WO2024038819A1 - Élément de maintien de pièce et stratifié - Google Patents

Élément de maintien de pièce et stratifié Download PDF

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Publication number
WO2024038819A1
WO2024038819A1 PCT/JP2023/029191 JP2023029191W WO2024038819A1 WO 2024038819 A1 WO2024038819 A1 WO 2024038819A1 JP 2023029191 W JP2023029191 W JP 2023029191W WO 2024038819 A1 WO2024038819 A1 WO 2024038819A1
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WO
WIPO (PCT)
Prior art keywords
layer
holding member
support
workpiece
workpiece holding
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Application number
PCT/JP2023/029191
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English (en)
Japanese (ja)
Inventor
亜樹子 田中
亮 伊関
達也 鈴木
瑞穂 水野
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2024038819A1 publication Critical patent/WO2024038819A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/26—Porous or cellular plastics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering

Definitions

  • the present invention relates to a work holding member and a laminate. More specifically, the present invention relates to a workpiece holding member and a laminate in which a workpiece is held on the workpiece holding member.
  • Patent Documents 1 and 2 Conventionally, in manufacturing electronic component devices, it has been known to mount electronic components on the surface of a workpiece such as a board, that is, to surface-mount electronic components on the workpiece (for example, Patent Documents 1 and 2 below).
  • Patent Document 1 discloses that in manufacturing a semiconductor device, which is an electronic component device, a semiconductor chip, which is an electronic component, is attached to the surface of a substrate (work), and a reflow treatment is performed on the semiconductor chip after being attached to the substrate. It is disclosed that the substrate is placed on a stage during mounting.
  • Patent Document 1 discloses that a semiconductor chip stack is obtained by stacking a plurality of semiconductor chips including bump electrodes in the height direction, and the semiconductor chip stack is placed on a support substrate (work). After placing the support substrate with the semiconductor chip stack attached on the first stage, which is a carrier plate, the first stage, which is a carrier plate, is placed on a stage in a heating furnace, which is a second stage. It is disclosed that a semiconductor device is manufactured by mounting a semiconductor chip on a support substrate, performing reflow processing on the support substrate, and mounting the semiconductor chip on the support substrate.
  • the reflow treatment is usually performed such that the peak top temperature in the heating furnace is approximately 270°C.
  • Patent Document 2 discloses that in manufacturing an organic EL device that is an electronic component device, a transparent electrode film such as an IZO film or an ITO film that is an electronic component is attached on a transparent substrate (work), and the transparent electrode film is annealed. It is disclosed that the transparent substrate is placed on a stage during mounting.
  • a transparent electrode film such as an IZO film or an ITO film that is an electronic component
  • Patent Document 2 discloses that after placing the transparent substrate on a substrate stage and attaching a transparent electrode film, which is an electronic component, on the transparent substrate by sputtering, an annealing treatment is performed. It is disclosed that an organic EL device is manufactured by mounting the transparent electrode film on a transparent substrate.
  • the annealing treatment is usually performed at a temperature of about 150° C. in order to fully develop the function of the transparent electrode film.
  • the board When electronic components are mounted on a board (work) as described above, the board is usually placed on a stage with some member interposed.
  • the substrate is placed on a stage with a work holding member including a support and a work holding layer laminated on the support.
  • the substrate is placed on the stage by placing the support body on the stage with the substrate (work) being held by the work holding layer of the work holding member.
  • the substrate (work) to which a semiconductor chip is attached or the substrate (work) to which a transparent electrode film is attached is attached to the workpiece holding member (more specifically , the work holding layer of the work holding member), but is removed from the work holding member after heat treatment during surface mounting of electronic components, such as after reflow treatment or annealing treatment. Therefore, from the viewpoint of efficiently manufacturing electronic component devices, it is preferable that the substrate (work) is sufficiently fixed to the workpiece holding member before heat treatment during surface mounting of electronic components, and It is preferable that the component can be easily removed from the workpiece holding member after heat treatment during surface mounting of the component.
  • the support and workpiece holding layer must be sufficiently fixed so that they do not separate even when the substrate (workpiece) is removed from the workpiece holding member. be.
  • sufficient studies have been made on a method for sufficiently fixing the workpiece holding layer on the support while maintaining the function of the workpiece holding layer.
  • the present invention is capable of sufficiently fixing the workpiece before heat treatment during surface mounting of electronic components, making it easy to remove the workpiece after heat treatment during surface mounting of electronic components, and maintaining the function of the workpiece holding layer.
  • An object of the present invention is to provide a workpiece holding member in which a workpiece holding layer is sufficiently fixed on a support body.
  • Another object of the present invention is to provide a laminate in which a workpiece is held by the workpiece holding member.
  • a workpiece holding member includes a support, an adhesive layer laminated on the support, and a workpiece holding layer laminated on the adhesive layer to hold the workpiece. It has been found that by forming the workpiece holding layer as a foam layer of a resin composition, the workpiece can be sufficiently fixed before heat treatment, and the workpiece can be easily removed after heat treatment.
  • the work holding layer in the work holding member can be formed on the support while maintaining the function of the work holding layer. was found to be able to be sufficiently fixed.
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition
  • a workpiece holding member, wherein the adhesive layer is a molecular adhesive layer.
  • the above-mentioned material satisfies any of the following (i) to (iii) when a peel test is conducted between the support and the workpiece holding layer according to the following procedures (1) to (3).
  • the workpiece holding member according to [1] or [2]. (1) In a double-sided adhesive tape having an acrylic adhesive layer on one side of the main surface of a polyester film base material and a silicone adhesive layer on the other side, a PET film is attached to the acrylic adhesive layer side, A sample is prepared in which a workpiece holding layer of a workpiece holding member is attached to the silicone adhesive layer side. (2) The sample is allowed to stand at 50°C for 24 hours, and then at 23°C for 30 minutes.
  • the molecular adhesive forming the molecular adhesive layer contains a compound having at least one of a first reactive group RG1 and a second reactive group RG2,
  • the first reactive group RG1 is at least one selected from the group consisting of an amino group and an azide group
  • the molecular adhesive further has a triazine ring, and the group containing the first reactive group RG1 and the group containing the second reactive group RG2 are bonded to the triazine ring, according to [5] above. Work holding member.
  • the work holding layer has a shear adhesion value S to the polyimide film of 1N/100mm2 or more before heating at a temperature of 150°C or higher, and a polyimide film after heating at a temperature of 150°C or higher for 5 minutes.
  • the workpiece holding member according to [1] or [2] above, wherein the value P of 90° peeling force against the surface of the workpiece is 7 N/20 mm or less.
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work;
  • a laminate comprising: a workpiece held on the workpiece holding layer;
  • a laminate, wherein the workpiece holding member is the workpiece holding member described in [1] or [2] above.
  • the workpiece can be sufficiently fixed before the heat treatment during surface mounting of electronic components, the workpiece can be easily removed after the heat treatment during surface mounting of electronic components, and the function of the workpiece holding layer is maintained. It is possible to provide a work-holding member in which the work-holding layer is sufficiently fixed on the support while the workpiece-holding layer remains in place.
  • FIG. 1 is a sectional view showing the configuration of a workpiece holding member according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing the structure of a laminate according to an embodiment of the present invention.
  • FIG. 3A is a cross-sectional view showing how a workpiece is held on the workpiece holding layer of the workpiece holding member.
  • FIG. 3B is a cross-sectional view showing a state in which a workpiece is held on the workpiece holding layer of the workpiece holding member.
  • FIG. 3C is a cross-sectional view showing how a semiconductor chip is attached onto a workpiece.
  • FIG. 3D is a cross-sectional view showing how a semiconductor chip mounted on a workpiece is sealed with resin.
  • FIG. 3E is a cross-sectional view showing how a workpiece to which a resin-sealed semiconductor chip is attached is removed from a workpiece holding member.
  • the work holding member according to the first embodiment of the present invention is A work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition,
  • the thickness of the adhesive layer is 2 ⁇ m or less.
  • the work holding member according to the second embodiment of the present invention is A work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition
  • the adhesive layer is a molecular adhesive layer.
  • a workpiece holding member according to an embodiment of the present invention will be described with reference to FIG. 1.
  • the work holding member according to the first embodiment of the present invention and the work holding member according to the second embodiment will be collectively referred to as the work holding member according to the embodiment of the present invention, or the present embodiment. It is sometimes referred to as a workpiece holding member.
  • the workpiece holding member 10 includes a support 1, an adhesive layer 2 laminated on the support 1, and a workpiece holding layer 3 laminated on the adhesive layer 2 to hold the workpiece. Be prepared.
  • the support 1 supports a workpiece holding layer 3 via an adhesive layer 2, which will be described later.
  • the support 1 is not particularly limited as long as it can support the workpiece holding layer 3 via the adhesive layer 2, but as described later, when the adhesive layer 2 is a molecular adhesive layer, It is preferable that the support 1 has a partial structure that strongly chemically bonds with the compound contained in the molecular adhesive layer. That is, the material of the support 1 is preferably selected such that the support 1 can form chemical bonds via the molecular adhesive layer.
  • the material of the support 1 is such that the main surface of the support 1 on the side on which the adhesive layer 2 is laminated is selected from the group consisting of a hydrocarbon group, a carbonyl group, a carboxyl group, and a hydroxyl group. It is preferably selected to have at least one selected reactive group and to form a chemical bond with the molecular adhesive layer.
  • a support 1 high adhesive strength can be obtained between the support 1 and the molecular adhesive layer, and peeling between the support 1 and the molecular adhesive layer can be prevented.
  • the work holding layer 3 can be sufficiently fixed on the body.
  • Examples of the material for the support 1 include acrylic resin, olefin resin, olefin ionomer resin, polyester resin, polyamide resin, rubber, metal, glass, and ceramic.
  • acrylic resins include homopolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers, (meth)acrylic monomers, and monomers copolymerizable with the same. Examples include copolymers with copolymers.
  • Examples of (meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- Examples include (meth)acrylic acid esters such as ethylhexyl (meth)acrylate; (meth)acrylic acid;
  • Monomers copolymerizable with (meth)acrylic monomers include ethylene; aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; cyano group-containing ethylenes such as acrylonitrile and methacrylonitrile; (meth)acrylamide monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; and the like.
  • resins other than acrylic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM ( (polyacetal), PEEK (polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), and the like.
