (C) may be an organohydrogen polysiloxane having the following units:1 / 2 The organohydrogensiloxane unit (M H unit, R is independently a monovalent organic group), composed of HRSiO 2 / 2 The organohydrogensiloxane unit (D H unit, R is independently a monovalent organic group).

[0148] On the other hand, when the curable silicone composition is used in a molding process, the content of the curing reactive functional group containing a carbon-carbon double bond in the composition is small. Therefore, from the viewpoint of the curing speed, its moldability and curability, the organohydrogenpolysiloxane may be the following organohydrogenpolysiloxane resin: 3 / 2 The monoorganosiloxane unit (T unit, R is a monovalent organic group or a silicon atom-bonded hydrogen atom) shown or the SiO 4 / 2 The branched unit of the siloxane unit (Q unit) shown in the figure has at least two HR2SiO 1 / 2 The diorganohydrogensiloxane units (M H Unit, R is independently a monovalent organic group), the molecular end has M H unit.

[0149] Particularly preferred organohydrogenpolysiloxanes are

[0150] The average composition formula (1) is as follows:

[0151] (R 5 3SiO 1 / 2 ) a (R 6 2SiO 2 / 2 ) b (R 6 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2)e (1)

[0152] (Where R 5 are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, R 6 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and all R 5 At least two of them are hydrogen atoms, and a, b, c, and d are numbers that satisfy the conditions of 0.01≤a≤0.6, 0≤b, 0≤c≤0.9, 0≤d≤0.9, and a+b+c+d=1 and c+d≥0.2. )

[0153] The organohydrogenpolysiloxane shown. It should be noted that the organohydrogenpolysiloxane may also have the following feature: the mass reduction rate after exposure to 100° C. under atmospheric pressure for 1 hour relative to the mass reduction rate before exposure is 10% by mass or less.

[0154] In the above formula, each R 5 are identical or different monovalent hydrocarbon groups having 1 to 12 carbon atoms or hydrogen atoms without aliphatic unsaturated carbon bonds, wherein at least two, preferably at least three, R 5 As R other than hydrogen atom 5 The monovalent hydrocarbon group is a group selected from the group consisting of, for example, alkyl groups such as methyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 5 The monovalent hydrocarbon groups shown may independently be methyl or phenyl.

[0155] In the formula, R 6 is a monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated carbon bond, and examples thereof include 5 The same group as the monovalent hydrocarbon group. 6 It may be a group selected from methyl and phenyl.

[0156] In the formula, a, b, c, and d are numbers that satisfy the following conditions: 0.01≤a≤0.6, 0≤b, 0≤c≤0.9, 0≤d≤0.9, and a+b+c+d=1 and c+d≥0.2. As specific examples, the following can be listed: H MT resin, M H T resin, M H MTQ resin, M H MQ resin, M H DQ resin and M H In the description of the above resins, M, D, T, and Q represent M units, D units, T units, and Q units, respectively. H represents an M unit having a hydrogen atom.

[0157] In the above formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 The alkyl group of R includes methyl and the like. 2 The group R 2 O 1 / 2 This corresponds to the hydroxyl group or alkoxy group of the organohydrogenpolysiloxane of the component (C).

[0158] In the above formula, e represents the general formula: R 2 O 1 / 2The unit is a hydroxyl group or an alkoxy group bonded to a silicon atom that may be contained in the organopolysiloxane resin. e satisfies 0≤e≤0.05 and 0≤e≤0.03. It should be noted that, as described above, in the above formula (1), the total of a, b, c and d, which are the sum of the siloxane units, is equal to 1.

[0159] As the component (C), an organohydrogenpolysiloxane represented by the following average composition formula (2) can be exemplified.

[0160] (HR 7 2SiO 1 / 2 ) f (R 7 2SiO 2 / 2 ) g (SiO 4 / 2 ) h (2)

[0161] In formula (2), R 7 Each is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and f, g and h are numbers satisfying the following conditions: 0.01≤f≤0.6, 0≤g≤0.9, 0.2≤h≤0.9, and f+g+h=1.

[0162] Specific examples of the monovalent hydrocarbon group are as follows: 5 The specific examples of the monovalent hydrocarbon groups shown in the table are the same as those shown in the table. 7 They may each independently be a group selected from a methyl group and a phenyl group.

[0163] In addition, as the component (C), an organohydrogenpolysiloxane represented by the following average formula (3) can be exemplified.

[0164] (HR 8 2SiO 1 / 2 ) i (R 8 2SiO 2 / 2 ) j (R 9 SiO 3 / 2 ) k (3)

[0165] In formula (3), R 8 and R 9 Each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and all R 9 10 mol % or more of the alkyl groups are aryl groups, and i, j and k are numbers satisfying the following conditions: 0.01≤i≤0.6, 0≤j≤0.9, 0.2≤k≤0.9 and i+j+k=1.

[0166] Specific examples of the monovalent hydrocarbon group are as follows: 5 The specific examples of the monovalent hydrocarbon groups shown in FIG. are the same as those shown in FIG. 9 As a condition that 10 mol% or more of the phenyl groups are present, R 9 They may each independently be a group selected from a methyl group and a phenyl group.

[0167] The organohydrogenpolysiloxane represented by the average composition formula (2) and the organohydrogenpolysiloxane represented by the average composition formula (3) may be used alone or in combination.

[0168] The content of the organohydrogenpolysiloxane of component (C) in the curable silicone composition is an amount sufficient to cure the curable silicone composition, and is an amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane of component (C) relative to the curing reactive functional groups containing carbon-carbon double bonds in components (A) and (B) (for example, alkenyl groups such as vinyl groups), such that the number of silicon-bonded hydrogen atoms per alkenyl group (hereinafter referred to as "SiH / Vi ratio") is 0.5 to 20.0, and particularly preferably an amount in the range of 1.0 to 10.

[0169] [Removal of volatile components]

[0170] On the other hand, regardless of the structure, these organohydrogenpolysiloxanes are preferably components that are not easily volatile at atmospheric pressure, especially at about 100°C at 1 atmosphere (1013.25hPa). This is because, in the production process of the curable hot-melt silicone sheet or film described later, in order to obtain a sheet or film without voids, it is necessary to melt-knead the components of the curable silicone composition and the resulting composition under reduced pressure in a temperature range of 50 to 150°C, and by using each component, a sheet or film without voids can be produced. Each component is exposed to a specified temperature under reduced pressure for a very short time, but if a large amount of active ingredients volatilize under this kneading condition, a problem will arise that a composition with designed characteristics cannot be obtained. In particular, the amount of organohydrogenpolysiloxane added as a crosslinking agent is small relative to the total mass of the curable silicone composition, so the characteristics of the composition (curing characteristics, physical properties of the cured product, etc.) will vary greatly from the expected values ​​due to the volatilization of these components. Therefore, the component (C) needs to be a component that is not easily volatile. Specifically, the mass reduction rate after exposure to 100° C. under atmospheric pressure for 1 hour relative to that before exposure can be 10 mass % or less, which is preferred depending on the application.

[0171] Furthermore, the curable silicone composition may include component (D) and / or (E) a filler or a pigment, wherein the component (D) is a catalyst that promotes the hydrosilylation reaction between the curing reactive group containing a carbon-carbon double bond and the component (C).

