CN114729254A - Adhesive composition, laminate, method for producing laminate, and method for producing electronic component - Google Patents

Adhesive composition, laminate, method for producing laminate, and method for producing electronic component Download PDF

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Publication number
CN114729254A
CN114729254A CN202080080020.8A CN202080080020A CN114729254A CN 114729254 A CN114729254 A CN 114729254A CN 202080080020 A CN202080080020 A CN 202080080020A CN 114729254 A CN114729254 A CN 114729254A
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China
Prior art keywords
group
component
adhesive composition
adhesive layer
laminate
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CN202080080020.8A
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Chinese (zh)
Inventor
吉冈孝广
鹈野和英
富冈有希
丸山贵史
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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Priority claimed from JP2019238291A external-priority patent/JP6802348B1/en
Priority claimed from JP2020110426A external-priority patent/JP2022007441A/en
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of CN114729254A publication Critical patent/CN114729254A/en
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    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

Abstract

An adhesive composition for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support which transmits light, the adhesive composition comprising: (a) light absorbers, polyisocyanates, and polyols; or (b) a light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.

Description

Adhesive composition, laminate, method for producing laminate, and method for producing electronic component
Technical Field
The invention relates to an adhesive composition, a laminate, a method for manufacturing the laminate, and a method for manufacturing an electronic component.
The present application claims priority based on Japanese patent application Nos. 2019-238291, filed in Japan at 27/12/2019, and 2020-110426, filed in Japan at 26/6/2020, and the contents thereof are incorporated herein.
Background
Semiconductor packages (electronic components) including semiconductor elements have various forms depending on their sizes, and examples thereof include WLP (Wafer Level Package), PLP (Panel Level Package), and the like.
As a technique for semiconductor packaging, a fan-in technique and a fan-out technique are given. As a semiconductor Package based on the Fan-in technology, a Fan-in WLP (Fan-in Wafer Level Package) or the like is known in which terminals located at an end portion of a bare chip are disposed in a chip region. As a semiconductor Package based on the Fan-out technology, a Fan-out WLP (Fan-out Wafer Level Package) or the like is known in which the terminal is disposed outside the chip region.
In recent years, particularly, a Fan-out type technique has been attracting attention as a method capable of realizing further high integration, thinning, miniaturization, and the like of a semiconductor Package, and is applied to, for example, a Fan-out type PLP (Fan-out Panel Level Package) in which a semiconductor element is arranged on a Panel and packaged.
In order to achieve miniaturization of a semiconductor package, it is important to reduce the thickness of a substrate in an assembled element. However, when the thickness of the substrate is reduced, the strength thereof is reduced, and the substrate is easily broken when the semiconductor package is manufactured. For this purpose, the following techniques are known: the substrate is temporarily bonded to the support using an adhesive, and after the substrate is processed, the substrate is separated from the support.
As the adhesive used for temporarily bonding the substrate and the support, a thermoplastic adhesive is often used in view of easy removal of the adhesive layer with a solvent or the like. For example, patent document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high boiling point solvent, and a low boiling point solvent.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/052315
Disclosure of Invention
Problems to be solved by the invention
On the other hand, in the manufacture of semiconductor packages, high-temperature processes such as film formation, firing, and die bonding are sometimes performed. If the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer decreases during high-temperature processing, and there is a concern that the substrate may be displaced or may sink. On the other hand, when the heat resistance of the adhesive is improved, the coatability to the substrate or the support tends to be lowered.
When a thermosetting adhesive is used for bonding the support and the substrate, problems such as positional deviation and sinking do not occur during high-temperature processing. However, it is difficult to remove the adhesive layer with a solvent or the like, and even when a separation layer is provided, it is difficult to remove the adhesive layer adhering to the substrate after the support is separated from the substrate by modification of the separation layer.
In addition, in the conventional adhesive, a separation layer is generally required to separate the support from the substrate after processing the substrate. Therefore, it is necessary to separately form the separation layer and the adhesive layer, which is troublesome.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition which does not require a release layer, has high heat resistance, and facilitates removal of an adhesive layer, a laminate produced using the adhesive composition, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition.
Means for solving the problems
In order to solve the above problem, the present invention employs the following configuration.
That is, the 1 st aspect of the present invention is an adhesive composition for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support which transmits light, the adhesive composition comprising: (a) light absorbers, polyisocyanates, and polyols; or (b) a light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.
The 2 nd aspect of the present invention is a laminate in which a support for transmitting light, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, wherein the adhesive layer is a cured product of the adhesive composition according to the 1 st aspect.
A 3 rd aspect of the present invention is a method for producing a laminate in which a support for transmitting light, an adhesive layer, and a semiconductor substrate are sequentially laminated, the method comprising: a step of applying the adhesive composition according to the above-mentioned 1 to the support or the semiconductor substrate to form an adhesive composition layer; a step of placing the semiconductor substrate on the support via the adhesive composition layer; and forming the adhesive layer by curing the adhesive composition layer.
The 4 th aspect of the present invention is a method for producing a laminate in which a support body for transmitting light, an adhesive layer, and an electronic device are laminated in this order, wherein the method for producing a laminate according to the 3 rd aspect further comprises an electronic device forming step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member after obtaining the laminate.
The 5 th aspect of the present invention is a method for manufacturing an electronic component, wherein, after obtaining a laminate by the method for manufacturing a laminate according to the 4 th aspect, the method comprises: irradiating the adhesive layer with light through the support to modify the adhesive layer, thereby separating the electronic device from the support; and a step of removing the adhesive layer attached to the electronic component by decomposing a urethane bond in the adhesive layer with an acid or an alkali.
Effects of the invention
According to the present invention, an adhesive composition which does not require a release layer, has high heat resistance, and can be easily removed from an adhesive layer, a laminate produced using the adhesive composition, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition can be provided.
Drawings
FIG. 1 is a schematic view showing one embodiment of a laminate to which the present invention is applied.
FIG. 2 is a schematic view showing one embodiment of a laminate to which the present invention is applied.
FIG. 3 is a schematic view showing one embodiment of a laminate to which the present invention is applied.
FIG. 4 is a schematic view showing one embodiment of a laminate to which the present invention is applied.
Fig. 5A and 5B are schematic process diagrams illustrating an embodiment of a method for manufacturing a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are sequentially laminated. Fig. 5A is a diagram illustrating an adhesive composition layer forming step.
Fig. 5B is a diagram illustrating a semiconductor substrate mounting process.
FIG. 6 is a diagram illustrating an adhesive layer forming step.
Fig. 7A and 7C are schematic process diagrams illustrating an embodiment of a method for manufacturing the laminate 120. Fig. 7A is a diagram illustrating a sealing process.
Fig. 7B is a diagram illustrating a grinding process.
Fig. 7C is a diagram illustrating a wiring layer forming step.
Fig. 8A to 8C are schematic process views for explaining an embodiment of a method for manufacturing a semiconductor package (electronic component) from the laminate 120. Fig. 8A is a diagram illustrating the stacked body 200.
Fig. 8B and 8B are views for explaining the separation step.
Fig. 8C is a view for explaining the adhesive layer removing step.
Detailed Description
In the present specification and claims, "aliphatic" refers to a relative concept with respect to aromatic, and is defined as a group, a compound, or the like having no aromatic character.
Unless otherwise specified, "alkyl" includes straight-chain, branched-chain and cyclic 1-valent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, "alkylene" includes linear, branched, and cyclic 2-valent saturated hydrocarbon groups.
The "haloalkyl group" is a group in which a part or all of hydrogen atoms of an alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
"fluoroalkyl" or "fluoroalkylene" refers to an alkyl group or an alkylene group in which a part or all of the hydrogen atoms of the alkylene group have been replaced with fluorine atoms.
The "structural unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When the term "may have a substituent" or "may have a substituent", the term includes the case where a hydrogen atom (-H) is substituted with a 1-valent group, and a methylene group (-CH)2-) both of which are substituted with a 2-valent group.
"exposure" is a concept including irradiation of radiation as a whole.
The "structural unit derived from hydroxystyrene" means a structural unit in which an ethylenic double bond of hydroxystyrene is broken. The "structural unit derived from a hydroxystyrene derivative" means a structural unit in which an ethylenic double bond of the hydroxystyrene derivative is broken.
The term "hydroxystyrene derivative" is intended to encompass compounds in which the hydrogen atom at the α -position of hydroxystyrene is substituted with another substituent such as an alkyl group or a haloalkyl group, and derivatives thereof. Examples of derivatives thereof include: a compound in which a hydrogen atom at the α -position is substituted with an organic group by a hydrogen atom of a hydroxyl group of hydroxystyrene which may be substituted with a substituent; a compound in which a substituent other than a hydroxyl group is bonded to a benzene ring of hydroxystyrene in which a hydrogen atom at the α -position may be substituted with a substituent; and so on. Unless otherwise specified, the α -position (α -position carbon atom) refers to a carbon atom to which a benzene ring is bonded.
Examples of the substituent substituted with the hydrogen atom at the α -position of hydroxystyrene include the same substituents as those listed as the substituent at the α -position in the above-mentioned α -substituted acrylate.
The alkyl group as the substituent at the α -position is preferably a linear or branched alkyl group, and specific examples thereof include alkyl groups having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl).
Specific examples of the haloalkyl group as the α -position substituent include groups obtained by substituting a part or all of hydrogen atoms of the above-mentioned "alkyl group as an α -position substituent" with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the α -substituent include groups obtained by substituting a part or all of the hydrogen atoms of the above-mentioned "alkyl group as an α -substituent" with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.
In the present specification and claims, depending on the structure represented by the chemical formula, chiral carbons exist, and enantiomers (enatiomers) and diastereomers (diastereomers) may exist, and in this case, these isomers are represented by a single formula. These isomers may be used alone or in the form of a mixture.
(adhesive composition)
An adhesive composition according to claim 1 of the present invention is an adhesive composition for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support that transmits light, the adhesive composition comprising: (a) light absorbers, polyisocyanates, and polyols; or (b) a light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.
< temporarily bonded object >
The adhesive composition according to the present embodiment can be used for forming an adhesive layer for temporarily bonding a semiconductor substrate or an electronic device to a support. In the present specification, "temporary bonding" means that an object to be bonded is temporarily (for example, during an arbitrary operation step) bonded. More specifically, in order to thin the device, transport the semiconductor substrate, mount the semiconductor substrate, and the like, the semiconductor substrate or the electronic device is temporarily bonded to the support and fixed (temporarily bonded) to the support, and after the completion of the process, the semiconductor substrate or the electronic device is separated from the support.