  • PPS polyphenylene sulfide
  • PA polyamide
  • PET polyethylene terephthalate
  • PES polyether sulfide
  • the rubber may be either natural rubber or synthetic rubber.
  • examples of the above-mentioned rubber include nitrile rubber (NBR), methyl methacrylate-butadiene rubber (MBR), styrene-butadiene rubber (SBR), acrylic rubber (ACM, ANM), urethane rubber (AU), and silicone rubber.
  • NBR nitrile rubber
  • MRR methyl methacrylate-butadiene rubber
  • SBR styrene-butadiene rubber
  • acrylic rubber ACM, ANM
  • AU urethane rubber
  • silicone rubber silicone rubber.
  • NBR nitrile rubber
  • MRR methyl methacrylate-butadiene rubber
  • silicone rubber silicone rubber
  • the metal examples include metals selected from gold, silver, copper, aluminum, iron, titanium, alloys containing one or more of these, and materials containing stainless steel. Among these, materials containing copper, aluminum, or titanium or materials containing stainless steel are preferred, and materials containing aluminum or stainless steel are more preferred.
  • the glass examples include alkali-free glass, soda glass, borosilicate glass, aluminosilicate glass, and the like.
  • Examples of the ceramic include silicon wafer, alumina ceramic, zirconia ceramic, silicon nitride ceramic, aluminum nitride ceramic, and silicon carbide ceramic.
  • the thickness of the support 1 is preferably 0.3 mm or more, more preferably 0.5 mm or more, and even more preferably 1.0 mm or more.
  • the thickness of the support 1 is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, and 2. It is more preferably .0 mm or less, and particularly preferably 1.5 mm or less.
  • the thickness of the support 1 can be measured using, for example, a thickness gauge.
  • a thickness gauge examples include the thickness gauge JA-257 manufactured by Ozaki Seisakusho Co., Ltd. (terminal size: top and bottom ⁇ 20 mm).
  • the support 1 has a ratio of the three-point bending stress to the linear expansion coefficient of 0.3 or more.
  • the support body 1 becomes easier to bend as the value of the three-point bending stress becomes lower, so that the workpiece held by the workpiece holding layer 3 becomes more likely to warp. Further, as the value of the linear expansion coefficient increases, the support 1 becomes more likely to expand, and therefore, the workpiece held on the workpiece holding layer 3 becomes more likely to warp as the support 1 expands. Therefore, in the workpiece holding member 10, in order to suppress the warping that occurs in the workpiece held on the workpiece holding layer 3 of the workpiece holding member 10, it is preferable that the linear expansion coefficient of the support body 1 is as high as possible. The lower the stress value, the better.
  • the ratio of the three-point bending stress to the linear expansion coefficient of the support 1 is preferably 0.3 or more.
  • the ratio is such that the linear expansion coefficient is high and the three-point bending stress is low, the support 1 is less likely to warp. Therefore, also in the heat treatment during surface mounting of electronic components, it is possible to suppress warping of the workpiece held by the workpiece holding layer 3, which is preferable.
  • the three-point bending stress of the support 1 is preferably 5 N/10 mm or more, more preferably 6 N/10 mm or more, even more preferably 7 N/10 mm or more, and preferably 8 N/10 mm or more. Particularly preferred.
  • the upper limit of the three-point bending stress of the support 1 is usually 200N/10mm.
  • the three-point bending stress of the support 1 can be measured using a tensile compression tester (model "TG-5KN", manufactured by Minevia) according to the following procedures (1) to (3).
  • a tensile compression tester model "TG-5KN", manufactured by Minevia
  • (1) A support with a width of 10 mm and a length of 100 mm is prepared as a test specimen.
  • the tensile tester grips the specimen at a location 35 mm away from the center toward one end in the length direction and at a location 35 mm away from the center toward the other end in the length direction. Grip each member.
  • the linear expansion coefficient of the support 1 is preferably 30 ⁇ 10 ⁇ 6 /°C or less, more preferably 25 ⁇ 10 ⁇ 6 /°C or less, and preferably 20 ⁇ 10 ⁇ 6 /°C or less. More preferred.
  • the lower limit of the linear expansion coefficient of the support 1 is usually 5 ⁇ 10 ⁇ 6 /°C.
  • the linear expansion coefficient of the support 1 can be measured by thermomechanical analysis (TMA method).
  • Thermomechanical analysis can be performed under the following conditions.
  • ⁇ Device name Thermomechanical analyzer (product name: "TMA/SS7100, manufactured by SII Nanotechnology")
  • ⁇ Measurement mode Tensile method ⁇ Temperature range: -50°C ⁇ 300°C ⁇ Temperature increase rate: 10°C/min
  • ⁇ Sample shape 5mm square, 10mm height prismatic
  • ⁇ Standard sample Alumina
  • the ratio of the value of the three-point bending stress to the value of the coefficient of linear expansion can be obtained by dividing the value of the three-point bending stress obtained as above by the value of the coefficient of linear expansion. Can be done.
  • the support 1 may be surface-modified.
  • surface modification include introduction of hydroxyl groups by corona treatment.
  • the arithmetic mean roughness Ra of the surface of the support 1 on which the adhesive layer 2 described later is laminated is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.4 ⁇ m or less. . Further, the arithmetic mean roughness Ra of the surface of the support 1 on which the adhesive layer 2 is laminated is preferably 0.01 ⁇ m or more, more preferably 0.015 ⁇ m or more.
  • the workpiece holding layer 3 can be more fully fixed to the support 1 via the adhesive layer 2. can do.
  • the arithmetic mean roughness Ra of the surface of the support 1 on which the adhesive layer 2 is laminated can be measured in accordance with JIS B 0601 (1994). As the measurement conditions, the following can be adopted.
  • ⁇ Measurement device Confocal laser microscope (model: LEXT OLS5000, manufactured by Olympus)
  • ⁇ Settings High precision settings
  • ⁇ Filter Gaussian filter
  • the adhesive layer 2 is laminated on the support 1 and adheres the support 1 and the workpiece holding layer 3.
  • the thickness of the adhesive layer 2 is 2 ⁇ m or less. Since the thickness of the adhesive layer 2 is 2 ⁇ m or less, the workpiece holding layer 3 can be sufficiently fixed onto the support body 1 while maintaining the function of the workpiece holding layer 3.
  • the thickness of the adhesive layer 2 is preferably 500 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 50 nm or less. Further, the thickness of the adhesive layer 2 may be 0.5 nm or more, and preferably 1 nm or more.
  • a PET film is attached to the acrylic adhesive layer side
  • a sample is prepared in which a workpiece holding layer of a workpiece holding member is attached to the silicone adhesive layer side.
  • the workpiece holding layer breaks in (ii) above means that the workpiece holding layer breaks before peeling occurs between the support and the workpiece holding layer.
  • Peeling occurs between the workpiece holding layer and the PET film means (a) Peeling occurs between the PET film and the acrylic adhesive layer, (b) Peeling occurs between the acrylic adhesive layer and the polyester (c) Peeling occurs between the polyester film base material and the silicone adhesive layer; (d) Peeling occurs between the silicone adhesive layer and the workpiece holding layer. This includes both cases of occurrence.
  • peeling occurs between the support and the workpiece holding layer means (e) peeling occurs between the workpiece holding layer and the adhesive layer, and (f) peeling occurs between the adhesive layer and the support. This includes any case where peeling occurs.
  • examples of the adhesive layer 2 include a molecular adhesive layer described below, a silicone adhesive, a polymer-type silane coupling agent, and the like.
  • the adhesive layer 2 is a molecular adhesive layer.
  • the molecular adhesive layer is not attached to the support and workpiece holding layer by intermolecular force like normal adhesives, but is bonded to the support and workpiece holding layer by chemical bonds such as covalent bonds. are chemically combined. Therefore, even if the support body and the workpiece holding layer are made of different materials or materials that are difficult to bond to, it is possible to form a workpiece holding member with excellent adhesive strength and high adhesion.
  • chemical bonds include covalent bonds, coordinate bonds, and ionic bonds, but do not include intermolecular forces.
  • the molecular adhesive layer can be formed using a molecular adhesive.
  • the molecular adhesive layer includes a compound having a first reactive group RG1 (hereinafter also referred to as first reactive group RG1 or RG1) that can form a chemical bond with the support and a chemical bond with the workpiece holding layer. It is preferable that at least one compound having a second reactive group RG2 (hereinafter also referred to as second reactive group RG2 or RG2) that can be formed is included.
  • first reactive group RG1 hereinafter also referred to as first reactive group RG1 or RG1
  • second reactive group RG2 hereinafter also referred to as second reactive group RG2 or RG2
  • the molecular adhesive may include a compound having at least one of the first reactive group RG1 and the second reactive group RG2.
  • first reactive group RG1 and the second reactive group RG2 may be different from each other.
  • the individual molecules constituting the molecular adhesive layer may be referred to as adhesive molecules.
  • adhesive molecules it is referred to as a molecular adhesive or an adhesive molecule regardless of whether it is in a state before or after forming a chemical bond with a support and a workpiece holding layer.
  • the molecular adhesive may contain components other than adhesive molecules (eg, a polymerization initiator).
  • the support and the workpiece holding layer have one adhesive molecule and the adhesive molecule has the first reactive group RG1 and the second reactive group RG2.
  • the bond may be formed by a chemical bond formed by the first reactive group RG1 of the adhesive molecule and the support, and a chemical bond formed by the workpiece holding layer and the second reactive group RG2 of the adhesive molecule.
  • first reactive group RG1 or the second reactive group RG2 can react with itself to form a chemical bond (for example, when the second reactive groups RG2 can react with each other to form a chemical bond)
  • multiple adhesive molecules may mediate the chemical bond between the support and the workholding layer.
  • the adhesive molecule may form a chemical bond by reaction between the silanol groups and/or alkoxysilyl groups.
  • tens to hundreds of adhesive molecules of the molecular adhesive layer can intervene in the chemical bond between the support and the workholding layer.
  • the fewest adhesive molecules intervening in the chemical bond between the support and the workholding layer can be a monolayer.
  • molecular adhesives contain many adhesive molecules that form such chemical bonds, they do not necessarily form a dense layer of adhesive molecules. If there are fewer reactive points to form chemical bonds in the support, the adhesive molecules may be sparsely present.
  • the first reactive group RG1 of the adhesive molecule may form a chemical bond with both the support and the workpiece holding layer.