[0172] [Ingredient (D)]

[0173] Component (D) is a catalyst for promoting the hydrosilylation reaction of the curing reactive group containing a carbon-carbon double bond and component (C), and examples thereof include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, preferably platinum-based catalysts. Examples of the platinum-based catalyst include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenyl siloxane complex of platinum, and platinum alkenyl siloxane complexes, and platinum alkenyl siloxane complexes are particularly preferred. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred from the viewpoint of good stability of the platinum-alkenylsiloxane complex. Furthermore, from the viewpoint of being able to improve the stability of the platinum-alkenylsiloxane complex, it is preferred to add alkenylsiloxanes such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and organosiloxane oligomers such as dimethylsiloxane oligomers to the complex, and it is particularly preferred to add alkenylsiloxanes. In addition, from the viewpoint of improving the workability and the pot life of the composition, these hydrosilylation catalysts may also be thermoplastic resin microparticles containing hydrosilylation catalysts as catalysts dispersed or encapsulated in thermoplastic resins such as silicone resins, polycarbonate resins, and acrylic resins, and in particular thermoplastic resin microparticles containing platinum-containing hydrosilylation catalysts. It should be noted that as catalysts that promote hydrosilylation reactions, non-platinum metal catalysts such as iron, ruthenium, and iron / cobalt can be used.

[0174] From the viewpoint of improving the stability, workability and service life of the curable silicone composition during production, at least a part of the component (D) may be thermoplastic resin microparticles containing (D1) a platinum-containing hydrosilylation catalyst, and the platinum-based hydrosilylation catalyst may be microparticles dissolved or dispersed in the thermoplastic resin, or microcapsule microparticles having a structure containing a platinum-based catalyst as a core in the shell of the thermoplastic resin. As the platinum-based catalyst, the same platinum alkenylsiloxane complex as described above can be exemplified. In addition, the thermoplastic resin is not particularly limited as long as it does not substantially penetrate the platinum-based catalyst at least during the production process and storage process of the curable silicone composition and does not substantially dissolve in the organopolysiloxane of the main component of the curable silicone composition, but the softening point or glass transition point of the thermoplastic resin is preferably above 80°C, and more preferably above 120°C. Specifically, silicone resins, polysilane resins, epoxy resins, acrylic resins, and methylcellulose polycarbonate resins can be preferably used. The softening point is the temperature at which the resin begins to flow due to its own weight or its own surface tension, and can be measured by observing the crushed particles under a microscope while raising the temperature at a certain speed. In addition, the glass transition point can be measured by DSC (Differential Scanning Calorimeter). In the present invention, it is preferred that either the softening point or the glass transition point is 120°C or above. This is because if the softening point or the glass transition point of the thermoplastic resin is lower than 120°C, the platinum component may begin to dissolve in the process of uniformly mixing the curable silicone composition described later. In addition, the average particle size of the thermoplastic microparticles containing the platinum catalyst is not limited, but is preferably in the range of 0.1 to 500 μm, and more preferably in the range of 0.3 to 100 μm. This is because it is difficult to prepare thermoplastic resin microparticles containing platinum catalysts having an average particle size less than the lower limit of the above range, and on the other hand, if the upper limit of the above range is exceeded, the dispersibility in the curable silicone composition is reduced.

[0175] The method for preparing such thermoplastic resin microparticles containing platinum hydrosilylation catalyst is not limited, and examples thereof include chemical methods such as interfacial polymerization or in-situ polymerization, and physical / mechanical methods such as coagulation or liquid drying. In particular, from the viewpoint of being easier to obtain microcapsule microparticles with a narrow particle size distribution, liquid drying and gas phase drying using a spray dryer are preferred. The microparticles obtained by these methods can be used directly, but in order to obtain a composition with excellent storage stability, it is desirable to wash the microparticles with a suitable washing solvent to remove the platinum catalyst attached to the surface. Here, a suitable washing solvent refers to a washing solvent having the property of not dissolving the thermoplastic resin but dissolving the platinum catalyst. As such a washing solvent, for example, alcohols such as methanol and ethanol; low molecular weight organopolysiloxanes such as hexamethyldisiloxane, etc. can be cited. The ratio of the catalyst for hydrosilylation reaction to the thermoplastic resin varies greatly depending on the method for producing the granular material, so it cannot be particularly limited, but it is preferred that the content of the platinum catalyst to the thermoplastic resin is 0.01% by mass or more. This is because if the content of the platinum catalyst is less than 0.01 mass %, the curable silicone composition may impair the physical properties of the cured product unless the thermoplastic resin fine particles containing the platinum catalyst occupy a large amount in the curable silicone composition.

[0176] The amount of the hydrosilylation catalyst as component (D) added is a catalytic amount, preferably an amount in the range of 0.01 to 500 ppm, 0.01 to 100 ppm, or 0.01 to 50 ppm in terms of metal atoms by mass relative to the entire composition (solid content).

[0177] Part or all of the component (D) may be a catalyst for hydrosilylation reaction which is inactive without high-energy ray irradiation but becomes active in the composition by irradiation with high-energy ray, a so-called high-energy ray-activated catalyst or a photoactivated catalyst. By using such a component (D), the composition as a whole can achieve the following characteristics: curing even at low temperature by irradiation with high-energy ray as a trigger, excellent storage stability, and easy reaction control, so excellent workability.

[0178] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, electron beams, and the like. In particular, ultraviolet rays, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices are included. Ultraviolet rays are preferred from the perspective of catalyst activation efficiency, and ultraviolet rays with a wavelength of 280 to 380 nm are preferred from the perspective of industrial utilization. In addition, the irradiation amount varies depending on the type of high-energy ray-activated catalyst, but in the case of ultraviolet rays, the cumulative irradiation amount at a wavelength of 365 nm is preferably 100 mJ / cm2 ~100J / cm 2 within the range.

[0179] Specific examples of component (D) include (methylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)dimethylethylplatinum (IV), (cyclopentadienyl)dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl)trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum (IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum (IV), trimethyl(acetylacetonate)platinum (IV), trimethyl(3,5- bis(hexafluoroacetylacetonate)platinum(II), bis(1-phenyl-1,3-butanedione)platinum(II), bis(1,3-diphenyl-1,3-propanedione)platinum(II), and bis(hexafluoroacetylacetonate)platinum(II). Among them, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedione)platinum(II) are preferred from the aspects of versatility and ease of acquisition.

[0180] The amount of the high energy ray activated catalyst used as component (D) is an effective amount and is not particularly limited as long as it is an amount that promotes the curing of the composition. Specifically, the metal atoms in the catalyst are 0.01 to 1,000 ppm by mass relative to the entire composition (solid component), and preferably the platinum metal atoms in component (D) are in an amount within the range of 0.1 to 500 ppm.

[0181] The component (E) is a filler or a pigment, and preferably includes a white or colored filler, particularly a white or colored inorganic filler, and may include a wavelength conversion component such as a phosphor as a part thereof, and may also include fine particles having other functions such as electrical conductivity and thermal conductivity.

[0182] Although there is no particular limitation on the function of the filler or pigment as component (E), the obtained cured product can be whitened or colored. In addition, it is expected to improve its mechanical strength or hardness, and can impart other functions such as optical functions such as wavelength conversion, thermal conductivity or electrical conductivity. As these components (E), white pigments, black pigments, phosphors, metal powders or other functional fillers can be exemplified, and components that provide white or colored cured products are particularly preferred. It should be noted that the shape of the filler or pigment as component (E) is not particularly limited, and can be spherical, spindle-shaped, flat, needle-shaped, irregularly shaped, etc.