Semiconductor substrate
The semiconductor substrate to which the adhesive composition according to the present embodiment is applied is not particularly limited, and may be a substrate generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by a support. Structures such as integrated circuits and metal bumps can be mounted on the semiconductor substrate.
The semiconductor substrate is typically a silicon wafer substrate, but is not limited thereto, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.
Electronic device
In the present specification, the "electronic device" refers to a member constituting at least a part of an electronic component. The electronic device is not particularly limited, and various mechanical structures and circuits may be formed on the surface of the semiconductor substrate. The electronic component may preferably be a composite of a member made of a metal or a semiconductor and a resin sealing or insulating the member. The electronic device may be a rewiring layer described later, and/or a semiconductor element or another element is sealed or insulated with a sealing material or an insulating material, and may have a single-layer or multi-layer structure.
Support for medical instruments
The support is a member for supporting a semiconductor substrate or an electronic device. As described later, the support is made of a member having a property of transmitting light and supporting the semiconductor substrate.
The adhesive composition of the present embodiment contains the component (a) or (b) described below.
(a) Light absorbers, polyisocyanates, and polyols.
(b) A light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.
Hereinafter, for convenience, the adhesive composition containing the component (a) is also referred to as "adhesive composition (a)", and the adhesive composition containing the component (b) is also referred to as "adhesive composition (b)".
Both the adhesive composition (a) and the adhesive composition (b) are curable adhesive compositions, and form a crosslinked structure by heating or the like and are cured. Therefore, an adhesive layer for temporarily bonding a semiconductor substrate or the like to a support can be formed by forming an adhesive composition layer between the semiconductor substrate or an electronic device (hereinafter, also referred to as "semiconductor substrate or the like" collectively) and the support and curing the adhesive composition layer.
On the other hand, the adhesive layer formed of the adhesive composition (a) or the adhesive composition (b) contains a light absorbing agent. Therefore, when light is irradiated to the adhesive layer through the support that transmits light, the light absorbing agent in the adhesive layer absorbs the light, and the adhesive layer is modified. This makes it possible to separate the semiconductor substrate or device temporarily bonded through the adhesive layer from the support body through which light is transmitted.
Further, the adhesive layer formed of the adhesive composition (a) or the adhesive composition (b) contains a urethane resin, and therefore, the adhesive layer can be decomposed by decomposing a urethane bond with an acid or an alkali. This makes it possible to remove residues of the adhesive layer adhering to the semiconductor substrate or device after separation from the light-transmitting support.
< adhesive composition (a) >
The adhesive composition (a) contains a light absorber, a polyisocyanate, and a polyol. In the adhesive composition (a), the polyisocyanate and the polyol are bonded and crosslinked with a urethane bond by heating. This cures the adhesive composition layer, thereby forming an adhesive layer that temporarily adheres the support, the semiconductor substrate, and the like. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light, and the adhesive layer is modified. This enables the support to be separated from the semiconductor substrate and the like. Further, the residue adhering to the adhesive layer of the semiconductor substrate or the like can be removed by decomposing the urethane bond with an acid or an alkali.
The light absorbing agent: (B) composition (ingredient)
The adhesive composition (a) contains a light absorbing agent (hereinafter, also referred to as "component (B)"). By adding the component (B) to the adhesive composition (a), the adhesive layer can be modified by irradiating light.
(B) The component (c) is not particularly limited as long as it has a light-absorbing ability. The component (B) may be a component that absorbs light of a wavelength depending on the wavelength of light irradiated when the support and the semiconductor substrate are separated from each other. For example, the component (B) can be a component that absorbs light in a wavelength range of 300 to 800 nm. (B) The component is preferably a component capable of absorbing light in a wavelength region of 400 to 700 nm, more preferably a component capable of absorbing light in a wavelength region of 450 to 600nm, and still more preferably a component capable of absorbing light in a wavelength region of 500 to 550 nm.
Examples of the component (B) include pigments and dyes.
Pigments
The pigment may be an organic pigment or an inorganic pigment. The pigment may be any of a black pigment and a color pigment.
Examples of the black organic pigment include perylene black (perylene black pigment), cyanine black, aniline black, and lactam black. Examples of the black inorganic pigment include carbon black (lamp black, acetylene black, thermal black, channel black, furnace black, and the like), chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, strontium titanate, chromium oxide, cerium oxide, and the like.
Examples of The colored Pigment include compounds classified as pigments (pigments) in The color index (c.i.; issued by The Society of Dyers and Colourists company), specifically, compounds to which The following color index (c.i.) number is assigned.
C.i. pigment yellow 1 (hereinafter, also referred to as "c.i. pigment yellow" merely as a reference), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;
c.i. pigment orange 1 (hereinafter, also referred to as "c.i. pigment orange" simply as a reference number), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
c.i. pigment violet 1 (hereinafter, also referred to as "c.i. pigment violet" simply as a reference number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
c.i. pigment red 1 (hereinafter, also referred to as "c.i. pigment red" simply as a reference), 2,3, 4,5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 52: 1. 53: 1. 57 and 57: 1. 57: 2. 58: 2. 58: 4. 60: 1. 63: 1. 63: 2. 64: 1. 81: 1. 83, 88, 90: 1. 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
c.i. pigment blue 1 (hereinafter, also referred to as "c.i. pigment blue" and simply referred to as "no"), 2, 15, and 15: 3. 15: 4. 15: 6. 16, 22, 60, 64, 66;
c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 37;
c.i. pigment brown 23, c.i. pigment brown 25, c.i. pigment brown 26, c.i. pigment brown 28;
c.i. pigment black 1, pigment black 7.
The particle size of the pigment can be suitably set, and is, for example, 10nm to 1000nm, preferably 10nm to 500nm, and more preferably 10nm to 300nm as a volume average particle size. The volume average particle diameter can be determined by a dynamic light scattering method.
The pigment may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Further, a plurality of pigments which absorb light in different wavelength regions may be used in combination, and for example, a black pigment and 1 or more kinds of color pigments may be used in combination.
Dyes or dyes
Examples of the dye include azo dyes (monoazo and polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, thiazole azo dyes), anthraquinone dyes (anthraquinone derivatives, anthrone derivatives), indigo dyes (indigo derivatives, thioindigo derivatives), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes), quinonimine dyes (oxazine dyes, thiazine dyes), methine dyes (cyanine dyes, azomethine dyes), quinoline dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, and perinone dyes.
The dyes may be commercially available. Examples of commercially available dyes include PC-5857 (manufactured by Oriental Industrial Co., Ltd.).
The dye can be used alone in 1 kind, also can be used in combination with more than 2 kinds. In addition, a plurality of dyes that absorb light in different wavelength regions may be used in combination.
(B) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.
The content of the component (B) in the adhesive composition (a) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 15% by mass, based on the total mass (100% by mass) of the adhesive composition (a). When the content of the component (B) is not less than the lower limit, the absorption efficiency of light in the adhesive layer is improved, and the modification of the adhesive layer is favorable. When the content of the component (B) is not more than the above upper limit, the balance with other components can be easily obtained.
The content of the component (B) in the adhesive composition (a) may be 5 mass% or more, or may be 10 mass% or more, based on the total mass (100 mass%) of the adhesive composition (a).
Polyisocyanate compound: (I) composition (ingredient)
The adhesive composition (a) contains a polyisocyanate compound (hereinafter, also referred to as "component (I)"). In the present specification, the "polyisocyanate compound" refers to a compound (polyisocyanate) having 2 or more isocyanate groups (-N ═ C ═ O) or a compound (blocked polyisocyanate) having 2 or more blocked isocyanate groups. The polyisocyanate is not particularly limited, and a polyisocyanate generally used for producing a polyurethane resin can be used without particular limitation.
The blocked polyisocyanate is a compound in which an isocyanate group of a polyisocyanate is blocked by a reaction with a blocking agent and is inactivated. The blocked polyisocyanate used as the component (I) is preferably one obtained by blocking an isocyanate group with a thermally dissociative blocking agent. Examples of the thermally dissociative blocking agent include oximes, diketones, phenols, and caprolactams. In the blocked polyisocyanate obtained by using the thermally dissociative blocking agent, an isocyanate group is inactive at normal temperature, and the thermally dissociative blocking agent is dissociated by heating to regenerate the isocyanate group.
Specific examples of the polyisocyanate include: aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and the like; and aromatic diisocyanates such as tolylene diisocyanate, 4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, dimethylbiphenyl diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and the like; and biuret, isocyanurate, and trimethylolpropane adducts thereof. The polyisocyanate may be used alone in 1 kind or in combination of 2 or more kinds.
The polyisocyanate may be any commercially available one. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (trade name, manufactured by Asahi Kasei Chemicals). These products may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the blocked isocyanate include compounds in which the isocyanate group of the polyisocyanate is blocked by a reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociative blocking agent, that is, a compound which is added to an isocyanate group and is stable at room temperature but is dissociated when heated to a dissociation temperature or higher to generate an isocyanate group, and a known compound can be used without particular limitation.
Specific examples of the blocking agent include: lactam compounds such as γ -butyrolactam, e-caprolactam, γ -valerolactam and propiolactam; oxime compounds such as methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime, acetone oxime, diacetyl monooxime, benzophenone oxime and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methanol, ethanol, isopropanol, t-butanol, trimethylolpropane and 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; active methylene compounds such as alkyl malonate, dialkyl malonate, alkyl acetoacetate, and acetylacetone; and so on. The number of the capping agents may be 1 or more.
Blocked polyisocyanates can be made by reacting a polyisocyanate with a blocking agent. The reaction of the polyisocyanate with the blocking agent is carried out, for example, in a solvent having no active hydrogen (1, 4-dioxane, cellosolve acetate, etc.) under heating at about 50 to 100 ℃ and in the presence of a blocking catalyst added as needed. The ratio of the polyisocyanate to the blocking agent to be used is not particularly limited, and is preferably 0.95: 1.0-1.1: 1.0, more preferably 1: 1.05 to 1.15. As the blocking catalyst, known ones can be used, and examples thereof include: metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, and potassium methoxide; tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; organic weak acid salts such as acetate, octanoate, myristate and benzoate; alkali metal salts of alkyl carboxylic acids such as acetic acid, caproic acid, caprylic acid, and myristic acid; and so on. The number of the capping catalysts may be 1 or more than 2.