  • an adhesive molecule (hereinafter referred to as a first adhesive molecule) that has formed a chemical bond between the support and the first reactive group RG1, and an adhesive that has formed a chemical bond between the workpiece holding layer and the first reactive group RG1.
  • An agent molecule (hereinafter referred to as a second adhesive molecule) is formed by forming a chemical bond between the second reactive group RG2 of the first adhesive molecule and the second reactive group RG2 of the second adhesive molecule.
  • the support and the work holding layer will be bonded by chemical bonds.
  • two adhesive molecules exist between the support and the workpiece holding layer.
  • first reactive group RG1 or the second reactive group RG2 can react with itself to form a chemical bond, then neither the first adhesive molecule nor the second adhesive molecule , one or more third adhesive molecules may intervene in the chemical bond between the support and the workholding layer.
  • the adhesive molecule may have at least one reactive group selected from the group consisting of, for example, an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, an epoxy group, a silanol group, and an alkoxysilyl group.
  • it has at least one reactive group selected from the group consisting of an amino group, an azide group, a silanol group, and an alkoxysilyl group.
  • An alkoxysilyl group produces a silanol group through a hydrolysis reaction.
  • the molecular adhesive forming the molecular adhesive layer contains a compound having at least one of a first reactive group RG1 and a second reactive group RG2, and the first reactive group RG1 is At least one selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and the second reactive group RG2 is at least one selected from a silanol group and an alkoxysilyl group. Preferably it is a seed.
  • the support 1 and the molecular adhesive layer can be prevented from peeling off, and the workpiece holding layer 3 can be sufficiently fixed onto the support 1 via the molecular adhesive layer.
  • the molecular adhesive forming the molecular adhesive layer contains a compound having a first reactive group RG1 and a second reactive group RG2, and the first reactive group RG1 is an amino group, an azide group,
  • the second reactive group RG2 is preferably at least one selected from the group consisting of a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and the second reactive group RG2 is preferably at least one selected from a silanol group and an alkoxysilyl group. .
  • the molecular adhesive forming the molecular adhesive layer contains a compound having at least one of a first reactive group RG1 and a second reactive group RG2, and the first reactive group RG1 is at least one selected from the group consisting of an amino group and an azide group, and the second reactive group RG2 is at least one selected from a silanol group and an alkoxysilyl group.
  • the molecular adhesive forming the molecular adhesive layer contains a compound having a first reactive group RG1 and a second reactive group RG2, and the first reactive group RG1 is an amino group, and The second reactive group RG2 is at least one selected from the group consisting of azide groups, and the second reactive group RG2 is at least one selected from a silanol group and an alkoxysilyl group.
  • the adhesive molecules can be used alone or in combination of two or more. Two or more types of adhesive molecules may be used as a mixture, or molecular adhesive layers each formed of two or more types of adhesive molecules may be laminated and used.
  • the molecular adhesive layer contains an adhesive molecule containing an amino group as the first reactive group RG1 and at least one selected from a silanol group and an alkoxysilyl group as the second reactive group RG2.
  • the adhesive molecule further has a triazine ring, and a group containing the first reactive group RG1 and a group containing the second reactive group RG2 are bonded to the triazine ring.
  • the first reactive group RG1 is at least one selected from the group consisting of an amino group and an azide group
  • the second reactive group RG2 is at least one selected from the group consisting of a silanol group and an alkoxysilyl group
  • One reactive group may form a chemical bond with the surfaces of the support 1 and the workpiece holding layer 3
  • the second reactive groups may form a chemical bond with each other.
  • the adhesive molecule is preferably a compound represented by the following general formula [I]. That is, it is preferable that the molecular adhesive contains a compound represented by the following general formula [I].
  • E represents a divalent linking group
  • F represents OH or an OH-generating group
  • Q 1 and Q 2 each independently represent N 3 or -NR 1 (R 2 ).
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, an aminoalkyl group, or -R-Si(R') n (OA) 3-n .
  • R represents a chain divalent hydrocarbon group having 1 to 12 carbon atoms.
  • each R' independently represents a chain hydrocarbon group having 1 to 4 carbon atoms.
  • A's each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 4 carbon atoms.
  • n represents an integer from 0 to 2.
  • the divalent linking group represented by E is not particularly limited, but can include a divalent hydrocarbon group and a divalent linking group containing a hetero atom.
  • examples of the divalent hydrocarbon group represented by E include branched, chain, or cyclic hydrocarbon groups having 1 to 12 carbon atoms; A chain hydrocarbon group is preferred. Among these, linear alkylene groups having 1 to 6 carbon atoms are preferred, and specific examples include methylene, ethylene, propylene, butylene, and pentamethylene groups, with ethylene being preferred.
  • R 201 represents a hydrogen atom, an alkyl group, an aminoalkyl group, or -R-Si(R') n (OA) 3-n , and preferably represents a hydrogen atom.
  • E 101 represents the divalent hydrocarbon group in the above E, and preferable ones are also the same.
  • *- represents a bond bonded to the triazine ring.
  • a in -R-Si(R') n (OA) 3-n represented by R 201 is the same as A described below, and preferable ones are also the same.
  • the OH-generating group in general formula [I] is a group containing a hydroxyl group, or a group that reacts with water or a compound containing a hydroxyl group to produce a hydroxyl group.
  • the OH-generating group preferably represents, for example, -Si(R') n (F1) 3-n , a halogen atom, or an alkoxy group, and is -Si(R') n (F1) 3-n. is more preferable.
  • F1 represents a hydroxyl group, an alkoxy group, or a halogen atom, and preferably represents a hydroxyl group or an alkoxy group.
  • halogen atom examples include fluorine, chlorine, and iodine, with chlorine being preferred.
  • F contains a silanol group or an alkoxysilyl group.
  • the hydrocarbon group having 1 to 24 carbon atoms represented by R 1 and R 2 is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms. Preferably, it is an alkyl group having 1 to 6 carbon atoms.
  • the aminoalkyl group represented by R 201 , R 1 and R 2 is preferably an aminoalkyl group having 1 to 12 carbon atoms, more preferably an aminoalkyl group having 1 to 6 carbon atoms, such as an aminomethyl group or an aminoethyl group. , aminopropyl group, aminobutyl group, aminopentyl group, and aminohexyl group are preferred, and aminoethyl group (-CH 2 CH 2 NH 2 ) is particularly preferred.
  • the chain-like divalent hydrocarbon group having 1 to 12 carbon atoms represented by R is preferably a chain-like divalent hydrocarbon group having 1 to 10 carbon atoms.
  • linear alkylene groups having 1 to 6 carbon atoms are preferred, and specific examples include methylene, ethylene, propylene, butylene, and pentamethylene groups, with ethylene being preferred.
  • Examples of the chain hydrocarbon group having 1 to 4 carbon atoms represented by R' and A include a methyl group, an ethyl group, a propyl group, and a butyl group, with an ethyl group being preferred.
  • n represents an integer from 0 to 2, and preferably n is 0.
  • Adhesive molecules having a triazine ring represented by the above general formula [I] at least one selected from the group consisting of an amino group and an azide group, and at least one selected from a silanol group and an alkoxysilyl group Adhesive molecules having the following are preferred.
  • the amino or azide group of this adhesive molecule is attached to the triazine ring.
  • the number of amino groups or azide groups bonded to the triazine ring is, for example, one or two.
  • the OH or OH-generating group is preferably indirectly bonded to the triazine ring (C atom) via a divalent linking group.
  • the number of indirectly bonded alkoxysilyl groups is one or two or more.
  • the azide group bonded to the triazine ring (electron localized conjugated skeleton) has a high decomposition energy to nitrene. Therefore, effects from near ultraviolet rays and visible light are unlikely to occur. Therefore, the workability of ultraviolet exposure is improved.
  • Nitranes that are attached to a triazine ring are more stable than those that are not. Bonding between nitrenes is suppressed. Hydrogen abstraction activity for C--H bonds and addition activity for unsaturated bonds are enhanced. That is, an effective reaction is possible with a small amount of exposure.
  • the alkoxysilyl group is bonded to the triazine ring (electron localization conjugated skeleton) via a spacer (for example, an amino group, an oxy group, and/or a hydrocarbon group). Therefore, when adhesive molecules are bonded to a support or a workpiece holding layer, the entropy effect for forming a chemical bond increases upon contact with the surface of the other support or workpiece holding layer. The improvement in the entropy effect is reflected in an increase in the frequency factor in the interfacial reaction after contact with the support or workpiece holding layer. And if the length of the spacer is too long, the cost will increase. In addition, a decrease in the amount of absorbed adhesive molecules occurs. Therefore, spacers of appropriate length are preferred. From this point of view, adhesive molecules represented by the following general formulas [Io], [Ia], and [Ib] are preferred.
  • R 101s each independently represents an aminoalkyl group or -R-Si(R') n (OA) 3-n .
  • R 102 represents -R-Si(R')n(OA) 3-n .
  • R 201 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, an aminoalkyl group, or -R-Si(R') n (OA) 3-n .
  • R represents a chain divalent hydrocarbon group having 1 to 12 carbon atoms.
  • each R' independently represents a chain hydrocarbon group having 1 to 4 carbon atoms.
  • A's each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 4 carbon atoms.
  • n represents an integer from 0 to 2.
  • aminoalkyl groups, R, R', A, and n in the general formulas [Io], [Ia], and [Ib] are the aminoalkyl groups, R, R', A, and n in the general formula [I], respectively. They have the same meaning and are also preferred.
  • R 101 preferably represents an aminoalkyl group
  • R 201 preferably represents a hydrogen atom
  • the alkoxysilyl group in the general formulas [Io], [Ia], and [Ib] is an OH-forming group (OH precursor) in most cases.
  • OH precursor OH-forming group
  • it may be treated with water (neutral water, acidic water, alkaline water), for example.
  • corona discharge treatment or plasma treatment may be performed.
  • water treatment is preferred.
  • the compound having a reactive group contained in the molecular adhesive the following compounds can be exemplified.
  • Examples of compounds having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N,N-dimethyl amino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, 3 -(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)
  • Examples of the compound having an azido group include (11-azidoundecyl)trimethoxysilane, (11-azidoundecyl)triethoxysilane, and the compounds (17) to (19) below.
  • Examples of compounds having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.