[0183] White pigment is a component that can give whiteness to the cured product and improve light reflectivity. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, and magnesium oxide; hollow fillers such as glass balls and glass beads; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. From the perspective of high light reflectivity and concealment, titanium oxide can be preferably exemplified. In addition, from the perspective of high light reflectivity in the UV field, aluminum oxide, zinc oxide, and barium titanate can be preferably exemplified. The average particle size or shape of the white pigment is not limited, but examples thereof include a preferred average particle size in the range of 0.05 to 10.0 μm or in the range of 0.1 to 5.0 μm. In addition, the white pigment can also be surface treated with a silane coupling agent, silica, aluminum oxide, or the like.

[0184] Black pigments are components that can impart blackness and light-shielding properties to cured products, but it goes without saying that they can also have other functions such as electrical conductivity represented by carbon black or graphene. More specifically, the black pigments include carbon black, graphite, activated carbon, graphene and other carbon-based black pigments; inorganic black pigments including iron oxide, magnetite, chromium iron oxide, chromium iron nickel oxide, copper chromate, chromite, manganese ferrite, nickel manganese iron oxide, and composite metal oxides of <one or more metals selected from iron, cobalt, and copper>; and organic black pigments such as aniline black, cyanine black, and perylene black.

[0185] The phosphor is a component formulated to convert the wavelength of light emitted from a light source (optical semiconductor element) when the cured product is used as a wavelength conversion material. The phosphor is not particularly limited, and examples thereof include yellow, red, green, and blue light-emitting phosphors composed of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, and oxysulfide-based phosphors widely used in light-emitting diodes (LEDs).

[0186] The present composition may contain inorganic fillers other than those mentioned above, for example, reinforcing fillers represented by silica, thermal conductive fillers, conductive fillers, etc., are listed to improve the mechanical strength of the cured product. Furthermore, for the purpose of stably blending in the present composition, component (E) may be surface treated by one or more selected from low molecular weight organosilicon compounds such as silanes and silazanes, organosilicon polymers or oligomers, and other known surface treatment agents. The amount of the surface treatment agent used is not particularly limited, but is generally in the range of 0.1 to 2.0% by mass relative to the overall mass of component (E). Furthermore, component (E) can be blended in a masterbatch state by mixing with other components (A) to (D) in advance.

[0187] The content of component (E) may be in the range of 0.1 to 100 parts by mass, 0.5 to 90 parts by mass, 0.5 to 80 parts by mass, or 1.0 to 50 parts by mass relative to the total amount of components (A) to (D) (100 parts by mass). If the amount added is below the above range, the coloring effect may be insufficient, and if it is above the above range, the melt viscosity of the obtained hot-melt composition may be too high. At the same time, when the composition is produced by the method described below, it may be difficult to knead the entire composition uniformly, the manufacturing device may be easily worn, the obtained composition may be easily faded, or the target color tone may not be achieved.

[0188] From the viewpoint of further improving practical use and storage stability, the curable silicone composition may contain a curing retardant (F) in addition to the above-mentioned components (A) to (E).

[0189] The structure of the curing retarder is not particularly limited, but the boiling point is preferably 200° C. or higher at atmospheric pressure. This is because, in the production process of the curable silicone composition sheet described later, when the raw materials are melt-kneaded under reduced pressure, if a compound with a low boiling point is used as the curing retarder, part or all of the curing retarder will volatilize during the production process of the composition, and the desired curing delay effect for the curable silicone composition may not be obtained.

[0190] The type of curing retarder is not particularly limited, and examples thereof include: alkynols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; enyne compounds such as 3-methyl-3-pentene-1-yne and 3,5-dimethyl-3-hexene-1-yne; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; alkynyloxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. Among these, compounds having a boiling point of 200° C. or higher at atmospheric pressure (e.g., vinyl-tris(1,1-dimethylpropynyloxy)silane, etc.) are particularly preferably used. The content of the curing retardant in the curable silicone composition is not particularly limited, but may be in the range of 1 to 10000 ppm by mass relative to the composition.

[0191] [Thickener]

[0192] Furthermore, the composition may contain a known thickener as another optional component unless the object of the present invention is impaired. The tackifier is not particularly limited as long as it is a component that improves the adhesion of the cured product formed by curing the present composition to the substrate. However, as an example, the components preferably exemplified by the applicant in the international patent application (PCT / JP2020 / 12027) of this case can be preferably used: silane compounds such as 3-glycidoxypropyltrimethoxysilane, organic siloxane oligomers, alkyl silicates, reaction mixtures of amino-containing organic alkoxysilanes and epoxy-containing organic alkoxysilanes disclosed in Japanese Patent Publication No. 52-8854 or Japanese Patent Publication No. 10-195085, cyclocarbon nitrogen siloxane derivatives having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule, silheterocyclopropane derivatives having an organic group containing an alkoxysilyl group, disilane compounds such as 1,6-bis(trimethoxysilyl)hexane, etc., and two or more components selected from them can also be used in combination. The content of the tackifier is not limited, but can be used, for example, in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the total of the present composition.

[0193] [Other additives]

[0194] In addition to the above-mentioned ingredients, materials known in the art may be added to the curable hot melt silicone composition as additives for silicone compositions. For example, in the present composition, as other optional ingredients, heat resistant agents such as iron oxide (iron red), cerium oxide, dimethylsilanol cerium, fatty acid cerium salt, cerium hydroxide, zirconium compounds, etc., as well as dyes, pigments other than white, flame retardants, etc. may also be contained.

[0195] [Resin cured product]

[0196] The cured resin of the present invention can be obtained by curing the curable silicone composition by one or more curing methods selected from heating and high-energy ray irradiation.

[0197] The heating temperature is preferably in the range of 50° C. to 180° C., more preferably 80° C. to 160° C. The heating time is 30 minutes to 5 hours, more preferably 30 minutes to 2 hours.

[0198] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, electron beams, and the like. In particular, ultraviolet rays, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices are included. Ultraviolet rays are preferred from the perspective of catalyst activation efficiency, and ultraviolet rays with a wavelength of 280 to 380 nm are preferred from the perspective of industrial utilization. In addition, the irradiation amount varies depending on the type of high-energy ray-activated catalyst, but in the case of ultraviolet rays, the cumulative irradiation amount at a wavelength of 365 nm is preferably 100 mJ / cm 2 ~100J / cm 2 within the range.

[0199] [Sheet]

[0200] The sheet-like resin cured product of the present invention can be formed by molding the above-mentioned curable silicone composition into a sheet and curing it. For example, a sheet composed of a curable silicone composition with an average thickness of 10 to 1000 μm has hot melt properties and heat curing properties at high temperatures, so it has excellent workability and melting properties, and is particularly advantageous for compression molding. In this case, including component (F), the composition containing all components (A) to (F) can be molded into a sheet.

[0201] Such a sheet-like curable silicone composition can be obtained by using a single-screw or twin-screw continuous kneader to make a uniform mixture of all the components, and then the mixture can be formed into a sheet or film of a predetermined thickness by a twin roll or the like. Alternatively, the granular curable hot-melt silicone composition described below can be obtained first, and then after adding component (F) as needed, the mixture can be kneaded uniformly by a kneader and then formed into a sheet or film adjusted to a desired thickness by a twin roll or the like molding machine.

[0202] The above-mentioned sheet-like curable silicone composition can be produced by using organopolysiloxane resin microparticles as a raw material (method A), or by dispersing an organopolysiloxane resin that is solid at room temperature and an arbitrary chain diorganopolysiloxane in an organic solvent and using the hot-melt solid component after removing the organic solvent as a raw material (hot bulk method) (method B).