The blocked polyisocyanate may be any commercially available one. Examples of commercially available blocked polyisocyanates include Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (trade name, manufactured by Asahi Kasei corporation).
The component (I) is preferably a blocked polyisocyanate obtained by blocking an isocyanate group with a thermally dissociative blocking agent.
(I) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.
The content of the component (I) in the adhesive composition (a) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 40% by mass, based on the total mass (100% by mass) of the adhesive composition (a). When the content of the component (I) is not less than the lower limit, the adhesive composition (a) can be cured well. When the content of the component (I) is not more than the upper limit, the balance with other components can be easily obtained.
Polyol: (O) ingredient
The adhesive composition (a) contains a polyol (hereinafter, also referred to as "component (O)"). The polyol is a compound having 2 or more hydroxyl groups (-OH). The polyol is not particularly limited, and a polyol generally used for producing a polyurethane resin can be used without particular limitation. The component (O) may be an aliphatic polyol or an aromatic polyol. The component (O) may be a low-molecular polyol (for example, a molecular weight of less than 500) or a high-molecular polyol (for example, a molecular weight of 500 or more).
Specific examples of the low-molecular polyol include: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, an alkanediol having 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, an alkane-1, 2-diol having 17 to 20 carbon atoms, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, 8-diol, 2-membered alcohols such as bisphenol A; 3-membered alcohols such as glycerin and trimethylolpropane; 4-membered alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; 5-membered alcohols such as xylitol; 6-membered alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; 7-membered alcohols such as mannitol; and 8-membered alcohols such as sucrose; and so on.
Examples of the polymer polyol include a phenol resin, a resin having a hydroxystyrene skeleton, a polyester polyol, a polyether polyol, a polyesteramide polyol, an acrylic polyol (acryl polyol), a polycarbonate polyol, a polyhydroxyalkane, a polyurethane polyol, and a vegetable oil polyol. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.
[ phenol resin ]
The phenolic resin may be Novolac type phenolic resin or Resol type phenolic resin. The Novolac-type phenol resin can be obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, referred to as "phenol") and an aldehyde in the presence of an acid catalyst. The Resol-type phenol resin can be obtained by addition condensation of a phenol and an aldehyde in the presence of a basic catalyst.
Examples of the phenols include: phenol; cresols such as m-cresol, p-cresol and o-cresol; xylenols such as 2, 3-xylenol, 2, 5-xylenol, 3, 5-xylenol, and 3, 4-xylenol; alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3, 5-trimethylphenol, 2,3, 5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol and the like; aryl phenols such as phenylphenol; polyhydric phenols such as 4, 4' -dihydroxybiphenyl, bisphenol a, resorcinol, hydroquinone, pyrogallol, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, and 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane.
Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxymethylene, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α -phenylpropanal, β -phenylpropanal, o-hydroxyphenylformaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, and 4-phenylbenzaldehyde.
The acid catalyst used in the addition condensation reaction is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The alkali catalyst used in the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium carbonate, hexamethylenetetramine, or the like can be used.
[ resin containing hydroxystyrene skeleton ]
The resin containing a hydroxystyrene skeleton is not particularly limited as long as it has a structural unit derived from hydroxystyrene or a hydroxystyrene derivative. Specific examples of the structural unit derived from hydroxystyrene or a hydroxystyrene derivative include a structural unit represented by the following general formula (a 10-1).
[ chemical formula 1]
Figure BDA0003647599760000151
[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Yax1Is a single bond or a 2-valent linking group. Wax1Is (n)ax1+1) a valent aromatic hydrocarbon radical. n isax1Is an integer of 1 to 3.]
In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The haloalkyl group having 1 to 5 carbon atoms in R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.
In the above formula (a10-1), Yax1Is a single bond or a 2-valent linking group.
As Yax1The 2-valent linking group in (2) may be, for example, a 2-valent hydrocarbon group which may have a substituent, or a 2-valent linking group containing a hetero atom, and these are suitable groups.
A 2-valent hydrocarbon group which may have a substituent:
Yax1when the hydrocarbon group is a 2-valent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
··Yax1Aliphatic hydrocarbon group of (1)
The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group having a ring in the structure.
Linear or branched aliphatic hydrocarbon radical
The number of carbon atoms of the linear aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3.
The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include methylene [ -CH ]2-]Ethylene [ - (CH)2)2-]Trimethylene [ - (CH)2)3-]Tetra-methylene [ - (CH)2)4-]Penta-methylene [ - (CH)2)5-]And the like.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include: -CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-etcAn alkyl methylene group; -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-isoalkylethylene; -CH (CH)3)CH2CH2-、-CH2CH(CH3)CH2-isoalkyltrimethylene groups; -CH (CH)3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2An alkylalkylene group such as an isoalkyltetramethylene group, and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The above-mentioned linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluoroalkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like.
Aliphatic hydrocarbon groups containing rings in the structure
Examples of the cyclic aliphatic hydrocarbon group having such a structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing 2 hydrogen atoms from an aliphatic hydrocarbon ring) having a ring structure which may contain a substituent containing a hetero atom, a group in which the cyclic aliphatic hydrocarbon group is bonded to an end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is present in the middle of the linear or branched aliphatic hydrocarbon group. Examples of the above-mentioned linear or branched aliphatic hydrocarbon group include the same groups as described above.
The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocycloparaffin. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from polycycloalkane (polycycloalkane), and the polycycloalkane is preferably a polycyclic alkane having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornene, tricyclodecane, tetracyclododecane, and the like.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the haloalkyl group as the substituent include groups in which a part or all of hydrogen atoms of the alkyl group are substituted with the halogen atom.
In the case of a cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure thereof may be substituted with a substituent containing a hetero atom. The substituent containing a hetero atom is preferably — O-, -C (═ O) -O-, -S (═ O)2-、-S(＝O)2-O-。
··Yax1Aromatic hydrocarbon radical in (1)
The aromatic hydrocarbon group is a hydrocarbon group having at least 1 aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Wherein the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include: a group (arylene or heteroarylene) obtained by removing 2 hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring; a group obtained by removing 2 hydrogen atoms from an aromatic compound having 2 or more aromatic rings (for example, biphenyl, fluorene, or the like); a group (aryl or heteroaryl) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring, wherein 1 hydrogen atom is substituted with an alkylene group (for example, a group obtained by further removing 1 hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and the like. The alkylene group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
The above aromatic hydrocarbon group may have a hydrogen atom substituted by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, the halogen atom, and the haloalkyl group as the substituent include those exemplified as substituents for substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
A heteroatom-containing 2-valent linking group:
Yax1in the case of a 2-valent linking group containing a hetero atom, those preferred as the linking groupExamples of the group include-O-, -C (═ O) -, -O-C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ NH) - (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S (═ O)2-、-S(＝O)2-O-, formula-Y21-O-Y22-、-Y21-O-、-Y21-C(＝O)-O-、-C(＝O)-O-Y21-、-[Y21-C(＝O)-O]m”-Y22-、-Y21-O-C(＝O)-Y22-or-Y21-S(＝O)2-O-Y22A group represented by (wherein Y is)21And Y22Each independently a 2-valent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3.]And the like.
When the heteroatom-containing 2-valent linking group is — C (═ O) -NH-, -C (═ O) -NH-C (═ O) -, -NH-C (═ NH) -, H thereof may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent (such as an alkyl group or an acyl group) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.
General formula-Y21-O-Y22-、-Y21-O-、-Y21-C(＝O)-O-、-C(＝O)-O-Y21-、-[Y21-C(＝O)-O]m”-Y22-、-Y21-O-C(＝O)-Y22-or-Y21-S(＝O)2-O-Y22In (Y)21And Y22Each independently a 2-valent hydrocarbon group which may have a substituent. Examples of the 2-valent hydrocarbon group include the same 2-valent hydrocarbon groups as those (2-valent hydrocarbon groups which may have a substituent) mentioned in the description of the 2-valent linking group.
As Y21The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.
As Y22The aliphatic hydrocarbon group is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group。
Of the formula [ Y21-C(＝O)-O]m”-Y22In the group represented by (A), m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. I.e., as formula- [ Y ]21-C(＝O)-O]m”-Y22A group represented by the formula-Y is particularly preferred21-C(＝O)-O-Y22-a group represented by (a). Among them, preferred is a compound represented by the formula- (CH)2)a’-C(＝O)-O-(CH2)b’-a group represented by (a). In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.
As Yax1Preferably a single bond, an ester bond [ -C (═ O) -O-]An ether bond (-O-) -, -C (-O) -NH-, a linear or branched alkylene group, or a combination thereof, and among these, a single bond is particularly preferable.
In the above formula (a10-1), Wax1Is (n)ax1+1) a valent aromatic hydrocarbon radical.
As Wax1The aromatic hydrocarbon group in (1) includes removal of (n) from the aromatic ringax1+1) hydrogen atoms. The aromatic ring herein is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be a monocyclic or polycyclic ring. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
In the above formula (a10-1), nax1Is an integer of 1 to 3, preferably 1 or 2, more preferably 1.
Specific examples of the structural unit represented by the above general formula (a10-1) are shown below.
In the formula, RαRepresents a hydrogen atom, a methyl group or a trifluoromethyl group.
[ chemical formula 2]
Figure BDA0003647599760000211
The resin containing a hydroxystyrene skeleton is preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, and more preferably a polymer of hydroxystyrene (polyhydroxystyrene).
[ polycarbonate polyol ]
Examples of the polycarbonate polyol include those obtained by reacting 1 or 2 or more kinds of diols selected from ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 9-nonanediol, 1, 8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, and the like, with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, and the like.
Among them, the polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).
[ chemical formula 3]
Figure BDA0003647599760000212
[ wherein Rp1And Rp2Each independently is a 2-valent hydrocarbyl group. np is an integer of 2 or more.]
In the above general formula (PC-1), Rp1And Rp2Each independently is a 2-valent hydrocarbyl group. The 2-valent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The 2-valent hydrocarbon group may be a group similar to Ya of the general formula (a10-1)x1The same 2-valent hydrocarbon groups as mentioned in (1). As Rp1And Rp2The 2-valent hydrocarbon group in (1) is preferably an aliphatic hydrocarbon group, more preferablyPreferably a linear or branched alkylene group. The 2-valent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. As Rp1And Rp2Specific examples of (2) include- (CH)2)6-, or- (CH)2)5-。
The polycarbonate polyol preferably has a weight average molecular weight (Mw) of 500 to 5000, more preferably 500 to 3000, still more preferably 500 to 2000, and particularly preferably 500 to 1000.