  • Examples of the compound having an isocyanate group include 3-(trimethoxysilyl)propylisocyanate and 3-(triethoxysilyl)propylisocyanate.
  • Examples of compounds having a ureido group include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.
  • Examples of compounds having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Can be mentioned.
  • Examples of compounds in which the molecular adhesive has two or more first reactive groups RG1 in one molecule include the following compounds (11) to (19).
  • the compound having the first reactive group RG1 and the second reactive group RG2 prevents the support 1 from peeling off from the molecular adhesive layer, and even allows the workpiece to be placed on the support 1 via the molecular adhesive layer.
  • the compounds (11) to (19) above are preferred.
  • the molecular adhesive layer can be laminated on the support, for example, as follows.
  • a treatment liquid (solution or dispersion) containing adhesive molecules is prepared.
  • Solvents used include water, alcohols (e.g. methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, cellosolve, carbitol), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone), aromatic hydrocarbons (e.g. benzene, toluene, xylene), aliphatic hydrocarbons (e.g. butane, hexane, octane, decane, dodecane, octadecane), esters (e.g.
  • ethers e.g. (tetrahydrofuran, butyl ether, ethyl butyl ether, anisole
  • halogen-containing solvents such as methylene chloride
  • amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone.
  • the content of adhesive molecules may be from 0.05 to 10% by weight, preferably from 0.10 to 1% by weight. This is because if the content of adhesive molecules is too small, the effect will be poor. On the contrary, the amount of reaction with the support is limited, and even if it is too large, it is meaningless. From this point of view, the above ratio is preferable.
  • a surfactant is added to the treatment liquid as necessary from the viewpoint of adjusting the surface tension.
  • nonionic surfactants e.g., nonionic surfactants consisting of a long alkyl chain and polyethylene glycol
  • cationic surfactants e.g., quaternary ammonium salts
  • anionic surfactants e.g., (organic carboxylates, sulfonates) are used.
  • the adhesive molecule contains an azide group
  • a molecular adhesive containing a compound represented by the following general formula [I'] where Q 1 is N 3 in the above general formula [I]
  • the support is irradiated with light (ultraviolet light).
  • E represents a divalent linking group
  • F represents OH or an OH-generating group
  • Q represents N 3 or -NR 1 (R 2 ).
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms, an aminoalkyl group, or -R-Si(R') n (OA) 3-n .
  • R represents a chain divalent hydrocarbon group having 1 to 12 carbon atoms.
  • each R' independently represents a chain hydrocarbon group having 1 to 4 carbon atoms.
  • A's each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 4 carbon atoms.
  • n represents an integer from 0 to 2.
  • the light is irradiated only at the locations where adhesive molecules are desired to be bonded to the support.
  • the light (ultraviolet) irradiation for example, a UV irradiation device (eg, high pressure mercury UV lamp, low pressure mercury UV lamp, fluorescent UV lamp (short ARC xenon lamp, chemical lamp), metal halide lamp) is used. Then, for example, ultraviolet light of 200 to 450 nm is irradiated. If the amount of irradiated light is too small, the reaction will be difficult to proceed. On the other hand, if the amount of irradiation light is too large, there is a risk of deterioration of the support. Therefore, the preferred amount of irradiation light (light source wavelength: 254 nm) is 1 mJ/cm 2 to 5 J/cm 2 , more preferably 5 mJ/cm 2 to 1 J/cm 2 .
  • a UV irradiation device eg, high pressure mercury UV lamp, low pressure mercury UV lamp, fluorescent UV lamp (short ARC xenon lamp, chemical lamp), metal
  • the support When the support has a complicated shape, it is effective to use a reflector to uniformly irradiate the support with UV light.
  • the reflecting plate include mirrors, surface-polished metal foils, AI mirror foils, SUS mirror foils, silver-plated mirror plates, and the like.
  • the shape, dimensions, material, etc. of the reflector are appropriately selected from the viewpoint of reflection efficiency.
  • the workpiece holding layer 3 holds the workpiece on the side opposite to the side supported by the support body 1 via the adhesive layer 2 .
  • the work holding layer 3 has adhesive properties.
  • adhesiveness is developed by the resin contained in the resin composition. Thereby, the workpiece holding layer 3 can hold the workpiece by adhesive force.
  • the workpiece is preferably one type selected from the group consisting of a ceramic substrate, a silicon substrate, a glass substrate, and a resin film substrate.
  • the resin film substrate include polyimide film, polyethylene naphthalate film, and the like.
  • the substrate When the workpiece is a substrate used for manufacturing a semiconductor device, the substrate may be a wired circuit board with a circuit formed on at least one surface. Further, the circuit may include a sensor element.
  • the thickness of the workpiece holding layer 3 is preferably 10 ⁇ m or more and 3500 ⁇ m or less.
  • the thickness of the workpiece holding layer 3 is more preferably 20 ⁇ m or more, even more preferably 30 ⁇ m or more, even more preferably 40 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
  • the thickness of the workpiece holding layer 3 is more preferably 750 ⁇ m or less, even more preferably 700 ⁇ m or less, even more preferably 650 ⁇ m or less, and particularly preferably 600 ⁇ m or less.
  • the thickness of the workpiece holding layer 3 can be measured using, for example, a 1/100 dial gauge whose measurement unit is a diameter ( ⁇ ) of 20 mm.
  • the ratio (H2/H1) of the thickness H2 of the support body 1 to the thickness H1 of the workpiece holding layer 3 is preferably 0.1 or more, more preferably 0.5 or more, and 1.0 or more. It is more preferable that
  • H2/H1 is preferably 100 or less, more preferably 70 or less, and even more preferably 50 or less.
  • the workpiece holding layer 3 is configured as a foam layer of a resin composition.
  • the resin composition preferably contains a silicone resin or a fluororesin.
  • the workpiece holding layer 3 is configured as a foam layer of a resin composition, the workpiece can be sufficiently fixed before the heat treatment, and the workpiece can be easily removed after the heat treatment. Further, since the workpiece holding layer 3 is configured as a foam layer, the foam layer has air bubbles and has excellent cushioning properties.
  • the bubbles may have various shapes. The shape of the bubble may be perfectly spherical, or may be approximately spherical with partial distortion. Further, the bubbles may be greatly distorted and have an irregular shape. In short, the bubbles may have any shape as long as they contain gas such as air inside.
  • the work can be held.
  • Layer 3 can be configured as a rubber layer.
  • the silicone rubber-containing composition include addition (hydrosilylation) reaction type silicone rubber compositions and organic peroxide curing type silicone rubber compositions.
  • the addition (hydrosilylation) reaction type silicone rubber composition includes an alkenyl group-containing organopolysiloxane having two or more alkenyl groups in one molecule, such as a vinyl group, and two or more SiH groups, preferably two or more SiH groups.
  • the organic peroxide-curable silicone rubber composition is prepared by adding an organic peroxide as a curing agent to an organopolysiloxane having two or more alkenyl groups in one molecule in a curing effective amount (usually 100% by mass of the organopolysiloxane). 1 to 10 parts by mass).
  • the fluororubber-containing composition usually contains a copolymer that has a fluorine atom bonded to a carbon atom constituting the main chain and has rubber elasticity.
  • fluororubbers examples include vinylidene fluoride (VdF)/hexafluoropropylene (HFP) copolymer, VdF/HFP/tetrafluoroethylene (TFE) copolymer, TFE/propylene copolymer, and TFE/ Examples include propylene/VdF copolymer, ethylene/HFP copolymer, ethylene/HFP/VdF copolymer, ethylene/HFP/TFE copolymer, and the like.
  • the workpiece holding layer 3 can be a foam layer.
  • the resin composition is a resin composition containing a fluororesin (hereinafter also referred to as a fluororesin-containing composition)
  • a fluororesin-containing composition by adding various blowing agents to the fluororesin-containing composition in addition to the fluororesin, The resin composition may be in a foamed state.
  • fluororesin contained in the fluororesin-containing composition examples include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene.
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • ETFE copolymers
  • blowing agents include chlorofluorocarbon gas, inert gas (argon, etc.), carbon dioxide, nitrogen, and hydrocarbons (propane, butane, pentane, hexane, etc.).
  • the fluororesin-containing composition may contain a nucleating agent in addition to the fluororesin and various foaming agents.
  • a nucleating agent examples include boron nitride (BN), silicon dioxide, titanium dioxide, alumina, and magnesia.
  • the workpiece holding layer 3 is foamed by foaming the silicone resin-containing composition by thermosetting it. It may also be configured as a body layer.
  • a silicone resin-containing composition that foams by thermosetting may be used.
  • silicone resin-containing compositions include those containing at least the following components (A) to (F) in the following mass ratios.
  • component (D-1) to component (D-2) is at least 1), (E) hydroxysilylation reaction catalyst, and (F) 0.001 parts by mass or more and 5 parts by mass or less of a curing retarder.
  • Component (A) is the main ingredient of the present silicone resin-containing composition.
  • alkenyl group in component (A) include a vinyl group, an allyl group, and a hexenyl group, and preferably a vinyl group.
  • silicon-bonded organic groups other than alkenyl groups in component (A) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; phenyl, tolyl, and xylyl groups.
  • Examples include aryl groups such as; aralkyl groups such as benzyl group and phenethyl group; and halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl group. Preferred is methyl group.
  • Component (A) specifically includes dimethylvinylsiloxy group-blocked dimethylpolysiloxane, dimethylvinylsiloxy group-blocked dimethylsiloxane/methylphenylsiloxane copolymer, trimethylsiloxy group-blocked methylvinylpolysiloxane, and trimethylsiloxy group-blocked dimethylsiloxane.
  • Examples include methylvinylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymer, and diorganopolysiloxane whose main chain is substantially linear is preferred.
  • Component (B) is a crosslinking agent for the present silicone resin-containing composition.
  • the bonding position of the silicon-bonded hydrogen atom in component (B) is not limited, and examples thereof include the molecular chain terminal and/or the molecular chain side chain.
  • Examples of silicon-bonded organic groups other than hydrogen atoms in component (B) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; phenyl, tolyl, and xylyl groups; Aryl groups; aralkyl groups such as benzyl groups and phenethyl groups; halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl groups, etc. are exemplified, and methyl groups are preferred.
  • Such component (B) includes dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane/methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, and trimethylsiloxy group-blocked methylhydrogenpolysiloxane.