[0203] Specifically, the former (method A) is a production method comprising the following steps:

[0204] Step 1: a step of mixing organopolysiloxane resin microparticles, a curing agent, and a functional filler selected as appropriate;

[0205] Step 2: a step of kneading the mixture obtained in step 1 while heating and melting it at a temperature of 120° C. or less;

[0206] Step 3: a step of laminating the heated, melted and kneaded mixture obtained in step 2 between two films each having at least one release surface to form a laminate; and

[0207] Step 4: A step of stretching the mixture in the laminate obtained in step 3 between rolls to form a curable hot-melt silicone sheet having a specific film thickness.

[0208] On the other hand, the latter (method B) is a production method comprising the following steps:

[0209] Step 1: a step of removing the organic solvent from a solution in which an organopolysiloxane resin that is solid at room temperature and an optional chain-like diorganopolysiloxane are dispersed or dissolved in an organic solvent at a temperature of 150° C. or higher to obtain a heat-fusible solid component;

[0210] Step 2: After adding all the curing agent to the hot-melt solid component obtained in step 1, the mixture is kneaded while being heated and melted at a temperature of 120° C. or less;

[0211] Step 3: a step of laminating the heated and molten mixture obtained in step 2 between two films each having at least one release surface to form a laminate; and

[0212] Step 4: A step of stretching the mixture in the laminate obtained in step 3 between rolls to form a curable hot-melt silicone sheet having a specific film thickness.

[0213] In addition, step 3 and step 4 may be continuous and integrated steps. For example, the heated and molten mixture obtained in step 2 may be sprayed or applied between films having at least one release surface just below the rollers for lamination, and at the same time, the gap between the rollers may be adjusted to stretch the film to a specific film thickness. In this way, a manufacturing method having a process that substantially combines step 3 and step 4 is also included in the scope of the above-mentioned manufacturing method.

[0214] That is, step 3 and step 4 may be performed continuously and integrally as follows: a step of spraying or applying the mixture obtained in step 2 between two release films, and sandwiching the mixture between two release films, for example, two long release films; and a step of continuously passing the two release films thus obtained and the laminate composed of the mixture sandwiched therebetween through rollers, stretching and molding the mixture between the release films, and adjusting the film thickness to a predetermined value to obtain the target laminate. Such a method of performing step 3 and step 4 integrally is also included in the above-mentioned manufacturing method.

[0215] In step 3 of the above-mentioned method A or method B, the step of laminating the heated and molten mixture between films is not particularly limited, and may be (i) a step of sandwiching the heated and molten mixture between the first and second release films by spraying or applying the heated and molten mixture from step 2 onto the first release film having a release surface, and then bringing the second release film into contact with the surface of the mixture opposite to the surface in contact with the first release film; or (ii) a step of sandwiching the heated and molten mixture between the first and second release films by spraying or applying the heated and molten mixture from step 2 onto the first and second release films having release surfaces. (ii) The following method can be exemplified: the first and second release films are brought close to each other by an appropriate method, such as two rollers, and the mixture from step 2 is sprayed or applied to the close portion of the two release films, and the mixture is sandwiched in the gap between the two release films simultaneously or substantially simultaneously. The above-mentioned steps 3 and 4 may be continuous steps.

[0216] It should be noted that regarding these manufacturing methods, the applicant and others proposed a method for manufacturing a curable silicone sheet and a manufacturing device therefor in Japanese Patent Application No. 2019-167832, Japanese Patent Application No. 2019-167833 and these priority claim applications (including international patent applications). In the present invention, this method and manufacturing device can also be applied when the curable hot-melt silicone composition is formed into sheets or films.

[0217] The curable silicone composition tends to increase in temperature and decrease in viscosity sharply under high temperature / high pressure (i.e., for example, in the manufacturing process of the above-mentioned laminate), and as a useful melt viscosity value for treating the curable silicone composition, a value measured under the same high temperature / high pressure conditions as when the curable silicone composition is actually used can be used. Therefore, the melt viscosity of the curable silicone composition can be measured under high pressure using a high-pressure flow tester (manufactured by Shimadzu Corporation) compared to measuring it using a rotational viscometer such as a rheometer. Specifically, the melt viscosity of the curable silicone composition at 100°C measured using a high-pressure flow tester can be in the range of 1 to 500 Pa·s, or in the range of 1 to 300 Pa·s. This is because, when the melt viscosity is within the above range, the curable silicone composition exhibits good gap filling performance when hot melted.

[0218] [Conductive column parts]

[0219] The conductive column component is a conductive column, preferably a metal column such as gold, silver, copper, nickel, etc., and more preferably a copper column. The conductive column component is preferably a conductive column with a short diameter of 50 to 500 μm and a long diameter of 50 to 500 μm, and more preferably a short diameter of 100 to 400 μm and a long diameter of 100 to 400 μm. In addition, the conductive column component is preferably a cylindrical column with a diameter of 50 to 500 μm and a height of 50 to 2000 μm, and more preferably a cylindrical column with a diameter of 100 to 400 μm and a height of 100 to 1000 μm.

[0220] In one embodiment, the conductive post module precursor for semiconductor manufacturing preferably has a sheet-shaped cured resin material that is a cured silicone material, and the conductive post member is a conductive post having a minor axis length of 50 to 500 μm and a major axis length of 50 to 500 μm.

[0221] In one embodiment, the conductive pillar module precursor for semiconductor manufacturing is preferably a sheet-shaped cured resin material obtained by curing a hydrosilylation reaction, and the conductive pillar member is a cylindrical copper pillar with a diameter of 50 to 500 μm and a height of 50 to 2000 μm.

[0222] [Conductive pillar module for semiconductor manufacturing]

[0223] The conductive post module for semiconductor manufacturing of the present invention is characterized by having a structure in which the conductive post members are supported by a sheet-like cured resin material, and the conductive post members are exposed from both surfaces of the sheet-like cured resin material.

[0224] exist Figure 2 , an embodiment of the conductive column module for semiconductor manufacturing of the present invention is shown. The conductive column module for semiconductor manufacturing of the present invention has the following structure: a plurality of conductive column components (2) are carried on a sheet-like resin cured material (1'), and the conductive column components are exposed from both sides of the sheet-like resin cured material.

[0225] [Semiconductor or semiconductor precursor]

[0226] The semiconductor or semiconductor precursor of the present invention is characterized in having the following structure: at least a portion of the conductive column component of the conductive column module for semiconductor manufacturing of the present invention is welded to a substrate, and the conductive column exposed from the surface on the opposite side of the sheet-like resin cured material is bonded to the semiconductor chip directly or via a conductive layer (reconfiguration layer).

[0227] exist Figure 3 In the figure, one embodiment of the semiconductor or semiconductor precursor of the present invention is shown. The semiconductor or semiconductor precursor of the present invention has the following structure: at least a part of the conductive column component (2) of the conductive column module (A) for semiconductor manufacturing of the present invention is soldered on a substrate (3), and the conductive column (2) exposed from the surface on the opposite side of the sheet-like resin cured product (1') is directly or via a conductive layer (reconfiguration layer) (5) Adhere to the semiconductor chip (4).

[0228] Specifically, the substrate may be a rigid substrate, a flexible substrate, a rigid-flexible substrate, a metal-based substrate, or any other substrate commonly used in the technical field. In addition, the reconfiguration layer may be a material commonly used in the technical field, or may be a material in which copper wires are arranged in an insulating layer such as polyimide, polybenzoxazole, or benzocyclobutene.

[0229] The semiconductor chip and the reconfiguration layer may use materials commonly used in the art.

[0230] In one embodiment, the semiconductor or semiconductor precursor of the present invention preferably has a structure in which the gaps between the substrate, the semiconductor chip, and the conductive pillar member are filled with a molded underfill material.