[ other polyols ]
Examples of the polyester polyol include: polyester polyols obtained by reacting dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid, dialkyl esters thereof or mixtures thereof with glycols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3' -dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol, or mixtures thereof; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polypentanolide, and poly (. beta. -methyl-. gamma. -valerolactone).
Examples of the polyether polyol include polyether polyols obtained by polymerizing an alkylene oxide compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran with a low-molecular-weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerol as an initiator.
Examples of the polyether polyol include polyether polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or a dialkyl ester thereof, or a mixture thereof with the polyether polyol.
Examples of the polyesteramide polyol include polyesteramide polyols obtained by using, as raw materials, aliphatic diamines having an amino group such as ethylenediamine, propylenediamine, and 1, 6-hexamethylenediamine in combination during the esterification reaction.
Examples of the acrylic polyol include polyesteramide polyols obtained by copolymerizing acrylic acid, methacrylic acid, or an ester thereof with hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like having 1 or more hydroxyl groups in 1 molecule, or a corresponding methacrylic acid derivative thereof, or the like.
Examples of the polyhydroxyalkane (polyhydroxyalkane) include liquid rubbers obtained by copolymerizing butadiene or butadiene with acrylamide or the like.
The polyurethane polyol is a polyol having 1 or more urethane bonds in the molecule, and examples thereof include a polyurethane polyol obtained by reacting a polyether polyol, a polyester polyol, a polyether polyol, or the like having a number average molecular weight of 200 to 20,000 with a polyisocyanate under a condition that the NCO/OH is preferably less than 1, more preferably 0.9 or less.
Examples of the vegetable oil-based polyol include castor oil, castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol. Among these, the vegetable oil-based polyol is preferably a castor oil-modified polyol, and more preferably a castor oil-modified diol.
Among the above, as the component (O), a phenol resin or a resin containing a hydroxystyrene skeleton is preferable, a Novolac resin or a resin containing a hydroxystyrene skeleton is more preferable, a polymer of hydroxystyrene or a hydroxystyrene derivative is further preferable, and a polyhydroxystyrene resin is particularly preferable.
As the component (O), 1 kind may be used alone, or 2 or more kinds may be used in combination.
The content of the (O) component in the adhesive composition (a) is preferably 50 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 60 to 85% by mass, based on the total mass (100% by mass) of the adhesive composition (a). When the content of the component (O) is not less than the lower limit, the adhesive composition (a) can be cured well. When the content of the component (I) is not more than the above upper limit, the balance with other components can be easily obtained.
The molar ratio (NCO/OH) of hydroxyl groups (-OH) in the component (O) to isocyanate groups (-NCO) in the component (I) contained in the adhesive composition (a) is preferably 0.1 to 1, more preferably 0.3 to 0.7.
In the adhesive composition (a), the mass ratio of the content of the component (I) to the content of the component (O) is preferably (I): 1: 10-10: 1, more preferably 2: 8-8: 2, more preferably 2: 8-5: 5.
< adhesive composition (b) >
The adhesive composition (b) contains a light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. The adhesive composition (b) is obtained by polymerizing and crosslinking a urethane resin containing a polymerizable carbon-carbon unsaturated bond by heating or the like. This cures the adhesive composition layer, thereby forming an adhesive layer that temporarily adheres the support, the semiconductor substrate, and the like. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light, and the adhesive layer is modified. This enables the support to be separated from the semiconductor substrate and the like. Further, the residue adhering to the adhesive layer of the semiconductor substrate or the like can be removed by decomposing the urethane bond with an acid or an alkali.
Light absorbers: (B) composition (ingredient)
The adhesive composition (B) contains a light absorber (component (B)). The component (B) is the same as the component (a) of the adhesive composition. The component (B) may contain a compound (B1) (hereinafter, also referred to as a component (B1)) which absorbs at least part of light in a wavelength range of 300 to 800nm and contains a polymerizable carbon-carbon unsaturated bond.
Component (B1)
(B1) The component (B) is a compound which absorbs at least part of light in a wavelength range of 300 to 800nm and contains a polymerizable carbon-carbon unsaturated bond. The component (B1) is a compound that does not belong to the component (P1) described later.
Since the component (B1) contains a polymerizable carbon-carbon unsaturated bond, it can react with a urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond (hereinafter, also referred to as a "component (P1)") described later and be cured, thereby forming an adhesive layer together with the component (P1). This allows the semiconductor substrate or the electronic device to be temporarily bonded to the support. Further, since the component (B1) absorbs at least a part of light in a wavelength range of 300 to 800nm, the component (B1) absorbs light and releases heat by irradiating the adhesive layer with light in a wavelength range of 300 to 800 nm. This enables modification of the adhesive layer.
(B1) The component (A) functions as a light absorber that absorbs light having a wavelength of 300 to 800 nm. (B1) The component can absorb light in a wavelength range of 300-800 nm and convert the light into heat energy of a degree capable of modifying the adhesive layer. (B1) The component is preferably a component capable of absorbing light in a wavelength region of 300 to 700 nm, more preferably a component capable of absorbing light in a wavelength region of 300 to 600nm, still more preferably a component capable of absorbing light in a wavelength region of 300 to 550nm, and particularly preferably a component capable of absorbing light in a wavelength region of 300 to 400 nm. (B1) The component preferably has an absorption peak in the above wavelength region. The component (B1) may be a component that absorbs light of a wavelength used for separating the support from the semiconductor substrate or the like, depending on the wavelength. The component (B1) includes, for example, a component capable of absorbing light having a wavelength of 355nm and converting the light into thermal energy to modify the adhesive layer.
The polymerizable carbon-carbon unsaturated bond contained in the compound (B1) is not particularly limited, but is preferably radical polymerizable. Examples of the polymerizable carbon-carbon unsaturated bond include a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. Examples of the polymerizable carbon-carbon double bond include, but are not limited to, a vinyl group, a methacryloyl group, and an acryloyl group. Examples of the polymerizable carbon-carbon triple bond include, but are not limited to, an ethynyl group and a propargyl group.
Examples of the compound (B1) include compounds represented by the following general formula (B1).
[ chemical formula 4]
Figure BDA0003647599760000251
[ wherein W is a 1-valent group containing a polymerizable carbon-carbon unsaturated bond; y is a single bond, or a 2-valent linking group selected from the group consisting of-O-, -CO-, -COO-, and-CONH-; n is an integer of 1-6; x is an n-valent atomic group having an aromatic condensed ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton in its structure. When n is 2 or more, a plurality of W and Y may be the same or different. ]
In the general formula (b1), W is a polymerizable group-containing group having a polymerizable carbon-carbon unsaturated bond. Examples of the polymerizable carbon-carbon unsaturated bond contained in W include a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. Examples of W include alkenyl and alkynyl groups. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 or 3 carbon atoms. Specific examples of the alkenyl group include a vinyl group, an isopropenyl group and the like. The alkynyl group preferably has 2 to 6 carbon atoms, more preferably has 2 or 3 carbon atoms, and still more preferably has 2 carbon atoms. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group and the like.
In the general formula (b1), Y is a single bond or a 2-valent linking group selected from the group consisting of-O-, -CO-, -COO-, and-CONH-. Among them, Y is preferably a single bond, -COO-, or-CONH-, and more preferably a single bond or-CONH-.
In the general formula (b1), n is an integer of 1 to 6. n is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1. When n is 2 or more, a plurality of W may be the same or different from each other, but preferably the same. When n is 2 or more, a plurality of Y may be the same or different from each other, but preferably the same.
In the general formula (b1), X is an n-valent atomic group having an aromatic condensed ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton in its structure.
[ n-valent atomic group having aromatic condensed ring skeleton ]
The fused ring skeleton having aromaticity includes a fused ring having at least 1 aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings in the fused ring is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. The condensed ring may be composed of only an aromatic ring or may be a condensed ring formed by an aromatic ring and an aliphatic hydrocarbon ring, but is preferably composed of only an aromatic ring. Specific examples of the condensed ring include naphthalene, anthracene, phenanthrene, pyrene, and the like. Among them, anthracene or phenanthrene is preferable.
Examples of X having a condensed ring skeleton having aromaticity include structures represented by the following general formulae (Xa-1) and (Xa-2). X represented by the general formula (Xa-1) is an atomic group having an anthracene skeleton, and X represented by the general formula (Xa-2) is an atomic group having a phenanthrene skeleton.
[ chemical formula 5]
Figure BDA0003647599760000261
[ in the formula, La1And La2Each independently represents a single bond or a 2-valent linking group, Ra1And Ra2Each independently represents a substituent. n is the same as n in the above formula (b 1). m represents an integer of 0 to 9, and m + n is not more than 10. When n is 2 or more, a plurality of L's are presenta1And La2May be the same or different from each other. When m is 2 or more, a plurality of R exista1And Ra2May be the same or different from each other. Is a chemical bond to Y in the general formula (b 1).]
In the general formulae (Xa-1) and (Xa-2), La1And La2Each independently represents a single bond or a 2-valent linking group. Examples of the above-mentioned 2-valent linking group include a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group may be linear or branched, and may contain a ring in the structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group having a ring structure preferably has 3 to 10 carbon atoms, and preferably has 3 to 6 carbon atoms.
The aliphatic hydrocarbon group may have a substituent. The substituent may be a substituent substituted for a hydrogen atom or a methylene group (-CH) in a carbon chain2-) substituted substituents. Examples of the substituent substituted for a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group and the like, and a hydroxyl group or an amino group is preferable. As methylene (-CH) in the para-carbon chain2-) includes, for example, -O-, -CO-, -NH-, -COO-, -CONH-, and the like.
The aromatic hydrocarbon group is a hydrocarbon group containing at least 1 aromatic ring. The aromatic ring included in the aromatic hydrocarbon group may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings included in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring is bonded to an aliphatic hydrocarbon group.
The above aromatic hydrocarbon group may have a substituent. The substituent may be a substituent substituted for a hydrogen atom of an aromatic ring, or a substituent substituted for a carbon atom of a ring constituting an aromatic ring with a hetero atom. Examples of the substituent substituted for a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group and the like, and a hydroxyl group or an amino group is preferable. Examples of the hetero atom substituting the ring of the aromatic ring include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and a nitrogen atom is preferable.