  • siloxane units represented by (CH 3 ) 3 SiO 1/2 siloxane units represented by H(CH 3 ) 2 SiO 1/2
  • SiO 4/2 examples include organopolysiloxanes consisting of siloxane units, and linear organopolysiloxanes are preferred.
  • component (B) is such that the silicon-bonded hydrogen atoms in component (B) are in the range of 0.4 to 20 moles per 1 mole of alkenyl group in component (A).
  • the amount is preferably in the range of 1.5 mol or more and 20 mol or less, and is more preferably the amount in the range of 1.5 mol or more and 10 mol or less.
  • Component (C) is a component for making the workpiece holding layer 3 obtained into a silicone sponge by removing the water in component (C) from the silicone crosslinked product obtained by crosslinking the present silicone resin-containing composition. be. Since component (C) is stably dispersed in component (A), the water in component (C) is preferably ion-exchanged water.
  • a foam is formed after crosslinking and curing by removing water in component (C).
  • the foam has a structure in which the path through which water is removed is communicated.
  • the foam formed by the present silicone resin-containing composition has an open cell structure.
  • the inorganic thickener in component (C) is blended to increase the viscosity of water, to easily disperse component (C) in component (A), and to stabilize the dispersion state of component (C). .
  • the inorganic thickeners may be natural or synthetic and include natural or synthetic smectite clays such as bentonite, montmorillonite, hectorite, saponite, sauconite, beidellite and nontronite; magnesium aluminum silicate; Examples include composites with water-soluble organic polymers such as carboxyvinyl polymers, and preferred are smectite clays such as bentonite and montmorillonite.
  • smectite clay for example, Smectone SA (manufactured by Kunimine Kogyo Co., Ltd.), which is a hydrothermally synthesized product, and Bengel (manufactured by Hojun Co., Ltd.), which is a naturally purified product, are available.
  • the pH of these smectite clays is preferably within the range of 5.0 or more and 9.0 or less in order to maintain the heat resistance of the silicone sponge.
  • the content of the inorganic thickener in component (C) is preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass, based on 100 parts by mass of water. More preferably, the amount is within a range of 5 parts by mass or less.
  • the content of component (C) is within the range of 100 parts by mass or more and 1000 parts by mass or less, and preferably within the range of 100 parts by mass or more and 800 parts by mass or less, based on 100 parts by mass of component (A). It is more preferably in the range of 100 parts by mass or more and 500 parts by mass or less, even more preferably in the range of 200 parts by mass or more and 500 parts by mass or less, and it is in the range of 200 parts by mass or more and 350 parts by mass or less. is particularly preferred.
  • the obtained workpiece holding layer 3 can have a low density, and when it is below the upper limit of the above range, the obtained workpiece This is because the holding layer 3 can have a uniform and fine open cell structure.
  • the surfactant component (D) consists of (D-1) a nonionic surfactant with an HLB value of 3 or more and (D-2) a nonionic surfactant with an HLB value of less than 3.
  • Component surfactants include glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.
  • Examples include ester, polyoxyethylene/polyoxypropylene block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene fatty acid amide.
  • Component (D) consists of components (D-1) and (D-2), and the mass ratio of component (D-1) to component (D-2) is 1 or more, and preferably 5 or more. It is preferably 8 or more, more preferably 10 or more, and particularly preferably 15 or more.
  • the mass ratio of component (D-1) to component (D-2) is preferably 100 or less, more preferably 80 or less, even more preferably 70 or less, and even more preferably 60 or less. It is especially preferable that it is 50 or less, and even more preferably that it is 50 or less.
  • the workpiece holding layer 3 can be made into a low-density one having a uniform and fine open cell structure, and if it is smaller than the above upper limit, it is possible to form the workpiece holding layer 3 with a low density having a uniform fine open cell structure. This is because the component (C) can be dispersed in the component (B) with good stability, and as a result, the workpiece holding layer 3 can have a uniform and fine open cell structure.
  • the content of component (D) is within the range of 0.1 parts by mass or more and 15 parts by mass or less, and within the range of 0.2 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of component (A). It is preferable. This is because when the content of component (D) is at least the lower limit of the above range, the workpiece holding layer 3 can have a uniform and fine open cell structure, and when it is below the upper limit of the above range, This is because the work holding layer 3 can have excellent heat resistance.
  • Component (E) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction in the present silicone resin-containing composition, and includes, for example, a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst.
  • platinum-based catalysts it is preferable to use platinum-based catalysts.
  • Such component (E) includes chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and olefins, vinyl siloxanes or acetylene compounds, platinum olefins, vinyl siloxanes or acetylene compounds.
  • Coordination compounds include tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium.
  • component (E) is sufficient to crosslink the present silicone resin-containing composition.
  • the amount of catalytic metal in component (E) should be in the range of 0.01 ppm or more and 500 ppm or less in terms of mass relative to the total amount of components (A) and (B).
  • the amount is in the range of 0.1 ppm or more and 100 ppm or less.
  • the present silicone resin-containing composition may contain (F) a curing retarder.
  • Such component (F) includes 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol, 1- Examples include alkyne alcohols such as ethynyl-1-cyclohexanol.
  • the content of component (F) is appropriately selected depending on the usage method and molding method of the present silicone resin-containing composition, but is generally 0.001 parts by mass per 100 parts by mass of component (A). The amount is within the range of 5 parts by mass or less.
  • the present silicone resin-containing composition may further contain (G) reinforcing silica fine powder.
  • a fine silica powder having a BET specific surface area of 50 m 2 /g or more and 350 m 2 /g or less is preferable, and a silica fine powder having a BET specific surface area of 80 m 2 /g or more and 250 m 2 /g or less is more preferable. preferable.
  • Examples of such fine silica powder include fumed silica and precipitated silica.
  • these fine silica powders may be surface-treated with organosilane or the like.
  • component (G) is 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of component (A).
  • component (G) is preferably 0.1 parts by mass or more based on 100 parts by mass of component (A).
  • the present silicone resin-containing composition may contain pigments such as carbon black and red iron to the extent that the object of the present invention is not impaired.
  • the present silicone resin-containing composition can be easily produced by uniformly mixing the above-mentioned components or a composition in which various additives are blended with these components as necessary using known kneading means.
  • mixer examples include a homomixer, paddle mixer, homodisper, colloid mill, vacuum mixing mixer, and rotation/revolution mixer. It is not particularly limited as long as it can be dispersed in.
  • the workpiece holding layer 3 is configured as a foam layer using the silicone resin-containing composition described above. That is, the workpiece holding layer 3 is constructed as a foam layer using a silicone resin-containing composition containing various foaming agents in addition to the silicone resin.
  • the apparent density of the workpiece holding layer 3 configured as a foam layer of a resin composition is preferably 0.05 g/cm 3 or more and 0.90 g/cm 3 or less.
  • the apparent density of the workpiece holding layer 3 is more preferably 0.10 g/cm 3 or more, and even more preferably 0.15 g/cm 3 or more. Further, the apparent density of the workpiece holding layer 3 is more preferably 0.85 g/cm 3 or less, and even more preferably 0.80 g/cm 3 or less.
  • the apparent density of the workpiece holding layer 3 can be measured according to the following procedures (1) to (5).
  • a test specimen is obtained by punching out the workpiece holding layer 3 configured as a foam layer into a rectangular shape in plan view using a punching die of 100 mm x 100 mm.
  • (3) Calculate the volume of the test body from the planar dimensions of the test body and the thickness of the test body.
  • the average cell diameter of the workpiece holding layer 3 configured as a foam layer of a resin composition is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the average cell diameter of the workpiece holding layer 3 is more preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more. Further, the average cell diameter of the workpiece holding layer 3 is more preferably 80 ⁇ m or less, and even more preferably 70 ⁇ m or less.
  • the average bubble diameter of the workpiece holding layer 3 can be measured using a low vacuum scanning electron microscope (“S-3400N Model Scanning Electron Microscope”, manufactured by Hitachi High-Tech Science Systems). Specifically, it can be determined by capturing an enlarged image of the cross section of the workpiece holding layer 3 using the low vacuum scanning electron microscope and analyzing the enlarged image.
  • S-3400N Model Scanning Electron Microscope manufactured by Hitachi High-Tech Science Systems.
  • the number of bubbles used for the image analysis can be, for example, 20.
  • the work holding layer 3 configured as a foam layer of a resin composition preferably has an arithmetic mean roughness Ra of 0.1 ⁇ m or more and 50 ⁇ m or less on the surface that comes into contact with the adhesive layer 2.
  • the arithmetic mean roughness Ra of the surface of the work holding layer 3 that comes into contact with the adhesive layer 2 is more preferably 0.2 ⁇ m or more, even more preferably 0.3 ⁇ m or more, and even more preferably 0.5 ⁇ m or more. It is even more preferable that it is, and it is especially preferable that it is 1.0 ⁇ m or more.
  • the arithmetic mean roughness Ra of the surface of the work holding layer 3 that comes into contact with the adhesive layer 2 is more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less.
  • the workpiece holding layer 3 can be sufficiently fixed to the support 1.
  • the arithmetic mean roughness Ra of the surface that comes into contact with the adhesive layer 2 is the arithmetic mean roughness Ra of the surface of the support 1 on which the adhesive layer 2 is laminated, as described above. It can be measured in the same manner as "Ra".
  • the work holding layer 3 configured as a foam layer of the resin composition has an open cell structure.
  • the open cell structure can be formed using a silicone resin-containing composition, for example, as described above.
  • the open-cell structure means a structure in which adjacent cells are connected to each other in the workpiece holding layer 3, which is the foam layer.
  • the adhesive layer 2 can be laminated on one side of the workpiece holding layer 3, which is the foam layer, and the workpiece (such as a substrate) can be laminated on the other side. ), between the adhesive layer 2 and one surface of the workpiece holding layer 3, which is a foam layer, and between the surface of the second adherend and the workpiece, which is a foam layer. It is possible to suppress air bubbles from being trapped between the holding layer 3 and the other surface.
  • the first adherend and the second adherend can be suitably held by the work holding layer 3, which is a foam layer.
  • the workpiece holding layer 3, which is the foam layer has an open cell structure, in the manufacture of electronic component devices, after mounting electronic components on a substrate, which is a workpiece, from the workpiece holding layer 3, which is a foam layer, The substrate can be easily peeled off without leaving any adhesive residue.