[0231] exist Figure 4 , an embodiment of the semiconductor or semiconductor precursor of the present invention is shown. The semiconductor or semiconductor precursor of the present invention has the following structure: the gap between the substrate (3), the semiconductor chip (4) and the conductive column component (A) is filled with a molded bottom filling material (6).

[0232] The mold underfill material may be a material commonly used in the art, and examples thereof include silicone resin and epoxy resin.

[0233] [Method for producing a semiconductor or a semiconductor precursor]

[0234] The method for producing a semiconductor or a semiconductor precursor of the present invention is characterized by comprising a step of bonding the conductive pillar member exposed from the conductive pillar module precursor for semiconductor manufacturing of the present invention to a semiconductor chip or a substrate.

[0235] [Method for manufacturing a conductive column module precursor for semiconductor manufacturing]

[0236] The method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is characterized by comprising the following steps (I) to (IV):

[0237] Step (I): a step of disposing a conductive column component on a molded component;

[0238] Step (II): a step of disposing at least one curable resin composition and an optional release liner on the conductive column member;

[0239] Step (III): a step of curing the curable resin composition into a sheet form by one or more curing mechanisms selected from heating and high-energy ray irradiation; and

[0240] Step (IV): a step of separating the conductive pillar module precursor for semiconductor manufacturing from the molded part after removing any of the release liners.

[0241] exist Figure 5 In the figure, one embodiment of the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is shown. First, a conductive column component (2) is arranged on a mold component (7) (step (I)), then a curable resin composition (1) and an optional release liner (8) are arranged on the conductive column component (2) (step (II)), and then, lamination is performed while applying a pressure in the range of 0.01 to 2.00 MPa under a heating range of 50 to 150°C, and then or simultaneously, the curable resin composition (1) is cured into a sheet (1') by one or more curing mechanisms selected from heating and high-energy ray irradiation (step (III)), and after removing the release liner, the conductive column module precursor for semiconductor manufacturing is separated from the mold component (7) (step (IV)). Figure 5 The photograph shown is a photograph of the conductive pillar module precursor for semiconductor manufacturing of the present invention taken from above.

[0242] In step (II) or (III), a release liner may be laminated on the surface of the curable resin composition, or the surface of the curable resin composition may be made uniform. Finally, the release liner is removed from the surface of the column module precursor for semiconductor manufacturing.

[0243] Optionally, in any process, the column module precursor for semiconductor manufacturing may be cut into small pieces.

[0244] The curable resin composition may be the above-mentioned curable silicone composition.

[0245] In one embodiment, it is preferably characterized in that the curable resin composition used in step (II) is a sheet of a curable resin composition having heat-melting properties, and the step is as follows: after the sheet of the curable resin composition is arranged on the conductive column component, the sheet of the curable resin composition is heated and melted, thereby at least a portion of the conductive column is supported inside the sheet of the curable resin composition.

[0246] The sheet of the curable resin composition can be formed of a laminate of the above-mentioned curable silicone composition.

[0247] [Laminated body]

[0248] The laminate of the curable silicone composition may also be a sheet material composed of the curable silicone composition sandwiched between two film substrates having a release layer. The film substrate having the release layer (generally referred to as a release film) can be peeled off from the sheet material composed of the curable silicone composition when using the sheet material. Hereinafter, the laminate is also referred to as a peelable laminate.

[0249] The method for producing the above-mentioned peelable laminate is not particularly limited, and as an example, a method including the following steps can be cited:

[0250] Step 1: A step of mixing the constituent components of the curable silicone composition described above;

[0251] Step 2: a step of kneading the mixture obtained in step 1 while heating and melting it;

[0252] Step 3: a step of forming a laminate by laminating the heated and molten mixture obtained in step 2 between two release films having at least one release surface in such a manner that the mixture is in contact with the release surface; and

[0253] Step 4: A step of pressing the laminate obtained in step 3 between rolls, rolling the mixture sandwiched between two release films, and forming a curable silicone composition sheet having a specific film thickness.

[0254] Furthermore, a roller having a cooling or temperature regulating function may be used according to arbitrary selection in step 4. In addition, after step 4, a step of cutting the laminated body including the obtained curable silicone composition sheet may be added.

[0255] It should be noted that the thickness of the release film is not particularly limited, and therefore, in general, it includes not only the term "film" but also the term "sheet". However, in this specification, it is referred to as a release film regardless of its thickness.

[0256] The temperature of the mixing step in the step 1 is not particularly limited, and heating may be performed as necessary to sufficiently mix the components. The heating temperature may be, for example, 50° C. or higher.

[0257] By peeling off the release film from the peelable laminate, a sheet composed of a curable hot-melt silicone composition can be obtained. The thickness of the sheet can be 10 to 1000 μm, and the sheet can be flat. Flat means that the thickness of the obtained sheet or film is within the range of ±100 μm or less, preferably within the range of ±50 μm or less, and more preferably within the range of ±30 μm or less.

[0258] The type of substrate material of the release film constituting the peelable laminate is not particularly limited, and for example, polyester film, polyolefin film, polycarbonate film or acrylic film can be appropriately used. The sheet-like substrate may be non-porous. The release film is a film having a release layer formed by subjecting one or both sides of a film composed of such a material to a treatment that imparts peelability, and such treatment is well known in the art.

[0259] The layer with peeling properties imparted on the surface of the release film is called a peeling layer, but the peeling layer is a structure used to make the sheet or film composed of the curable silicone composition easily peelable from the film-like substrate, and may also be called a peeling liner, a separator, a release layer or a peeling coating. Preferably, the peeling layer can be formed as a peeling layer with peeling coating ability of a silicone-based peeling agent, a fluorine-based peeling agent, an alkyd-based peeling agent or a fluorosilicone-based peeling agent. Alternatively, fine concave-convex shapes may be physically formed on the surface of the film-like substrate to reduce its adhesion with the curable silicone composition, or the substrate may be composed of a material that is difficult to adhere to the layer composed of the curable hot-melt silicone composition of the present invention or its cured product. In particular, in the laminated body of the present invention, it is preferred to use a peeling layer formed by curing the fluorosilicone-based peeling agent as the peeling layer.

[0260] The above-mentioned laminate can be used, for example, in the following manner: after peeling off one of the two release films constituting the laminate, an uncured sheet composed of a curable silicone composition that is not in contact with the release film is applied to the adherend, and then the uncured sheet or film-like component is peeled off from the other film-like substrate, i.e., the release film.

[0261] The curable silicone composition can be handled in the form of a sheet or film at room temperature and is a non-flowing solid at 25°C. Here, non-flowing means that it does not deform and / or flow in the absence of external force. Preferably, the curable silicone composition does not deform and / or flow at 25°C and in the absence of external force when formed into pellets or tablets. Such non-flowing can be evaluated, for example, as follows: the molded composition is placed on a hot plate at 25°C. Even if the composition is in the absence of external force or a certain load is applied, the composition does not substantially deform and / or flow. When non-flowing at 25°C, the composition at this temperature has good shape retention and low surface adhesion, so the composition can be easily handled even in an uncured state.

[0262] In addition, the softening point of the curable silicone composition is preferably 100° C. or less. Such a softening point refers to the temperature at which the deformation in the height direction is 1 mm or more when a 100-gram load is pressed on a 22 mm high composition from above for 10 seconds on a hot plate, and the load is removed and the deformation of the composition is measured.