In the general formulae (Xa-1) and (Xa-2), Ra1And Ra2Each independently represents a substituent. As Ra1And Ra2Examples thereof include alkyl and hydroxyA group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, a nitrile alkyl group, an alicyclic group, or the like. The alkyl group, alkoxy group, and cyanoalkyl group preferably have 1 to 5 carbon atoms, and more preferably have 1 to 3 carbon atoms. The alicyclic group preferably has 1 to 6 carbon atoms. Examples of the nitrile alkyl group include a malonyl nitrile group. The alicyclic group may be an alicyclic hydrocarbon ring or an alicyclic heterocyclic ring. Examples of the alicyclic heterocyclic ring include alicyclic heterocyclic rings containing a sulfur atom, a nitrogen atom, or an oxygen atom. Specific examples of the alicyclic heterocyclic ring include dithiolane.
In the general formulae (Xa-1) and (Xa-2), m represents an integer of 0 to 9. m is preferably 0 to 6, more preferably 0 to 5, further preferably 0 to 3, and particularly preferably 0 to 2.
In the general formulae (Xa-1) and (Xa-2), n is the same as n in the above formula (b 1).
m and n have a relationship of m + n ≦ 10.
[ n-valent radical having benzophenone skeleton ]
Examples of X having a benzophenone skeleton include structures represented by the following general formula (Xb).
[ chemical formula 6]
Figure BDA0003647599760000281
[ in the formula, Lb1And Lb2Each independently represents a single bond or a 2-valent linking group, Rb1And Rb2Each independently represents a substituent. p and q each independently represent an integer of 0 to 5, and p + q is n. n is the same as n in the above formula (b 1). m1 and m2 each independently represent an integer of 0 to 5, m1+ p is not more than 5, and m2+ q is not more than 5. When p is 2 or more, a plurality of L's are presentb1May be the same or different from each other. When q is 2 or more, a plurality of L's existb2May be the same or different from each other. When m1 is 2 or more, a plurality of R's are presentb1May be the same or different from each other. When m2 is 2 or more, a plurality of R's are presentb2May be the same or different from each other.Is a chemical bond to Y in the general formula (b 1).]
In the general formula (Xb), Lb1And Lb2Each independently represents a single bond or a 2-valent linking group. The 2-valent linking group may be the group bonded to L in the formulae (Xa-1) and (Xa-2)a1And La2The same groups as mentioned in (1). L isb1And Lb2Preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent(s) is preferably one having 1 to 5 carbon atoms, more preferably one having 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or a methylene group (-CH) constituting a carbon chain2-) is partially substituted with-O-, -CO-, -NH-, -COO-, -CONH-.
In the general formula (Xb), Rb1And Rb2Each independently represents a substituent. As Rb1And Rb2Examples thereof include the compounds represented by the above formulae (Xa-1) and (Xa-2) in which R is the same as that in the above formulaea1And Ra2The same groups as mentioned above.
In the general formula (Xb), p and q each independently represent an integer of 0 to 5, and p + q is n. N is the same as n in the formula (b 1).
In the general formula (Xb), m1 and m2 each independently represent an integer of 0 to 5, m1+ p is not more than 5, and m2+ q is not more than 5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
[ n-valent atomic group having dibenzoylmethane skeleton ]
Examples of X having a dibenzoylmethane skeleton include structures represented by the following general formula (Xc).
[ chemical formula 7]
Figure BDA0003647599760000291
[ in the formula, Lc1And Lc2Each independently represents a single bond or a 2-valent linking group, Rc1And Rc2Each independently represents a substituent. p and q each independently represent an integer of 0 to 5, and p + q is n. n is the same as n in the above formula (b1). m1 and m2 each independently represent an integer of 0 to 5, m1+ p is not more than 5, and m2+ q is not more than 5. When p is 2 or more, a plurality of L's are presentc1May be the same or different from each other. When q is 2 or more, a plurality of L's existc2May be the same or different from each other. When m1 is 2 or more, a plurality of R's are presentc1May be the same or different from each other. When m2 is 2 or more, a plurality of R's are presentc2May be the same or different from each other. Is a chemical bond to Y in the general formula (b 1).]
In the general formula (Xc), Lc1And Lc2Each independently represents a single bond or a 2-valent linking group. The 2-valent linking group may be the group bonded to L in the formulae (Xa-1) and (Xa-2)a1And La2The same groups as mentioned in (1). L isc1And Lc2Preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent(s) is preferably one having 1 to 5 carbon atoms, more preferably one having 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or a methylene group (-CH) constituting a carbon chain2-) is partially substituted with-O-, -CO-, -NH-, -COO-, -CONH-.
In the general formula (Xc), Rc1And Rc2Each independently represents a substituent. As Rc1And Rc2Examples thereof include the compounds represented by the above formulae (Xa-1) and (Xa-2) in which R is the same as that in the above formulaea1And Ra2The same groups as mentioned in (1).
In the general formula (Xc), p and q each independently represent an integer of 0 to 5, and p + q is n. N is the same as n in the formula (b 1).
In the general formula (Xc), m1 and m2 each independently represent an integer of 0 to 5, m1+ p is not more than 5, and m2+ q is not more than 5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
[ n-valent atomic group having dibenzoylbenzene skeleton ]
Examples of X having a dibenzoylbenzene skeleton include structures represented by the following general formula (Xd).
[ chemical formula 8]
Figure BDA0003647599760000301
[ in the formula, Ld1、Ld2And Ld3Each independently represents a single bond or a 2-valent linking group, Rd1、Rd2And Rd3Each independently represents a substituent. p and q each independently represent an integer of 0 to 5, r represents an integer of 0 to 4, and p + q + r is n. n is the same as n in the above formula (b 1). m1 and m2 each independently represent an integer of 0 to 5, m3 represents an integer of 1 to 4, m1+ p is not more than 5, m2+ q is not more than 5, and m3+ r is not more than 4. When p is 2 or more, a plurality of L's are presentd1May be the same or different from each other. When q is 2 or more, a plurality of L's existd2May be the same or different from each other. When r is 2 or more, a plurality of L's are presentd3May be the same or different from each other. When m1 is 2 or more, a plurality of R's are presentd1May be the same or different from each other. When m2 is 2 or more, a plurality of R's are presentd2May be the same or different from each other. When m3 is 2 or more, a plurality of R's are presentd3May be the same or different from each other. Is a chemical bond to Y in the general formula (b 1).]
In the general formula (Xd), Ld1、Ld2And Ld3Each independently represents a single bond or a 2-valent linking group. The 2-valent linking group may be the group bonded to L in the formulae (Xa-1) and (Xa-2)a1And La2The same groups as mentioned in (1). L isd1、Ld2And Ld3Preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent(s) is preferably one having 1 to 5 carbon atoms, more preferably one having 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or a methylene group (-CH) constituting a carbon chain2-) is partially substituted with-O-, -CO-, -NH-, -COO-, -CONH-.
In the general formula (Xd), Rd1、Rd2And Rd3Each independentlyRepresents a substituent. As Rd1、Rd2And Rd3Examples thereof include the compounds represented by the above formulae (Xa-1) and (Xa-2) in which R is the same as that in the above formulaea1And Ra2The same groups as mentioned in (1).
In the general formula (Xd), p and q each independently represent an integer of 0 to 5, r represents an integer of 0 to 4, and p + q + r is n. N is the same as n in the formula (b 1).
In the general formula (Xd), m1 and m2 each independently represent an integer of 0 to 5, m3 represents an integer of 1 to 4, m1+ p is not more than 5, m2+ q is not more than 5, and m3+ r is not more than 4. m1, m2 and m3 are preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
[ n-valent group having benzotriazole skeleton ]
Examples of X having a benzotriazole skeleton include structures represented by the following general formula (Xe).
[ chemical formula 9]
Figure BDA0003647599760000321
[ wherein, LeRepresents a single bond or a 2-valent linking group, ReRepresents a substituent. n is the same as n in the above formula (b 1). m represents an integer of 0 to 4, and m + n is not more than 5. When n is 2 or more, a plurality of L's are presenteMay be the same or different from each other. When m is 2 or more, a plurality of R existeMay be the same or different from each other. Is a chemical bond with Y in the general formula (b 1).]
In the general formula (Xe), LeRepresents a single bond or a 2-valent linking group. The 2-valent linking group may be the group bonded to L in the formulae (Xa-1) and (Xa-2)a1And La2The same groups as mentioned in (1). L iseThe hydrocarbon group may preferably be a single bond or a substituted hydrocarbon group, and preferably a single bond, an alkyl group which may have a substituent, or a group in which 1 hydrogen atom of the benzene ring is substituted with an alkyl group. The alkyl group which may have a substituent and the alkyl group bonded to the benzene ring preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
In the general formula (Xe), ReRepresents a substituent. As ReExamples thereof include the compounds represented by the formula (Xa-1) and the formula (Xa-2) mentioned abovea1And Ra2The same groups as mentioned in (1).
In the general formula (Xe), m represents an integer of 0 to 4. m is preferably 0 to 3, more preferably 0 to 2, and further preferably 0 or 1.
In the general formula (Xe), n is the same as n in the above formula (b 1). In this case, n is an integer of 1 to 5.
m and n have a relationship of m + n ≦ 5.
Compound (B1) is preferably a compound represented by the following general formula (B1-1) or (B1-2).
[ chemical formula 10]
Figure BDA0003647599760000322
[ in the formula, R11、R12And R13Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; y is1Is a single bond or a 2-valent linking group selected from the group consisting of-O-, -CO-, -COO-, and-CONH-, n1Is an integer of 1 to 6; x1N is an aromatic condensed ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton or a benzotriazole skeleton1A valence radical. n is1When the number is 2 or more, a plurality of R's are present11、R12And R13And Y1May be the same or different from each other.]
[ chemical formula 11]
Figure BDA0003647599760000331
[ wherein, R21Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; y is2Is a single bond, or a 2-valent linking group selected from the group consisting of-O-, -CO-, -COO-, and-CONH-; n is2Is an integer of 1 to 6; x2The structure of the compound contains aromatic condensed ring skeleton, benzophenone skeleton and dibenzoyl methaneN of a skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton2A valence radical. n is a radical of an alkyl radical2When the number is 2 or more, a plurality of R's exist21And Y2May be the same or different from each other.]
In the general formula (b1-1), R11、R12And R13Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R11And R12Each independently is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. R13Preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.