  • the holding ability (adsorption ability) of the workpiece holding layer 3 can be restored by washing with water, thereby improving the repeatability of the workpiece holding layer 3. Can be done.
  • the workpiece holding layer 3, which is the foam layer has an open cell structure, each of the above effects can be sufficiently exhibited even if the thickness of the workpiece holding layer 3, which is the foam layer, is made thin. Can be done.
  • the open cell ratio is preferably 90% or more, more preferably 90% or more and 100% or less, and 92% or more and 100% or less. It is more preferably 95% or more and 100% or less, particularly preferably 99% or more and 100% or less, and most preferably substantially 100%.
  • the work holding layer 3 which is the foam layer
  • 90% or more of all the cells have a cell diameter of 80 ⁇ m or less, and more preferably that 92% or more of all the cells have a cell diameter of 80 ⁇ m or less.
  • the diameter of 95% or more of all cells is 80 ⁇ m or less, even more preferably that the diameter of 97% or more of all cells is 80 ⁇ m or less, and the diameter of substantially 100% of all cells is 80 ⁇ m or less.
  • the foam layer can exhibit better air release properties, and the surface of the substrate or adhesive layer 2 and the surface of the foam layer can be It is possible to further suppress air bubbles from getting caught in between.
  • the work holding layer 3 has a shear adhesion value S to the polyimide film of 1N/100mm2 or more before heating at a temperature of 150°C or higher, and a polyimide film after heating at a temperature of 150°C or higher for 5 minutes. It is preferable that the value P of the 90° peeling force against the film is 7 N/20 mm or less.
  • the workpiece holding layer 3 preferably has a shear adhesive force value S of 1 N/100 mm 2 or more with respect to the polyimide film before heating at a temperature of 150° C. or higher.
  • 150°C is the temperature of the annealing process when a transparent electrode film such as an IZO film or an ITO film is mounted on a transparent substrate by sputtering or the like and then annealed and mounted in the production of organic EL devices. It is.
  • the value S of the shear adhesive force is more preferably 2N/100mm2 or more, even more preferably 3N/100mm2 or more, even more preferably 4N/100mm2 or more, and even more preferably 5N/100mm2 or more. It is particularly preferable that
  • the value S of the shear adhesive force is preferably 10 N/100 mm 2 or less, more preferably 9 N/100 mm 2 or less, even more preferably 8 N/100 mm 2 or less, and 7 N/100 mm 2 or less. It is even more preferable that it is below, and it is particularly preferable that it is below 6N/100mm 2 .
  • the upper limit of the temperature of 150°C or higher is preferably 270°C.
  • 270° C. is the peak top temperature of a heating furnace (reflow furnace) when a semiconductor chip is mounted on a printed circuit board and then subjected to reflow processing in the manufacture of semiconductor devices.
  • the ratio (S/P) of the shear adhesive force value S to the 90° peeling force value P is the workpiece holding property before heating and the workpiece holding property after heating. From the viewpoint of both ease of removal, the number is preferably 5 or more, more preferably 50 or more, and even more preferably 100 or more. Further, the S/P is preferably 1000 or less, more preferably 900 or less, and even more preferably 800 or less, from the viewpoint of achieving both workpiece retention before heating and ease of removing the workpiece after heating.
  • the value S of the shear adhesion of the workpiece holding layer 3 to the support 1 before heating at a temperature of 150° C. or higher is determined using the following procedure (1) using a tensile tester (model: DT9503-1000N, manufactured by Tansui Corporation). ) to (4). Further, as the polyimide film, for example, the product name "Kapton 100H” manufactured by DuPont-Toray Co., Ltd. can be used.
  • the work holding layer 3 preferably has a 90° peel force value P of 7 N/20 mm or less with respect to the polyimide film after being heated at a temperature of 150° C. or higher for 5 minutes.
  • the peel force value P is more preferably 5 N/20 mm or less, even more preferably 1 N/20 mm or less, even more preferably 0.1 N/20 mm or less.
  • the lower limit of the peel force value P is usually 0.01 N/20 mm.
  • the upper limit of the temperature of 150°C or higher is preferably 270°C.
  • the 90° peeling force of the workpiece holding layer 3 against the polyimide film after heating at a temperature of 150°C or higher for 5 minutes was determined using a tensile tester (model: AGS-X-5000N, manufactured by Shimadzu Corporation) as follows ( It can be measured according to the steps 1) to (4).
  • a tensile tester model: AGS-X-5000N, manufactured by Shimadzu Corporation
  • the polyimide film for example, the product name "Kapton 100H" manufactured by DuPont-Toray Co., Ltd. can be used.
  • the second laminate After obtaining a second laminate by placing a 20 mm wide polyimide film on the exposed surface of the work holding layer 3 (the opposite surface to the side to which the support 1 is attached), the second laminate is A 2 kg roller is moved back and forth once on the workpiece holding layer 3 to press the polyimide film onto the workpiece holding layer 3 to obtain a test piece for evaluation of 90° peeling force.
  • the work holding member 10 is used, for example, to mount electronic components on the surface of a work.
  • the work holding member 10 is used for mounting a semiconductor chip on the surface of a printed circuit board in the production of semiconductor devices, and is used for mounting a transparent substrate on the surface of a printed circuit board in the production of organic EL devices. It is used to mount a transparent electrode film such as an IZO film or an ITO film thereon.
  • the laminate 20 includes a support 1', an adhesive layer 2' laminated on the support 1', and a layer laminated on the adhesive layer 2'.
  • the work holding member 10' includes a work holding layer 3' for holding the work and a work holding layer 3', and a work 4 held on the work holding layer 3'.
  • the workpiece holding member 10' is configured as the workpiece holding member 10 according to the present embodiment described above. That is, the support 1', the adhesive layer 2', and the workpiece holding layer 3' are also configured in the same manner as the support 1, the adhesive layer 2, and the workpiece holding layer 3 described above.
  • the workpiece 4 is preferably one type selected from the group consisting of a ceramic substrate, a silicon substrate, a glass substrate, and a resin film substrate.
  • Examples of the resin film substrate include polyimide film, polyethylene naphthalate film, and the like.
  • the workpiece 4 (substrate) can be sufficiently fixed before the heat treatment during surface mounting of electronic components, and the workpiece 4 (substrate) can be sufficiently fixed during surface mounting of electronic components. After the heat treatment, the work 4 (substrate) can be easily removed from the work holding layer 3', and the work holding layer 3' is sufficiently fixed onto the support 1' via the adhesive layer 2'.
  • the work holding member 10 according to this embodiment can be manufactured, for example, by the following manufacturing method.
  • the method for manufacturing the workpiece holding member 10 according to the embodiment of the present invention includes the steps of laminating the adhesive layer 2 on the support 1 and laminating the workpiece holding layer 3 on the adhesive layer 2.
  • the method for manufacturing the workpiece holding member according to the present embodiment will be explained below using a case where a molecular adhesive layer is used as the adhesive layer 2 as an example, but the method for manufacturing the workpiece holding member according to the present embodiment is limited to this. It is not something that will be done.
  • the method for manufacturing the workpiece holding member 10 includes a step of applying a molecular adhesive to the support 1 (step A), and a step of applying the molecular adhesive to the support 1.
  • the method includes a step (step B) of heating the applied molecular adhesive and the workpiece holding layer 3 in a state where they face each other.
  • a molecular adhesive is applied to the support 1.
  • the molecular adhesive those explained in the section of the above-mentioned molecular adhesive layer can be used, and among them, it is preferable to use one containing a compound represented by the above general formula [I'].
  • the method further includes a step (step C) of irradiating the molecular adhesive with light (ultraviolet light). The irradiation with light (ultraviolet light) is as explained in the section regarding the molecular adhesive layer above.
  • the molecular adhesive can be applied to one main surface of the support 1, for example, as follows. For example, a molecular adhesive solution containing a molecular adhesive is prepared, this solution is applied onto one main surface of the support 1, and the resulting coating film is then dried or the molecular adhesive is applied to the support. Perform processing to fix it to 1.
  • the solvent used when preparing the molecular adhesive solution is not particularly limited.
  • solvents include alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, cellosolve, and carbitol; ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, methyl propionate, and phthalate.
  • Ester solvents such as acid methyl; halogen-containing solvents such as methylene chloride; aliphatic hydrocarbon solvents such as butane, hexane, octane, decane, dodecane, and octadecane; ether solvents such as tetrahydrofuran, butyl ether, ethyl butyl ether, anisole, etc. Solvents; aromatic compound solvents such as benzene, toluene and xylene; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone; water; and the like. These can be used alone or in combination of two or more.
  • the concentration of the molecular adhesive in the molecular adhesive solution is not particularly limited. Its concentration is preferably 0.05 to 10% by weight, more preferably 0.10 to 1% by weight. By setting the concentration of adhesive molecules to 0.05% by mass or more, the molecular adhesive can be efficiently applied onto the support 1. Further, by setting the content to 10% by mass or less, unintended reactions of the molecular adhesive solution can be suppressed, and the stability of the solution is excellent.
  • the method for applying the molecular adhesive solution is not particularly limited, and any known application method can be used.
  • coating methods include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, dip coating, curtain coating, die coating, and gravure coating. etc. Among these, bar coating and gravure coating are preferred.
  • a drying process is usually performed to dry the resulting coating film, such as by air drying or by putting it into a drying mechanism.
  • a drying process is usually performed to dry the resulting coating film, such as by air drying or by putting it into a drying mechanism.
  • the drying temperature adjusted by the drying mechanism is preferably 30 to 110°C, more preferably 30 to 90°C, even more preferably 30 to 80°C. Depending on the drying time, the temperature may be 30 to 70°C. Thereby, the adhesive heat of the molecular adhesive can be lowered, and deactivation of the molecular adhesive can be suppressed.
  • the drying time is usually 1 second to 120 minutes, preferably 10 seconds to 10 minutes, more preferably 20 seconds to 10 minutes, particularly preferably 30 seconds to 10 minutes. Depending on the drying temperature, the drying time may be 20 seconds to 5 minutes, or 30 seconds to 3 minutes.