[0263] In one embodiment, the method for producing a conductive column module precursor for semiconductor manufacturing of the present invention is characterized in that the curable resin composition used in step (II) is a hydrosilylation reaction curable silicone sheet having heat-melting properties, and the step is as follows: after the hydrosilylation reaction curable silicone sheet is arranged on the conductive column component, the hydrosilylation reaction curable silicone sheet is heated and melted, thereby at least a portion of the conductive column component is supported inside the curable resin composition sheet, and,

[0264] Step (III) is a step of curing the hydrosilylation reaction-curable silicone sheet into a sheet form by one or more curing mechanisms selected from heating and high-energy ray irradiation.

[0265] The heating and melting temperature of the hydrosilylation reaction-curable silicone sheet is preferably in the range of 50°C to 150°C, or 50 to 120°C.

[0266] The heating temperature and time for curing the hydrosilylation reaction curable silicone sheet, and the type and irradiation amount of the high energy ray are as described above. It is preferred to heat after irradiating the high energy ray.

[0267] In one embodiment, the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention preferably further comprises the following step after the above-mentioned step (IV): after bonding any exposed conductive column component to a semiconductor chip or substrate, the conductive column is exposed on both sides of the sheet-like resin cured material by shaving off at least one side of the sheet-like resin cured material.

[0268] exist Figure 6 An embodiment of a conductive column module precursor manufactured by the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is shown. The conductive column module precursor has the following structure: a plurality of conductive column components (2) are supported on a sheet-like cured resin (1'), and the conductive column components are exposed from both sides of the sheet-like cured resin.

[0269] In addition, as another embodiment, the method for manufacturing a conductive pillar module precursor for semiconductor manufacturing of the present invention is characterized by comprising the following steps (I') to (V'):

[0270] Step (I'): a step of disposing a conductive column component on a first molding component;

[0271] Step (II'): a step of disposing a second molding component on the conductive column component;

[0272] Step (III'): a step of filling the gap between the conductive column member, the first molding member, and the second molding member with a curable resin composition;

[0273] Step (IV'): a step of curing the curable resin composition into a sheet by one or more curing mechanisms selected from heating and high-energy ray irradiation; and

[0274] Step (V'): a step of separating the first molding member and the second molding member from the conductive pillar module precursor for semiconductor manufacturing.

[0275] exist Figure 7 , an embodiment of the method for manufacturing a conductive column module precursor for semiconductor manufacturing of the present invention is shown. The method comprises: first, disposing a conductive column component (2) on a first mold component (7) (step (I')), then disposing a second mold component (7) on the conductive column component (2) (step (II')), further, filling the gap between the conductive column component (2), the first mold component (7) and the second mold component (7) with a curable resin composition (1) (step (III')), and further, curing the curable resin composition (1) into a sheet (1') by one or more curing mechanisms selected from heating and high-energy ray irradiation (step (IV')), and finally, separating the first and second mold components (7) from the conductive column module precursor (A) for semiconductor manufacturing (step (V')).

[0276] In addition to storage stability, the curable resin composition or its sheet has excellent fluidity at high temperatures and low viscosity. Therefore, by heating the composition or sheet before final curing, it can be softened or fluidized. For example, even if there are fine irregularities or gaps on the adherend surface of the adherend, the irregularities or gaps can be seamlessly filled to form a bonding surface with the adherend.

[0277] [Method for producing a semiconductor or a semiconductor precursor]

[0278] The method for producing a semiconductor or a semiconductor precursor of the present invention is characterized by comprising the following steps (L1) to (L5):

[0279] Step (L1): a step of closely attaching the conductive pillar module precursor for semiconductor manufacturing of the present invention to a carrier member;

[0280] Step (L2): a step of bonding the conductive pillar member on one side of the conductive pillar module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a semiconductor chip;

[0281] Step (L3): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin;

[0282] Step (L4): a step of soldering the conductive column member exposed in step (L3) to a substrate; and

[0283] Process (L5): A process of filling the gaps between the substrate, the semiconductor chip, and the conductive pillar members with a molded underfill material.

[0284] exist Figure 8 Detailed Description of the Invention One embodiment of a method for producing a semiconductor or semiconductor precursor of the present invention by flip chip packaging is shown. The present invention comprises: first, making the conductive column module precursor (A) for semiconductor manufacturing of the present invention closely attached to the carrier component (9) (process (L1)), then, preferably by thermal compression bonding, making the single-sided conductive column component (2) of the conductive column module precursor (A) for semiconductor manufacturing exposed from the sheet-like resin cured material (1') bonded to the semiconductor chip (4) (process (L2)), further, after removing the carrier component (9) from the conductive column module precursor (A) for semiconductor manufacturing, at least one side of the sheet-like resin cured material (1') is shaved off to expose the conductive column component (2) on the surface of the sheet-like resin cured material (1') (process (L3)), and further, welding the conductive column component (2) exposed in process (L3) to the substrate (3) (process (L4)), and finally, filling the gap between the substrate (3), the semiconductor chip (4) and the conductive column component (2) with a molded bottom filling material (6) (process (L5)).

[0285] In addition, as another embodiment, the method for producing a semiconductor or a semiconductor precursor of the present invention is characterized by comprising the following steps (L1') to (L5'):

[0286] Step (L1'): a step of making the conductive column module precursor for semiconductor manufacturing of the present invention adhere closely to a carrier member;

[0287] Step (L2'): a step of bonding the conductive column component on one side of the conductive column module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a substrate by welding;

[0288] Step (L3'): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin;

[0289] Step (L4'): a step of bonding the conductive pillars exposed in step (L3') directly or via a conductive layer (reconfiguration layer) to a semiconductor chip; and

[0290] Step (L5'): a step of filling the gaps between the substrate, the semiconductor chip, and the conductive pillars with a molded underfill material.

[0291] exist Fig. 9 In the present invention, an embodiment of a method for manufacturing a semiconductor or semiconductor precursor of the present invention by post-chip packaging using an RDL (reconfiguration layer) is shown. The method comprises: first, making the conductive column module precursor (A) for semiconductor manufacturing of the present invention closely attached to a carrier component (9) (process (L1')), then, by using a solder reflow, making the single-sided conductive column component (2) of the conductive column module precursor (A) for semiconductor manufacturing exposed from a sheet-like resin cured material (1') bonded to a substrate (3) (process (L2')), and further, after removing the carrier component (9) from the conductive column module precursor (A) for semiconductor manufacturing, the sheet-like resin cured material At least one surface of (1') is shaved off to expose the conductive column (2) on the surface of the sheet-like resin cured product (1') (process (L3')). In addition, a conductive layer (reconfiguration layer) (5) is bonded to the conductive column (2) exposed in process (L3'), and a semiconductor chip (4) is bonded thereto (process (L4')). Finally, a molded bottom filling material (6) is used to fill the gap between the substrate (3), the semiconductor chip (4) and the conductive column (2) (process (L5')).

[0292] Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

[0293] Example

[0294] The following is a detailed description of the manufacturing method and characteristics of the conductive column module precursor for semiconductor manufacturing of the present invention through examples. It should be noted that in the following description, Me, Vi, and Ph in the average unit formula represent methyl, vinyl, and phenyl, respectively. In addition, for the conductive column module precursor for semiconductor manufacturing of each embodiment, the bonding characteristics and the trust characteristics of the precursor are measured by the following method. The results are shown in Table 1.

[0295] [Adhesion properties of film samples]

[0296] A 200 μm thick silicone film, a 160 μm thick PET (polyethylene terephthalate) film, and a 150 μm thick polyimide film were cut into 1 cm × 1 cm pieces and sandwiched between two copper plates to form a laminated structure consisting of three layers: copper, sample film, and copper. The PET film and polyimide film were pressed at a pressure of 30 MPa using a hot press set at 100°C and 120°C, respectively, to form an integrated product. For the silicone film, after lamination, the irradiation dose was 10 J / cm 2 The obtained adhesive test body was subjected to an adhesive test by a tensile test to measure the adhesive strength. In addition, in order to confirm the reliability of the adhesive properties, the obtained adhesive test body was aged and cooled in a chamber at 85°C and 85% humidity for 336 hours. After 500 cycles, the adhesive strength was measured again.