In the general formula (b1-1), Y1The same as Y in the above general formula (b 1).
In the general formula (b1-1), X1The same as X in the above general formula (b 1).
In the general formula (b1-1), n1The same as n in the above general formula (b 1). n is1When the number is 2 or more, a plurality of R's are present11、R12And R13May be the same or different from each other. n is1When the number is 2 or more, plural Y's are present1May be the same or different from each other. n is1When the number is 2 or more, there are plural X' s1May be the same or different from each other.
In the general formula (b1-2), R21Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R21The hydrogen atom, methyl group or ethyl group is preferable, the hydrogen atom or methyl group is more preferable, and the hydrogen atom is further preferable.
In the general formula (b1-2), Y2The same as Y in the above general formula (b 1).
In the general formula (b1-2), X2The same as X in the above general formula (b 1).
In the general formula (b1-2), n2The same as n in the above general formula (b 1). n is2When the number is 2 or more, a plurality of R's exist21May be the same or different from each other. n is2When the number is 2 or more, plural Y's are present2May be the same or different from each other. n is2When the number is 2 or more, the product is storedAt a plurality of X2May be the same or different from each other.
Specific examples of the compound (B1) having a fused ring skeleton having aromaticity are shown below, but the compound is not limited thereto.
[ chemical formula 12]
Figure BDA0003647599760000341
[ chemical formula 13]
Figure BDA0003647599760000351
[ chemical formula 14]
Figure BDA0003647599760000352
Specific examples of the compound having a benzophenone skeleton (B1) are shown below, but the present invention is not limited thereto.
[ chemical formula 15]
Figure BDA0003647599760000361
Specific examples of the compound having a dibenzoylmethane skeleton (B1) are shown below, but the compound is not limited thereto.
[ chemical formula 16]
Figure BDA0003647599760000362
Specific examples of the compound having a dibenzoylbenzene skeleton (B1) are shown below, but the compound is not limited thereto.
[ chemical formula 17]
Figure BDA0003647599760000371
Specific examples of the compound having a benzotriazole skeleton (B1) are shown below, but the compound is not limited to these.
[ chemical formula 18]
Figure BDA0003647599760000372
(B1) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.
The content of the component (B1) in the adhesive composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and may be 10 parts by mass or more, or 15 parts by mass or more, based on 100 parts by mass of the polyurethane resin (P1) described later. (B1) The upper limit of the content of the component (b) is not particularly limited, and may be, for example, 30 parts by mass or less or 20 parts by mass or less with respect to 100 parts by mass of a polyurethane resin (P1) described later. The content of the component (B1) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably 5 to 15 parts by mass, based on 100 parts by mass of the polyurethane resin (P1) described later. When the content of the component (B1) is not less than the lower limit, the light absorption efficiency in the adhesive layer is improved, and the adhesive layer is favorably modified. When the content of the component (B1) is not more than the above upper limit, the balance with other components can be easily obtained.
(B) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.
The content of the component (B) in the adhesive composition (B) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 15% by mass, based on the total mass (100% by mass) of the adhesive composition (B). When the content of the component (B) is not less than the lower limit, the absorption efficiency of light in the adhesive layer is improved, and the modification of the adhesive layer is favorable. When the content of the component (B) is not more than the upper limit, the balance with other components can be easily obtained.
The content of the component (B) in the adhesive composition (B) may be 5 mass% or more, or may be 10 mass% or more, based on the total mass (100 mass%) of the adhesive composition (B).
Polyurethane resin containing polymerizable carbon-carbon unsaturated bond: (P1) ingredient
The adhesive composition (b) contains a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond (hereinafter, also referred to as "component P1"). The component (P1) can be polymerized and cured by a polymerizable carbon-carbon unsaturated bond to form an adhesive layer. This allows the semiconductor substrate or the electronic device to be temporarily bonded to the support. Further, the urethane bond in the component (P1) has a property of being decomposable by an acid or a base. Therefore, the adhesive layer can be easily removed by a treatment liquid containing an acid or an alkali.
The polymerizable carbon-carbon unsaturated bond contained in the component (P1) is not particularly limited, but is preferably radical polymerizable. The polymerizable carbon-carbon unsaturated bond may be a polymerizable carbon-carbon double bond or a polymerizable carbon-carbon triple bond, but is preferably a polymerizable carbon-carbon double bond. Examples of the polymerizable carbon-carbon double bond include a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon unsaturated bond contained in the component (P1) may be 1 type or 2 or more types.
The equivalent weight of the polymerizable carbon-carbon unsaturated bond contained in the component (P1) is preferably 200 to 2000 g/eq.more preferably 300 to 1500 g/eq.more preferably 400 to 1200 g/eq.more preferably 500 to 1000 g/eq.. When the polymerizable carbon-carbon unsaturated bond equivalent is equal to or more than the lower limit of the above preferable range, the elastic modulus, heat resistance, and the like of the adhesive layer are further improved. When the polymerizable carbon-carbon unsaturated bond equivalent is not more than the upper limit of the above preferable range, the adhesive layer is not excessively hardened, and the cleaning property is improved. The above equivalent number is the molecular weight of the polyurethane resin per 1 equivalent of the polymerizable carbon-carbon unsaturated bond.
The weight average molecular weight (Mw) of the component (P1) is preferably 5,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 12,000 to 30,000, and particularly preferably 13,000 to 25,000.
The component (P1) can be synthesized by a polyaddition reaction of a polyisocyanate compound (component (I)) and a polyol (component (O)). That is, the component (P1) may be a reaction product of the component (I) and the component (O). Preferably, at least one of the component (I) and the component (O) contains a polymerizable carbon-carbon unsaturated bond.
Polyisocyanate compound: (I) composition (I)
The component (I) used for synthesizing the component (P1) includes the same components as those listed as the component (I) in the adhesive composition (a).
(I) The components can be used alone in 1 kind, also can be combined with more than 2 kinds. For example, a mixture of an aliphatic diisocyanate and an aromatic diisocyanate may be used as the component (I). The aliphatic diisocyanate is preferably hydrogenated xylylene diisocyanate. The aromatic diisocyanate is preferably 4, 4-diphenylmethane diisocyanate.
Polyol: (O) component
Examples of the (O) component used for synthesizing the (P1) component include a polyol containing a polymerizable carbon-carbon unsaturated bond (hereinafter, also referred to as "O1" component) and other polyols (hereinafter, also referred to as "O2" component).
A polyol having a polymerizable carbon-carbon unsaturated bond ((O1) component)
The component (O1) includes a polyol containing at least 1 selected from the group consisting of a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon unsaturated bond of the component (O1) may be 1 or 2 or more.
Examples of the component (O1) include esters of 3-or more-membered polyhydric alcohols with methacrylic acid, acrylic acid, or derivatives thereof. The 3-or more-membered polyol is preferably a 3-or more-membered low-molecular-weight polyol. Examples of the 3-or more-membered low-molecular-weight polyol include: 3-membered alcohols such as glycerin and trimethylolpropane; 4-membered alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; 5-membered alcohols such as xylitol; 6-membered alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; 7-membered alcohols such as mannitol; and 8-membered alcohols such as sucrose; and so on.
Specific examples of the (O1) component include glycerol mono (meth) acrylate, diglycerol tri (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, diglycerol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, and the like.
"(meth) acrylate" is a concept including both methacrylate and acrylate, and means methacrylate or acrylate.
The component (O1) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among them, the (O1) component is preferably a diol containing a methacryloyl group or an acryloyl group, and more preferably glycerol mono (meth) acrylate or pentaerythritol di (meth) acrylate.
Other polyol ((O2) component)
The component (O2) is a polyol other than the above-mentioned component (O1). The component (O2) is not particularly limited, and may be an aliphatic polyol or an aromatic polyol. The component (O2) may be a low-molecular polyol (for example, having a molecular weight of less than 500) or a high-molecular polyol (for example, having a molecular weight of 500 or more).
Examples of the low-molecular-weight polyol include the same low-molecular-weight polyols as those listed in the description of the component (O) in the adhesive composition (a). As the low molecular weight polyol, 2-membered alcohol (diol) is preferable.
When a low-molecular-weight polyol is used as the (O2) component, the ratio of the low-molecular-weight polyol to the (O1) component (low-molecular-weight polyol/(O1) component (mass ratio)) is preferably 0.01 to 0.1, and more preferably 0.03 to 0.08.
The polymer polyol includes the same polymer polyols as those described in the description of the component (O) in the adhesive composition (a) (except for the polymer polyol belonging to the component (O1)).
The polymer polyol is preferably a polycarbonate polyol or a vegetable oil polyol. The polycarbonate polyol is preferably an aliphatic polycarbonate polyol, and more preferably an aliphatic polycarbonate diol. The vegetable oil-based polyol is preferably a castor oil-modified polyol, and more preferably a castor oil-modified diol.
When a polycarbonate polyol is used as the component (O2), the ratio of the polycarbonate polyol to the component (O1) (polycarbonate polyol/(O1) component (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and still more preferably 0.4 to 3.
When a vegetable oil polyol is used as the (O2) component, the ratio of the vegetable oil polyol to the (O1) component (vegetable oil polyol/(O1) component (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and still more preferably 0.4 to 2.5.
The component (O2) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among the above, the component (O2) is preferably a polycarbonate polyol or a low molecular weight polyol in view of adjusting the viscosity of the adhesive composition (b) and the hardness of the adhesive layer. In addition, from the viewpoint of improving the heat resistance of the adhesive layer, a castor oil-modified polyol may be used as the (O2) component.
From the viewpoints of adjusting the viscosity of the adhesive composition (b), heat resistance of the adhesive layer, and the like, the (O) component is preferably a combination of the (O1) component and the (O2) component. The component (O2) is preferably a low-molecular polyol, a polycarbonate polyol, a castor oil-modified polyol, or a combination thereof. Specific examples of the component (O2) combined with the component (O1) include: a combination of a polycarbonate polyol, a castor oil-modified polyol, and a low-molecular polyol; a combination of a polycarbonate polyol and a castor oil-modified polyol; and polycarbonate polyols, and the like.
The mass ratio of the (O1) component to the (O2) component is preferably (O1): (O2) ═ 1: 5-5: 1, more preferably 1: 4-2: 1, more preferably 1: 4-1: 1, particularly preferably 1: 4-1: 2. when the mass ratio of the (O1) component to the (O2) component is in the above range, the elastic modulus, heat resistance, and the like of the adhesive layer can be improved.