  • Drying mechanisms include, for example, batch-type drying mechanisms such as air ovens, heat rolls, and hot air through mechanisms (in which the object to be dried moves and passes through an open drying oven while being heated and dried while being blown by air). Continuous drying mechanisms such as drying equipment, etc. Note that devices that can be used as part of these drying mechanisms, such as high-frequency heating, heat medium circulation heaters such as oil heaters, and heaters themselves such as far-infrared heaters, can also be used as the drying mechanism. Among these, the hot air through mechanism is preferred from the viewpoint of improving productivity.
  • a pretreatment step is included in which the surface to which the molecular adhesive is applied is subjected to a cleaning treatment or a surface treatment. Good too.
  • the pretreatment step allows the support and the workpiece holding layer to be bonded more firmly.
  • Examples of the cleaning treatment include alkaline degreasing treatment and the like.
  • Alkaline degreasing is a process in which the surface is washed with an alkaline cleaning solution, then washed with distilled water, and then dried.
  • Examples of the surface treatment include corona treatment, sputter etching treatment, plasma treatment, and the like.
  • Examples of corona treatment include a method of discharging in normal pressure air using a corona treatment machine.
  • the corona treatment is performed by irradiating the surface of the support with discharge using a corona surface treatment device using a high frequency power source.
  • the discharge amount in the corona treatment is preferably 10 to 500 W ⁇ min/m 2 , more preferably 30 to 300 W ⁇ min/m 2 , and even more preferably 50 to 200 W ⁇ min/m 2 .
  • the amount of discharge can be set within the above range by appropriately adjusting the discharge output intensity (kW) and the processing speed (m/min) of corona treatment.
  • the discharge output intensity is preferably 0.05 kW or more, more preferably 0.08 kW or more, and still more preferably 0.10 kW or more.
  • sputter etching process for example, energetic particles derived from a gas collide with the surface of the support. At the part of the support where the particles collide, atoms or molecules present on the surface of the support are released to form reactive groups, thereby improving adhesion.
  • the sputter etching process can be carried out, for example, by placing the support in a chamber, then reducing the pressure in the chamber, and then applying a high frequency voltage while introducing atmospheric gas.
  • the atmospheric gas is, for example, at least one selected from the group consisting of rare gases such as helium, neon, argon, and krypton, nitrogen gas, and oxygen gas.
  • the frequency of the high frequency voltage to be applied is, for example, 1 to 100 MHz, preferably 5 to 50 MHz.
  • the pressure inside the chamber when applying the high frequency voltage is, for example, 0.05 to 200 Pa, preferably 1 to 100 Pa.
  • the sputter etching energy (product of processing time and applied power) is, for example, 1 to 1000 J/cm 2 , preferably 2 to 200 J/cm 2 .
  • Examples of the plasma treatment include a method of discharging in normal pressure air using a plasma discharge machine. This can be done by setting the support in a plasma device and irradiating it with plasma using a predetermined gas.
  • the conditions for the plasma treatment can be set to any appropriate conditions as long as the effects of the present invention can be obtained.
  • the above plasma treatment may be a plasma treatment performed under atmospheric pressure or a plasma treatment performed under reduced pressure.
  • the pressure (degree of vacuum) during plasma treatment is, for example, 0.05 Pa to 200 Pa, preferably 0.5 Pa to 100 Pa.
  • the frequency of the high frequency power source used for plasma processing is, for example, 1 MHz to 100 MHz, preferably 5 MHz to 50 MHz.
  • the amount of energy during plasma treatment is preferably 0.1 J/cm 2 to 100 J/cm 2 , more preferably 1 J/cm 2 to 20 J/cm 2 .
  • the plasma treatment time is preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes.
  • the gas supply amount during plasma treatment is preferably 1 sccm to 150 sccm, more preferably 10 sccm to 100 sccm.
  • Examples of the reactive gas used in the plasma treatment include gases such as water vapor, air, oxygen, nitrogen, hydrogen, ammonia, and alcohol (eg, ethanol, methanol, isopropyl alcohol). By using such a reactive gas, a support with excellent adhesiveness can be obtained. Further, an inert gas such as helium, neon, argon, etc. may be used in combination with the reactive gas.
  • the type of surface treatment can be selected as appropriate depending on the material constituting the support.
  • the molecular adhesive applied on the support and the workpiece holding layer are heated while facing each other.
  • a pretreatment step is performed in which a surface of the workpiece holding layer to be made to face the molecular adhesive is subjected to a cleaning treatment or a surface treatment. may have.
  • the pretreatment step allows the support and the workpiece holding layer to be bonded more firmly.
  • the pretreatment step may include cleaning treatment such as alkaline degreasing treatment, and surface treatment such as corona treatment, sputter etching treatment, plasma treatment, etc., in the same manner as described for the support above.
  • a molecular adhesive layer is formed with the molecular adhesive fixed to the support and the workpiece holding layer.
  • Heating may be performed from the support side, from the workpiece holding layer side, or from both.
  • the heating temperature is preferably 40 to 250°C, more preferably 60 to 200°C, and still more preferably 80 to 120°C.
  • the heating temperature when heating from the support side is preferably 40 to 250°C, more preferably 60 to 200°C, and even more preferably 90 to 110°C.
  • the heating temperature when heating from the work holding layer side is preferably 40 to 250°C, more preferably 60 to 200°C, and even more preferably 80 to 110°C.
  • the heating time is preferably 1 second to 120 minutes, more preferably 1 minute to 60 minutes, and still more preferably 1 minute to 30 minutes.
  • the heating method is not particularly limited, and a mechanism and device similar to the above-mentioned drying mechanism can be used.
  • the above heating may be performed while applying pressure.
  • the pressurizing pressure is preferably 0.01 MPa or more and 50 MPa or less, more preferably 0.1 MPa or more and 5 MPa or less.
  • the pressurizing time is preferably 0.1 minutes or more and 200 minutes or less.
  • the pressurizing method is not particularly limited, and a known hot press machine (for example, precision constant temperature press machine CYPT-10 manufactured by Shinto Kogyo Co., Ltd.) can be used.
  • a known hot press machine for example, precision constant temperature press machine CYPT-10 manufactured by Shinto Kogyo Co., Ltd.
  • a method for manufacturing an electronic component according to an embodiment of the present invention includes: On the work holding layer 3 of a work holding member 10 comprising a support 1, an adhesive layer 2 laminated on the support 1, and a work holding layer 3 laminated on the adhesive layer 2 and holding the work. a workpiece holding step S1 of holding the workpiece 4; an electronic component mounting step S2 of mounting an electronic component on one surface of the workpiece 4 held on the workpiece holding layer 3; The method includes a workpiece removal step S3 in which the workpiece 4 on which the electronic component is mounted is removed from the workpiece holding layer 3 of the workpiece holding member 10. Furthermore, in the electronic component manufacturing method according to the present embodiment, the workpiece holding member is configured as the workpiece holding member 10 according to the present embodiment described above.
  • the substrate is preferably a wired circuit board having a circuit formed on at least one surface.
  • the work holding member 10 is constructed by laminating the adhesive layer 2 on the support 1 and laminating the work holding layer 3 on the adhesive layer 2 before holding the substrate, which is the work 4, on the work holding layer 3. This can be obtained by
  • Lamination of the adhesive layer 2 on the support 1 can be carried out by the method described above.
  • the work holding layer 3 can be laminated onto the adhesive layer 2 by the method described above.
  • the workpiece holding layer 3 can be formed on the adhesive layer 2 by coating the adhesive layer 2 with a resin composition that is a raw material for the workpiece holding layer 3 and drying it.
  • the workpiece holding step S1 is carried out.
  • the semiconductor chip SC includes a semiconductor chip body CB and a bump electrode BE arranged on one surface of the semiconductor chip body CB.
  • connection conductor portion is formed on one surface of the substrate serving as the work 4 (not shown).
  • attachment of the semiconductor chip SC onto the substrate serving as the work 4 is carried out by connecting the bump electrodes BE of the semiconductor chip SC to the connecting conductor portions of the substrate serving as the work 4.
  • the bump electrode BE of the semiconductor chip SC is connected to the connection conductor portion of the substrate, which is the workpiece 4, by placing the semiconductor chip SC on the substrate, which is the workpiece 4, with the bump electrode BE in contact with the connection conductor portion. After obtaining the aggregate, this can be carried out by heating the aggregate in a reflow oven (reflow treatment).
  • the reflow process is usually performed such that the peak top temperature in the reflow oven is 270°C.
  • the workpiece holding member used in the semiconductor device manufacturing method is the workpiece holding member 10 according to the present embodiment, it is possible to suppress the substrate, which is the workpiece 4, from warping even after the reflow process.
  • the substrate serving as the work 4 can be sufficiently fixed on the work holding layer of the work holding member.
  • the SC is resin-sealed with a sealing resin ER.
  • thermosetting resin such as an epoxy resin or a phenol resin is usually used.
  • the temperature at which the sealing resin ER is thermally cured e.g., 150° C.
  • the electronic component mounting step S2 in the semiconductor device manufacturing method is performed.
  • a semiconductor package P is formed on the substrate serving as the work 4.
  • the workpiece 4 or substrate is removed from the workpiece holding layer 3 by using a suction device, for example, with a suction force greater than the force with which the workpiece holding layer 3 holds the workpiece 4 or the substrate. This can be carried out by suctioning the surface of the semiconductor package P on the side where there is no surface.
  • the workpiece holding member used in the semiconductor device manufacturing method is the workpiece holding member 10 according to the present embodiment, after the reflow treatment, the holding force (adhesive force) of the workpiece holding layer 3 to the substrate serving as the workpiece 4 is reduced. is getting smaller.
  • the substrate serving as the work 4 can be easily removed from the work holding layer 3.
  • the substrate which is the workpiece 4
  • the substrate holding layer 3 can be efficiently removed from the workpiece holding layer 3 even with a relatively small suction force.
  • the semiconductor package P with the work 4 from which the substrate serving as the work 4 has been removed from the work holding layer 3 may be used as a semiconductor device as it is.
  • the semiconductor package P with the workpiece 4 may be divided into a plurality of semiconductor devices by using a dicing blade or the like to include a predetermined number of semiconductor chips SC.
  • a plasma treatment step S1' in which the substrate, which is the workpiece 4, is treated with plasma discharge may be performed between the workpiece holding step S1 and the electronic component mounting step S2.
  • the plasma treatment step S1' can be performed using various known plasma cleaning apparatuses.
  • the substrate pad metal surface exposed on the surface of the substrate serving as the work 4 can be cleaned to remove organic contaminants.