[0297] [Thermal stability of conductive pillar module precursor for semiconductor manufacturing]

[0298] Conductive pillars made of copper were placed on each sample film using a chip transfer device. The transfer process was carried out at room temperature for the silicone film, while the process was carried out at 100°C and especially 120°C while heating the stage for the PET and polyimide films. Only for the structure composed of the silicone film and the conductive pillars, after this process, the irradiation dose was 10 J / cm 2 The organic silicon film was cured by irradiating ultraviolet light with a wavelength of 365 nm in a manner and then exposing at 120° C. for one hour. The obtained structure was placed in an oven set at 250° C. for 30 seconds, and the warping of the structure and the movement of the conductive pillars were visually confirmed.

[0299] [Softening point]

[0300] The curable sample film composition (applicable only to silicone films) is formed into The pellets were placed on a heating plate set at 25°C to 100°C and pressed from above with a load of 100 grams for 10 seconds. After the load was removed, the deformation of the pellets was measured. The temperature at which the deformation in the height direction became 1 mm or more was defined as the softening point.

[0301] [Cure Characteristics]

[0302] According to the method specified in JIS K 6300-2:2001 "Unvulcanized rubber - Physical properties - Part 2: Method for determining vulcanization properties by a vibration vulcanization tester", a curable sample film composition (only applicable to silicone films) was vulcanized at a molding temperature (160°C) for 600 seconds using CURELASTOMETER (registered trademark) (PREMIER MDR manufactured by Alpha Technologies) to determine the curing properties. It should be noted that for the measurement, a block of about 5 g of the curable hot-melt silicone composition was weighed, clamped with a PET film having a thickness of 50 μm, and placed on the lower mold, and the time point when the upper mold was closed was taken as the start of the measurement. It should be noted that an R-type mold for rubber was used, the amplitude angle was set to 0.53°, the vibration frequency was set to 100 times / minute, and the torque range was set to the maximum of 230 kgf·cm for measurement. As the measurement result, the time (ts-1) required before the torque value of 1 dNm is exceeded was read in seconds.

[0303] [Production of silicone film]

[0304] Next, by the method shown in Reference Example 1, a hot-melt mixture of an organopolysiloxane resin and a linear organopolysiloxane was prepared.

[0305] [Reference Example 1: Hot-melt mixture 1]

[0306] It is a white solid at 25°C, with the average unit formula:

[0307] (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0308] 2.40 kg of the organopolysiloxane resin (vinyl content = 1.9 mass %) shown;

[0309] It is a white solid at 25°C, with the average unit formula:

[0310] (Me3SiO 1 / 2) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0311] 4.46 kg of the organopolysiloxane resin (vinyl content = 0 mass %) shown; and, by the formula:

[0312] ViMe2SiO(Me2SiO) 800 SiViMe2

[0313] 2.69 kg of dimethyl polysiloxane (vinyl content = 0.09 mass%) with dimethyl vinyl siloxane groups at both ends of the molecular chain;

[0314] The mixture was dissolved in 4.00 kg of xylene using a three-in-one motor in a barrel. The obtained solution was fed to a twin-screw extruder set at a maximum reaching temperature of 230°C, and xylene and low molecular weight organopolysiloxane components were removed under a vacuum degree of -0.08 MPa to obtain a hot-melt mixture 1. The mixture 1 was placed in a cylindrical barrel and cooled to solidify.

[0315] [Production Example 1]

[0316] The hot melt mixture 1 obtained in Reference Example 1 was melted at 170°C by a hot melt machine for cylindrical drums (VersaPail melter manufactured by Nordson). Fig.10 Line 11 is shown feeding a twin screw extruder at 9.55 kg / hr.

[0317] Then, the formula:

[0319] (PhSiO 3 / 2 ) 0.4 (HMe2SiO 1 / 2 ) 0.6 The organohydrogenpolysiloxane shown (the amount of volatile components when aged in an oven at 100°C under atmospheric pressure for 1 hour, i.e., the mass reduction rate is 3.4% by mass) 0.30 kg / hr. Methyltri-1,1-dimethyl-2-propynyloxysilane (boiling point = 245°C (1012.35 hPa)) in an amount of 300 ppm relative to the entire composition

[0320] The mixture consists of Fig.10 The feed line 13-a is shown as a feed. The set temperature of the input part is 150°C.

[0321] Next,

[0322] ViMe2SiO(Me2SiO) 800 SiViMe2

[0323] 0.15 kg / hr of dimethylvinylsiloxane (vinyl content = 0.09 mass%) capped at both ends of the molecular chain, and

[0324] A mixture of (methylcyclopentadienyl)trimethylplatinum (IV) (6.0 ppm by mass as platinum metal relative to the entire composition) Fig.10 The material was fed through pipeline 13-b (the set temperature of the input part was 80°C), and degassed and melt-kneaded at a vacuum degree of -0.08 MPa in the extruder.

[0325] The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened product. A release film (manufactured by TAKARAIN CORPORATION, FL2-01) with a width of 330 mm and a thickness of 125 μm was conveyed at a speed of 1.0 m / min, and the mixture was supplied to the release film at a supply rate of 5 kg / hr. The mixture was sandwiched between two release films in such a way that the release surface of the release film and the mixture were in contact with each other to form a laminate. Next, the laminate was pressurized between rollers controlled at a temperature of 90°C to stretch the above-mentioned mixture between the release films, thereby forming a laminate in which a curable hot-melt silicone composition film with a thickness of 300 μm was sandwiched between two release films, and then the entire laminate was cooled by air cooling. Fig.10 The structure of the manufacturing apparatus is shown. By peeling off the release film from the obtained laminated body, a bubble-free, flat, homogeneous, non-sticky, transparent curable hot-melt silicone composition film with a softening temperature of 85°C can be obtained. The irradiation dose is 10 J / cm 2 The obtained curable hot-melt silicone composition film was irradiated with ultraviolet rays having a wavelength of 365 nm, and then its curability at 100° C. was measured by the above-mentioned method. As a result, its ts-1 was 59 seconds.

[0326] Example 1

[0327] The hot melt silicone composition film obtained in Manufacturing Example 1 (hereinafter referred to as "silicone film") was used to evaluate the above-mentioned adhesive properties and thermal stability of the conductive pillar module precursor. The results are shown in Table 1. The obtained structure was placed in an oven set at 250°C for 30 seconds, and the warping of the structure and the movement of the conductive pillars were visually confirmed. The results are shown in Fig.11 .

[0328] Example 2

[0329] The above-mentioned adhesive properties and thermal stability of the conductive pillar module precursor were evaluated using a polyethylene terephthalate (PET) film. The results are shown in Table 1. The obtained structure was placed in an oven set at 250°C for 30 seconds, and the warping of the structure and the movement of the conductive pillars were visually confirmed. The results are shown in Fig.11 .

[0330] Example 3

[0331] The above-mentioned adhesive properties and thermal stability of the conductive pillar module precursor were evaluated using a polyimide (PI) film. The results are shown in Table 1. The obtained structure was placed in an oven set at 250°C for 30 seconds, and the warping of the structure and the movement of the conductive pillars were visually confirmed. The results are shown in Fig.11 .