The (P1) component can be synthesized by: the component (I) and the component (O) are mixed and copolymerized according to a known method for synthesizing a polyurethane resin. (I) The copolymerization of the component (A) and the component (O) is preferably carried out in the presence of a known urethanization catalyst such as a bismuth catalyst. In addition, in order to avoid polymerization of the polymerizable carbon-carbon unsaturated bond in the (O1) component, a polymerization inhibitor may be added to the reaction system.
The ratio (mass ratio) of the (I) component to the (O) component used for synthesizing the (P1) component is, for example, preferably (I): (O) ═ 10: 90-60: 40, more preferably 20: 80-50: 50, more preferably 25: 75-45: 55. the molar ratio (NCO/OH) of the hydroxyl group (-OH) in the component (O) to the isocyanate group (-NCO) in the component (I) is preferably 60: 40-40: 60, more preferably 55: 45-45: 55.
the component (P1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the component (P1) in the adhesive composition (b) is not particularly limited as long as it is a concentration at which the composition can be applied to a support or the like. The content of the component (P1) in the adhesive composition (b) is preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and still more preferably 30 to 60% by mass, based on the total mass (100% by mass) of the adhesive composition (b).
Polymerization initiator: (A) composition(s)
The adhesive composition (b) contains a polymerization initiator (hereinafter, also referred to as component (a)). The polymerization initiator is a component having a function of promoting a polymerization reaction. Examples of the component (a) include a thermal polymerization initiator and a photopolymerization initiator.
Examples of the thermal polymerization initiator include peroxides and azo polymerization initiators.
Examples of the peroxide in the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, and peroxyesters. As such a peroxide, specifically, examples thereof include acetyl peroxide, dicumyl peroxide, t-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, Benzoyl Peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetrahydronaphthalene hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl peroxytriphenylacetate, t-butyl hydroperoxide, t-butyl performate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perphenylacetate, t-butyl peroxy4-methoxyacetate, t-butyl peroxyN- (3-tolyl) carbamate and the like.
Among the above peroxides, commercially available products such as a trade name "Percumyl (registered trademark)", a trade name "Perbutyl (registered trademark)", a trade name "Peroyl (registered trademark)", and a trade name "Perocta (registered trademark)", which are manufactured by japan fat and oil industries, for example, can be used.
Examples of the azo polymerization initiator in the thermal polymerization initiator include 2,2 '-azobispropane, 2' -dichloro-2, 2 '-azobispropane, 1' -azo (methylethyl) diacetate, 2 '-azobis (2-amidinopropane) hydrochloride, 2' -azobis (2-aminopropane) nitrate, 2 '-azobisisobutane, 2' -azobisisobutylamide, 2 '-azobisisobutyronitrile, 2' -azobis-2-methylpropionate, 2 '-dichloro-2, 2' -azobisbutane, 2 '-azobis-2-methylbutyronitrile, 2' -azobisisobutyric acid dimethyl ester, dimethyl ester, 1,1 '-azobis (1-methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylpropanedinitrile 4, 4' -azobis-4-cyanopentanoic acid, 3, 5-dihydroxymethylphenylazo-2-allylmalononitrile, 2 '-azobis-2-methylpentanonitrile, dimethyl 4, 4' -azobis-4-cyanopentanoate, 2 '-azobis-2, 4-dimethylvaleronitrile, 1' -azobiscyclohexanecarbonitrile, 2 '-azobis-2-propylbutyronitrile, 1' -azobis-1-chlorophenylethane, 2-methyl-ethyl-methyl-2-azobis-4-pentanoic acid, 2, 5-dihydroxymethyl-phenylazo-2-methyl-carbonitrile, 2-methyl-propanenitrile, 2-azobis-2-methyl-2-ethyl-methyl-pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl-2-methyl-2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-methyl-2-methyl pentanoic acid, 2-methyl pentanoic acid, 2-1, 2-methyl-, 1,1 ' -azobis-1-cyclohexanecarbonitrile, 1 ' -azobis-1-cycloheptanenitrile, 1 ' -azobis-1-phenylethane, 1 ' -azobisisopropylbenzene, ethyl 4-nitrophenylazobisbenzylcyanoacetate, phenylazodiphenylmethane, 4-nitrophenylazotriphenylmethane, 1 ' -azobis-1, 2-diphenylethane, poly (bisphenol A-4,4 ' -azobis-4-cyanovalerate), poly (tetraethyleneglycol-2, 2 ' -azobisisobutyrate), and the like.
Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethan-1-one, bis (4-dimethylaminophenyl) one, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropane-1-one -ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetyloxime), 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, 4-benzoyl-4' -methyldimethylsulphide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, methyl 4-dimethylamino-2-isobutylbenzoic acid, methyl 4-dimethylaminobenzoate, methyl 4-dimethylamino-2-ethylhexylbenzoic acid, methyl 4-dimethylamino-2-isopentylbenzoate, methyl-2-isobenzoate, methyl-ol, methyl-4-methyl-2-dimethylamino-methyl-yl-2-ethyl-methyl-hydroxybenzoate, methyl-4-ethyl-4-methyl-amino-2-methyl-ethyl-hydroxybenzoate, methyl-4-methyl-ethyl-methyl-2-ethyl-methyl-hydroxybenzoate, ethyl-methyl-ethyl-phenyl-4-methyl-phenyl-methyl-4-methyl-ethyl-ben-l-ben-yl-ben-ol, n-ol, c acid, p-ol, p-ben-ol, p-ol, Benzyl-beta-methoxyethyl ketal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2, 4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumyl peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, methyl ethyl thioxanthone, 1, 2-propylthioxanthone, 2-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthene, 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, 2-mercaptobenzothiazole, and mixtures thereof, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4 ' -bisdimethylaminobenzophenone (i.e., Michler's ketone), 4 ' -bisdiethylaminobenzophenone (i.e., EthylMichler's ketone), 4 ' -dichlorobenzophenone, 3-dimethyl-4-methoxybenzophenone, methyl ethyl methyl benzophenone, methyl imidazole, methyl, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-tert-butyldichloroacetophenone, alpha-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthiothioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 4-dimethylaminobenzoate pentyl ester, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-tris (trichloromethyl) s-triazine, 2-methyl-4, 6-bis (trichloromethyl) s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-triazine, and mixtures thereof, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, and the like.
As the photopolymerization initiator, commercially available products such as "IRGACURE OXE 02", "IRGACURE OXE 01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name, manufactured by BASF Co., Ltd.), and "NCI-831" (trade name, manufactured by ADEKA Co., Ltd.) can be used, for example.
(A) The component (A) may be used alone in 1 kind, or may be used in combination with 2 or more kinds. The component (a) is preferably a thermal polymerization initiator, and more preferably a peroxide. The amount of the component (A) used can be adjusted depending on the amount of the component (P1). The content of the polymerization initiator in the adhesive composition (b) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the (P1) component.
< optional ingredients >
The adhesive composition (a) and the adhesive composition (b) may contain optional components in addition to the above components within a range not impairing the effects of the present invention. The optional components are not particularly limited, and examples thereof include a polymerization inhibitor, a solvent component, a plasticizer, an auxiliary binder, a stabilizer, a colorant, and a surfactant.
Polymerization inhibitor
The polymerization inhibitor is a component having a function of preventing a radical polymerization reaction by heat or light. The polymerization inhibitor shows high reactivity to radicals.
The polymerization inhibitor preferably has a phenol skeleton. For example, the polymerization inhibitor may be a hindered phenol-based antioxidant, and examples thereof include pyrogallol, benzoquinone, hydroquinone, methylene blue, t-butylcatechol, monobenzyl ether, methylhydroquinone, pentaquinone, pentoxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4 ' - (1-methylethylidene) bis (2-methylphenol), 4 ' - (1-methylethylidene) bis (2, 6-dimethylphenol), 4 ' - [1- [ 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl ] ethylene ] bisphenol, 4 ' -ethylidene tris (2-methylphenol), 4 ' -ethylidene trisphenol, 1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, and the like, 2, 6-di-tert-butyl-4-methylphenol, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 4 ' -butylidenebis (3-methyl-6-tert-butylphenol), 4 ' -thiobis (3-methyl-6-tert-butylphenol), 3, 9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name IRGANOX1010 manufactured by BASF corporation), tris (3, 5-di-t-butylhydroxybenzyl) isocyanurate, thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], and the like.
The polymerization inhibitor may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The content of the polymerization inhibitor may be determined as appropriate depending on the kind of the resin component, the use of the adhesive composition, and the use environment.
(surfactants)
Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.
Examples of the fluorine-based surfactant include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (both BM Chemie Co., Ltd.), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (both DIC Co., Ltd.), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (both Sumitomo 3M Limited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (both Asahi Nippon Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (both Toray Silicon Co., Ltd.).
Examples of the silicone surfactant include unmodified silicone surfactants, polyether-modified silicone surfactants, polyester-modified silicone surfactants, alkyl-modified silicone surfactants, aralkyl-modified silicone surfactants, and reactive silicone surfactants. Commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topika K1000, Topika K2000, Topika K5000 (manufactured by Kikusho Kogyo Co., Ltd.), XL-121 (polyether modified silicone surfactant, manufactured by Clariant Co., Ltd.), BYK-310 (polyester modified silicone surfactant, manufactured by BYK Chemie Co., Ltd.), and the like.
The surfactant may be used alone in 1 kind, or may be used in combination with 2 or more kinds. The surfactant is preferably a silicone surfactant, and more preferably a polyester-modified silicone surfactant. When the adhesive composition (a) contains a surfactant, the content of the surfactant is preferably 0.01 to 1 part by mass, more preferably 0.5 to 0.5 part by mass, based on the total mass (100 parts by mass) of the component (I) and the component (O). When the adhesive composition (b) contains a surfactant, the content of the surfactant is preferably 0.01 to 1 part by mass, more preferably 0.5 to 0.5 part by mass, per 100 parts by mass of the component (P1).
Composition of solvent
Examples of the solvent component include hydrocarbon solvents, petroleum solvents, and other solvents other than the above solvents. Hereinafter, the hydrocarbon solvent and the petroleum solvent are also collectively referred to as "(S1) component". The solvent component other than the (S1) component is also referred to as "(S2) component".