  • the semiconductor chip SC may be subjected to plasma treatment before being resin-sealed with the sealing resin ER.
  • the plasma treatment of the semiconductor chip SC can be performed in the same manner as the plasma treatment step S1' described above.
  • an underfill process is performed in which the periphery of the bump electrode BE is sealed with an underfill material such as an epoxy resin. may be implemented.
  • the underfill material can be placed around the bump electrode BE where it is difficult for the sealing resin ER to spread, so resin sealing with the sealing resin ER can be performed with high precision. .
  • the method for manufacturing an electronic component device has been described above by taking the method for manufacturing a semiconductor device as an example, the method for manufacturing an electronic component device can be applied to methods other than methods for manufacturing semiconductor devices.
  • the method for manufacturing an electronic component device can also be applied to a method for manufacturing an organic EL device.
  • a transparent substrate is used as a workpiece, and in the electronic component mounting step S2, a transparent electrode film such as IZO or ITO, which is an electronic component, is mainly attached to the transparent substrate, which is a workpiece, by sputtering or the like.
  • the transparent electrode film is annealed at a temperature of about 150°C.
  • the transparent substrate that is the workpiece can be sufficiently fixed on the workpiece holding layer of the workpiece holding member.
  • the transparent substrate serving as the workpiece can be relatively easily removed from the workpiece holding layer.
  • workpiece holding member and laminate according to this embodiment are not limited to the above embodiment.
  • the workpiece holding member and laminate according to this embodiment are not limited to the above-described effects.
  • the workpiece holding member and the laminate according to this embodiment can be modified in various ways without departing from the gist of the present invention.
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work,
  • the work holding layer is configured as a foam layer of a resin composition
  • a workpiece holding member, wherein the adhesive layer is a molecular adhesive layer.
  • the above-mentioned material satisfies any of the following (i) to (iii) when a peel test is conducted between the support and the workpiece holding layer according to the following procedures (1) to (3).
  • the workpiece holding member according to [1] or [2]. (1) In a double-sided adhesive tape having an acrylic adhesive layer on one side of the main surface of a polyester film base material and a silicone adhesive layer on the other side, a PET film is attached to the acrylic adhesive layer side, A sample is prepared in which a workpiece holding layer of a workpiece holding member is attached to the silicone adhesive layer side. (2) The sample is allowed to stand at 50°C for 24 hours, and then at 23°C for 30 minutes.
  • the molecular adhesive forming the molecular adhesive layer contains a compound having at least one of a first reactive group RG1 and a second reactive group RG2,
  • the first reactive group RG1 is at least one selected from the group consisting of an amino group and an azide group
  • the molecular adhesive further has a triazine ring, and the group containing the first reactive group RG1 and the group containing the second reactive group RG2 are bonded to the triazine ring, according to [5] above. Work holding member.
  • the work holding layer has a shear adhesion value S to the polyimide film of 1N/100mm2 or more before heating at a temperature of 150°C or higher, and a polyimide film after heating at a temperature of 150°C or higher for 5 minutes.
  • a work holding member comprising a support, an adhesive layer laminated on the support, and a work holding layer laminated on the adhesive layer to hold the work;
  • a laminate comprising: a workpiece held on the workpiece holding layer;
  • a laminate, wherein the workpiece holding member is the workpiece holding member described in [1] to [18] above.
  • Example 1 A stainless steel plate (SUS304BA) was used as a support.
  • the planar dimensions of the stainless steel plate (SUS304BA) were 30 mm x 30 mm, and the thickness was 0.5 mm.
  • the thickness of the stainless steel plate was measured according to the method described in the embodiment section above. The same applies to each of the following examples.
  • a 0.5% by mass ethanol solution of 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazide as a molecular adhesive was applied onto a stainless steel plate (SUS304BA).
  • a molecular adhesive layer was formed by UV irradiation (265 nm, 100 mJ/cm 2 ) using a UV-LED irradiation device manufactured by Quark Technology. Subsequently, a silicone foam layer was used as the workpiece holding layer.
  • the silicone foam layer was produced according to the following procedures (a) to (e) using each of the materials (1) to (10) shown in Table 1 below in the amounts shown in Table 1 below.
  • the thickness of the silicone foam obtained according to the above procedure was 0.2 mm (200 ⁇ m). Further, the silicone foam had an open cell structure, the open cell ratio was 100%, and the average cell diameter was 8 ⁇ m. Furthermore, the apparent density of the silicone foam was 0.55 g/cm 3 .
  • the thickness of the silicone foam was measured according to the method described in the embodiment section above. The same applies to each of the following examples.
  • One surface of the silicone foam produced above was subjected to corona treatment at a discharge amount of 122 W ⁇ min/m 2 .
  • the molecular adhesive layer formed on a stainless steel plate (SUS304BA) and the corona-treated surface of the silicone foam were bonded together and heated in an oven at 90° C. for 10 minutes to produce the workpiece holding member of Example 1.
  • Example 2 N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine was applied as a molecular adhesive onto a stainless steel plate (SUS304BA).
  • the workpiece of Example 2 was prepared in the same manner as in Example 1, except that a molecular adhesive layer was formed by applying a 0.5% by mass aqueous solution and drying it in an oven at 80°C for 10 minutes. A holding member was produced.
  • Example 3 The support was glass (soda glass), and N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2, A workpiece holding member of Example 3 was produced in the same manner as Example 2 except that the concentration of 4-diamine was 0.1% by mass.
  • Example 4 The support is A5052P (Al-Mg alloy), and N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine- in the molecular adhesive layer.
  • a workpiece holding member of Example 4 was produced in the same manner as Example 2 except that the concentration of 2,4-diamine was 0.1% by mass.
  • Comparative example 3 Instead of forming a molecular adhesive layer on SUS304BA, DOWSIL SE9186 (manufactured by DOW, one-component, room temperature curing silicone adhesive) was applied as an adhesive to a thickness of 1 mm, and silicone foam was formed.
  • a work holding member of Comparative Example 3 was produced in the same manner as in Example 1, except that one of the two was pasted together and placed in an oven at 150°C for 30 minutes to bond the support and work holding layer. .
  • Shear adhesive strength S Regarding the workpiece holding layer according to each example, the value S of shear adhesion to the polyimide film before heating at a temperature of 150° C. or higher was measured according to the method described in the above embodiment section. Note that the thickness of the polyimide film was 25 ⁇ m. Moreover, as the polyimide film, the product name "Kapton 100H" manufactured by DuPont-Toray was used. The results are shown in Table 2 below.
  • adhesion between support and workpiece holding layer For each example, the adhesion between the support and the workpiece holding layer was evaluated according to the method described in the embodiment section above. That is, a peel test was conducted according to the following procedures (1) to (3), and the adhesion between the support and the workpiece holding layer was evaluated according to the following (i) to (iii).
  • Double-sided adhesive tape having an acrylic adhesive layer on one side of the main surface of a polyester film base material and a silicone adhesive layer on the other side (manufactured by Nitto Denko Corporation, No. 5302A, tape thickness: 0. 085 mm), PET film (manufactured by Toray Industries, Ltd., A sample was prepared in which a workpiece holding layer of a workpiece holding member was bonded to the silicone adhesive layer side. (2) The sample was allowed to stand at 50°C for 24 hours, and then at 23°C for 30 minutes.
  • repeatability of work holding layer was evaluated. Repeatability is determined by whether any marks remain after placing the workpiece (printed circuit board formed on a glass epoxy board (FR4)) on the workpiece holding member and heat-pressing it at 175°C, 10MPa, for 2 minutes. The evaluation was based on whether
  • the workpiece holding members of Examples 1 to 4 had good fixing properties and removability, so they could sufficiently fix the workpiece before the heat treatment when surface mounting electronic components. It was found that the workpiece was easy to remove after the heat treatment. It was also found that the adhesion between the support and the workpiece holding layer was high, and the workpiece holding layer was sufficiently fixed on the support.
  • the workpiece holding member of Comparative Example 1 uses an adhesive as the adhesive layer, and the thickness of the adhesive layer is also large, resulting in poor repeatability of the workpiece holding layer. Therefore, it was found that the function of the workpiece holding layer could not be maintained. Furthermore, in Comparative Example 2, since a foam layer was not used as the workpiece holding layer, the fixing properties and releasability were poor. Furthermore, in Comparative Example 3, a liquid adhesive was used as the adhesive layer, and the thickness of the adhesive layer was also large, resulting in poor repeatability of the workpiece holding layer. Therefore, it was found that the function of the workpiece holding layer could not be maintained.

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  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un élément de maintien de pièce comprenant : un corps de support ; une couche adhésive qui est stratifiée sur le corps de support ; et une couche de maintien de pièce qui est stratifiée sur la couche adhésive et qui permet de maintenir une pièce. La couche de maintien de pièce est conçue sous la forme d'une couche de corps en mousse comprenant une composition de résine. La couche adhésive a une épaisseur inférieure ou égale à 2 µm.
PCT/JP2023/029191 2022-08-19 2023-08-09 Élément de maintien de pièce et stratifié WO2024038819A1 (fr)

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JP2022131311 2022-08-19

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015098719A1 (fr) * 2013-12-27 2015-07-02 株式会社朝日Ｆｒ研究所 Puce microchimique thermoconductrice
WO2015098720A1 (fr) * 2013-12-27 2015-07-02 株式会社朝日Ｆｒ研究所 Puce microchimique tridimensionnelle
JP2019065079A (ja) * 2017-09-28 2019-04-25 日東電工株式会社 仮固定シート
JP2021160300A (ja) * 2020-04-01 2021-10-11 日東電工株式会社 仮固定複合体
JP2021174853A (ja) * 2020-04-23 2021-11-01 信越ポリマー株式会社 部品保持治具

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015098719A1 (fr) * 2013-12-27 2015-07-02 株式会社朝日Ｆｒ研究所 Puce microchimique thermoconductrice
WO2015098720A1 (fr) * 2013-12-27 2015-07-02 株式会社朝日Ｆｒ研究所 Puce microchimique tridimensionnelle
JP2019065079A (ja) * 2017-09-28 2019-04-25 日東電工株式会社 仮固定シート
JP2021160300A (ja) * 2020-04-01 2021-10-11 日東電工株式会社 仮固定複合体
JP2021174853A (ja) * 2020-04-23 2021-11-01 信越ポリマー株式会社 部品保持治具

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