[0332] [Table 1]

[0333]

[0334]

[0335] From the results in Table 1, it can be seen that the silicone film does not lose its adhesive properties to copper even after humidity aging or hot and cold cycles, but the adhesion of PET or polyimide to copper decreases after the durability test. Fig.11 The results show that any of the silicone film, PET film, and polyimide film can be used to manufacture the conductive column module precursor for semiconductor manufacturing, but when exposed to the same temperature (250°C) as the temperature applied in the reflow process for a short time, the columns in the PET film moved and warping was observed in the film, while the columns in the polyimide film did not move, but warping was observed in the film. From the above results, it can be seen that the silicone film is most suitable for making the conductive column module precursor for semiconductor manufacturing.

[0336] Industrial Applicability

[0337] The conductive pillar module precursor for semiconductor manufacturing of the present invention can be used for secondary wiring of a substrate of a flip chip package in semiconductor manufacturing, or for forming a redistribution layer (RDL) in a last chip (RDL first) package.

[0338] Explanation of symbols

[0339] A: Conductive column module precursor for semiconductor manufacturing

[0340] 1: Curable resin composition

[0341] 1': Resin cured product

[0342] 2: Conductive column parts

[0343] 3: Substrate

[0344] 4: Semiconductor chips

[0345] 5: Conductive layer (reconfiguration layer)

[0346] 6: Molded Underfill

[0347] 7: Molded parts

[0348] 8: Release liner

[0349] 9: Carrier components

[0350] 11: Hot melt machine

[0351] 12: Extruder

[0352] 13-a: Powder feeder

[0353] 13-b: Pump

[0354] 13-c: Pump

[0355] 14-a: Peel-off sheet

[0356] 14-b: Peel-off sheet

[0357] 15-a: stretching roller (can also be equipped with any temperature adjustment function)

[0358] 15-b: stretching roller (can also be equipped with any temperature adjustment function)

[0359] 16: Film thickness gauge

[0360] 17-a: Cooling roller

[0361] 17-b: Cooling roller

[0362] 18: Slicer

[0363] 19: Foreign matter inspection machine

Claims

1. A conductive column module precursor for semiconductor manufacturing, comprising a structure in which a conductive column member is supported by a sheet-like cured resin.

2. The conductive pillar module precursor for semiconductor manufacturing according to claim 1, wherein: The sheet-shaped resin cured material is an organic silicon cured material, and the conductive column component is a conductive column with a short diameter of 50 to 500 μm and a long diameter of 50 to 500 μm.

3. The conductive pillar module precursor for semiconductor manufacturing according to claim 1, wherein: The sheet-shaped resin cured material is an organic silicon cured material obtained by curing through a hydrosilation reaction, and the conductive column component is a cylindrical copper column with a diameter of 50 to 500 μm and a height of 50 to 2000 μm.

4. A conductive post module for semiconductor manufacturing, comprising a structure in which a conductive post member is supported by a sheet-like cured resin material, and the conductive post member is exposed from both sides of the sheet-like cured resin material.

5. A semiconductor or semiconductor precursor having the following structure: at least a portion of the conductive column component of the conductive column module for semiconductor manufacturing described in claim 4 is welded on a substrate, and the conductive column exposed from the surface on the opposite side of the sheet-like resin cured material is bonded to the semiconductor chip directly or via a conductive layer (reconfiguration layer). 6 . The semiconductor or semiconductor precursor according to claim 5 , further comprising a structure in which gaps between the substrate, the semiconductor chip and the conductive pillar member are filled with a molded underfill material. 7 . A method for manufacturing a semiconductor or a semiconductor precursor, comprising the step of bonding the conductive pillar member exposed from the conductive pillar module precursor for semiconductor manufacturing according to claim 1 to a semiconductor chip or a substrate.

8. The method for manufacturing a conductive pillar module precursor for semiconductor manufacturing according to claim 1, comprising the following steps (I) to (IV): Step (I): a step of disposing a conductive column component on a molded component; Step (II): a step of disposing at least one curable resin composition and any release liner on the conductive column component; Step (III): a step of curing the curable resin composition into a sheet by one or more curing mechanisms selected from heating and high-energy ray irradiation; and Step (IV): a step of separating the conductive pillar module precursor for semiconductor manufacturing from the molded part after removing any of the release liners.

9. A manufacturing method, which is the manufacturing method of the conductive column module precursor for semiconductor manufacturing according to claim 8, characterized in that: The curable resin composition used in step (II) is a sheet of a curable resin composition having heat-melting properties, and the step is as follows: after the sheet of the curable resin composition is arranged on the conductive column component, the sheet of the curable resin composition is heated and melted, thereby at least a portion of the conductive column is supported inside the sheet of the curable resin composition.

10. A manufacturing method, which is the manufacturing method of the conductive column module precursor for semiconductor manufacturing according to claim 8, characterized in that: The curable resin composition used in the step (II) is a hydrosilylation-curable silicone sheet having heat-melting properties, and the step is as follows: after the hydrosilylation-curable silicone sheet is arranged on the conductive column component, the hydrosilylation-curable silicone sheet is heated and melted, thereby at least a part of the conductive column component is supported inside the sheet of the curable resin composition, and The step (III) is a step of curing the hydrosilylation reaction-curable silicone sheet into a sheet-like shape by one or more curing mechanisms selected from heating and high-energy ray irradiation.

11. The method for manufacturing a conductive column module precursor for semiconductor manufacturing according to claim 8, further comprises the following step after the step (IV): after bonding any exposed conductive column component to a semiconductor chip or substrate, the conductive column is exposed on both sides of the sheet-like resin cured material by shaving off at least one side of the sheet-like resin cured material.

12. The method for manufacturing a conductive pillar module precursor for semiconductor manufacturing according to claim 1, comprising the following steps (I') to (V'): Step (I'): a step of disposing a conductive column component on a first molding component; Step (II'): a step of disposing a second molding component on the conductive column component; Step (III'): a step of filling the gap between the conductive column member, the first molding member, and the second molding member with a curable resin composition; Step (IV'): a step of curing the curable resin composition into a sheet by one or more curing mechanisms selected from heating and high-energy ray irradiation; and Step (V′): a step of separating the first molding member and the second molding member from the conductive pillar module precursor for semiconductor manufacturing.

13. A method for producing a semiconductor or a semiconductor precursor, comprising the following steps (L1) to (L5): Step (L1): a step of making the conductive column module precursor for semiconductor manufacturing according to claim 1 closely adhere to a carrier component; Step (L2): a step of bonding the conductive pillar member on one side of the conductive pillar module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a semiconductor chip; Step (L3): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin; Step (L4): a step of soldering the conductive column component exposed in step (L3) onto a substrate; as well as, Process (L5): A process of filling the gaps between the substrate, the semiconductor chip, and the conductive pillar members with a molded underfill material.

14. A method for producing a semiconductor or a semiconductor precursor, comprising the following steps (L1') to (L5'): Step (L1'): a step of making the conductive column module precursor for semiconductor manufacturing according to claim 1 closely adhere to a carrier component; Step (L2'): a step of bonding the conductive column component on one side of the conductive column module precursor for semiconductor manufacturing, which is exposed from the sheet-like cured resin, to a substrate by welding; Step (L3'): after removing the carrier member from the conductive pillar module precursor for semiconductor manufacturing, at least one surface of the sheet-like cured resin is shaved off to expose the conductive pillars on the surface of the sheet-like cured resin; Step (L4'): a step of bonding the conductive pillars exposed in step (L3') directly or via a conductive layer (reconfiguration layer) to a semiconductor chip; and Step (L5'): a step of filling the gaps between the substrate, the semiconductor chip, and the conductive pillars with a molded underfill material.

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