Examples of the hydrocarbon solvent include straight-chain, branched or cyclic hydrocarbons. Examples of the hydrocarbon solvent include: linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons such as isooctane, isononane, and isododecane; alicyclic hydrocarbons such as p-menthane, o-menthane, m-menthane, diphenyl-menthane, 1, 4-terpene diol, 1, 8-terpene diol, camphane, norbornane, pinane, thujane, terpenoids, longifolene, alpha-terpinene, beta-terpinene, gamma-terpinene, alpha-pinene, beta-pinene, alpha-thujonone, beta-thujonone, cyclohexane, cycloheptane, and cyclooctane; and aromatic hydrocarbons such as toluene, xylene, indene, pentalene, indan, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetrahydronaphthalene), and decahydronaphthalene (decahydronaphthalene).
The petroleum solvent is a solvent purified from heavy oil, and examples thereof include white kerosene, paraffin solvents, and isoparaffin solvents.
Examples of the component (S2) include terpene solvents having an oxygen atom, a carbonyl group, an acetoxy group or the like as a polar group, and examples thereof include geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α -terpineol, β -terpineol, γ -terpineol, terpinen-1-ol, terpinen-4-ol, dihydroabietyl acetate, 1, 4-cineol, 1, 8-cineol, borneol, carvone, ionone, thujone, camphor and the like.
Further, as the (S2) component, there may be mentioned: lactones such as γ -butyrolactone; ketones such as acetone, methyl ethyl ketone, Cyclohexanone (CH), methyl-n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; derivatives of polyhydric alcohols such as compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, and compounds having an ether bond such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and the like of the polyhydric alcohols or the compounds having an ester bond, or monophenyl ethers of the compounds having an ester bond (among them, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME)) are preferable; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, tolylmethyl ether, diphenyl ether, dibenzyl ether, phenetole, and butylphenyl ether.
The solvent component can be used alone in 1 kind, also can be combined with 2 or more and use. The solvent component is preferably an inactive solvent component with respect to the above-mentioned component (B), component (I) and component (O), or the above-mentioned component (B) and component (P1). Examples of the preferable solvent component include ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixed solvents thereof.
The adhesive composition (a) can be prepared by adding optional components to the above-mentioned component (B), component (I) and component (O) as appropriate and mixing them.
The adhesive composition (B) can be prepared by dissolving and mixing the component (B), the component (P1), and the component (a), and optional components added as needed, in a solvent component.
The content of the solvent component in the adhesive composition (b) may be appropriately adjusted according to the thickness of the adhesive composition layer. The content of the solvent component is preferably in the range of 40 to 90% by mass, for example, with respect to the total mass (100% by mass) of the adhesive composition. That is, the concentration of the solid content (the total amount of the components added after removal of the solvent component) in the adhesive composition of the present embodiment is preferably within a range of 10 to 80 mass%. When the content of the solvent component is within the above-mentioned preferable range, the viscosity can be easily adjusted.
When a polymerization initiator is used, the polymerization initiator may be compounded by a known method immediately before the adhesive composition is used. The polymerization initiator or polymerization inhibitor may be blended in the form of a solution prepared by dissolving the above-mentioned component (S2) in advance. The amount of the component (S2) used may be appropriately adjusted depending on the kind of the polymerization initiator or polymerization inhibitor, and is, for example, preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the component (S1). When the amount of the component (S2) used is within the above-mentioned preferable range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.
According to the adhesive composition of the present embodiment, when temporarily adhering a semiconductor substrate or the like to a support, an adhesive composition layer is formed between the semiconductor substrate or the like and the support and cured. This enables the formation of an adhesive layer for temporarily adhering the semiconductor substrate or the like to the support. The adhesive layer is cured by the crosslinked structure, and therefore, has high heat resistance and does not decrease in elastic modulus even at high temperatures (e.g., 200 ℃ or higher). Therefore, even when high-temperature processing is performed during processing of a semiconductor substrate or an electronic device, defects such as misalignment and sinking are unlikely to occur.
On the other hand, when the adhesive layer is irradiated with light such as laser light, the component (B) in the adhesive layer absorbs the light, and the adhesive layer is modified. This reduces the adhesive strength of the adhesive layer, and the semiconductor substrate and the like can be separated from the support. Therefore, a separation layer is not required.
Further, since the adhesive layer contains a urethane resin, the adhesive layer can be decomposed by decomposing a urethane bond with an acid or an alkali. Therefore, even when the residue of the adhesive layer adheres to the semiconductor substrate or the like separated from the support, the residue of the adhesive layer can be easily removed by cleaning with an acid or an alkali.
(laminated body)
The laminate according to claim 2 of the present invention is a laminate in which a support for transmitting light, an adhesive layer, and a semiconductor substrate or an electronic device are sequentially laminated, wherein the adhesive layer is a cured product of the adhesive composition according to claim 1.
Fig. 1 shows an embodiment of the laminate according to embodiment 2.
The laminate 100 shown in fig. 1 includes a support 1 that transmits light, an adhesive layer 3, and a semiconductor substrate 4. In the laminate 100, the support 1, the adhesive layer 3, and the semiconductor substrate 4 are laminated in this order.
Fig. 2 shows another embodiment of the laminate according to embodiment 2.
The laminate 200 shown in fig. 2 has the same configuration as the laminate 100, except that an electronic component 456 formed of the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 is laminated on the adhesive layer 3.
Fig. 3 shows another embodiment of the laminate according to embodiment 2.
The laminate 300 shown in fig. 3 has the same configuration as the laminate 100 except that the electronic device is formed of the wiring layer 6.
Fig. 4 shows another embodiment of the laminate according to embodiment 2.
The laminate 400 shown in fig. 4 has the same configuration as the laminate 100, except that an electronic device 645 including the wiring layer 6, the semiconductor substrate 4, and the sealing material layer 5 is laminated on the adhesive layer 3.
< support >
The support is a member for supporting a semiconductor substrate or an electronic device. The support has a characteristic of transmitting light. The support is bonded to the semiconductor substrate or the electronic device via the adhesive layer. Therefore, the support preferably has strength necessary for preventing breakage or deformation of the semiconductor substrate when thinning the device, transporting the semiconductor substrate, and mounting the semiconductor substrate.
As a material of the support, for example, glass, silicon, acrylic resin, or the like can be used. Examples of the shape of the support include, but are not limited to, a rectangular shape and a circular shape. As the support, in order to achieve higher density integration and higher production efficiency, a support having a large size of a circular support or a large panel having a quadrangular shape in plan view may be used.
< adhesive layer >
The adhesive layer is provided for temporarily adhering the semiconductor substrate or the electronic device to the support. The adhesive layer is a cured product of the adhesive composition according to embodiment 1. The adhesive composition according to embodiment 1 can be cured by heating the adhesive composition. The thickness of the adhesive layer is, for example, preferably in the range of 1 μm to 200 μm, more preferably in the range of 5 μm to 150 μm.
As described above, the adhesive layer is a cured product of the adhesive composition, and the material (cured product) constituting the adhesive layer preferably satisfies the following characteristics.
That is, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 200 ℃ is preferably 1.0X 104Pa or more, more preferably 5.0X 104Pa or more, more preferably 1.0X 105Pa or above. Further, the complex elastic modulus at 200 ℃ is more preferably 1.0X 106Pa or more, more preferably 5.0X 106Pa or more, particularly preferably 1.0X 107Pa or above. The upper limit of the complex elastic modulus at 200 ℃ is, for example, 1.0X 1010Pa or less.
When the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 250 ℃ is preferably 5.0X 106Pa or more, more preferably 1.0X 107Pa or above. The upper limit of the complex elastic modulus at 250 ℃ is, for example, 1.0X 1010Pa or less.
The complex elastic modulus of the cured product was measured using a dynamic viscoelasticity measuring apparatus Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition was applied to a release agent-attached PET film, heated at 180 ℃ for 1 hour in an oven under a nitrogen atmosphere to form a test piece having a thickness of 50 μm, and then the adhesive composition was measured on the test piece (having a size of 5 mm. times.40 mm and a thickness of 50 μm) peeled off from the PET film by using the above-mentioned measuring apparatus. As the measurement conditions, the following conditions may be adopted: the temperature was raised from the initial temperature of 50 ℃ to 300 ℃ at a temperature raising rate of 5 ℃ per minute under a stretching condition of a frequency of 1 Hz.
< semiconductor substrate or electronic device >
The semiconductor substrate or the electronic device is temporarily bonded to the support via the adhesive layer.
Semiconductor substrate
The semiconductor substrate is not particularly limited, and the same semiconductor substrate as that exemplified in the above "(adhesive composition)" can be exemplified. The semiconductor substrate may be a semiconductor element or other elements, and may have a single-layer or multi-layer structure.
Electronic device
The electronic device is not particularly limited, and the same electronic devices as those exemplified in the above "(adhesive composition)" can be exemplified. The electronic component is preferably a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and may further include a semiconductor substrate.
In the stacked body 200 shown in fig. 2, the electronic component 456 is composed of the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6. In the laminate 300 shown in fig. 3, the electronic component 6 is constituted by the wiring layer 6. In the stacked body 400 shown in fig. 4, the electronic component 645 is constituted by the wiring layer 6, the semiconductor substrate 4, and the sealing material layer 5.
[ layer of sealing material ]
The sealing material layer is provided to seal the semiconductor substrate, and is formed using a sealing material. The sealing material is a member capable of insulating or sealing a member made of metal or semiconductor.
As the sealing material, for example, a resin composition can be used. The sealing material layer 5 is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3, not on each of the semiconductor substrates 4. The resin used for the sealing material is not particularly limited as long as it can seal and/or insulate a metal or a semiconductor, and examples thereof include epoxy-based resins and silicone-based resins.
The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles.
Wiring layer
The wiring Layer is also called RDL (Redistribution Layer) and is a wiring body of a thin film constituting a wiring connected to a substrate, and may have a single-Layer or multi-Layer structure. The wiring layer may be on a dielectric (silicon oxide (SiO)x) And photosensitive resin such as photosensitive epoxy) and a wiring formed by using a conductor (for example, metal such as aluminum, copper, titanium, nickel, gold, and silver, and alloy such as silver-tin alloy).
In the laminate of fig. 1 to 4, the support 1 and the adhesive layer 3 are adjacent to each other, but the present invention is not limited thereto, and another layer may be formed between the support 1 and the adhesive layer 3. In this case, the other layer may be made of a material that transmits light. This makes it possible to add a layer that provides appropriate properties to the multilayer body 100 to 400, for example, without preventing light from entering the adhesive layer 3. The wavelength of light that can be used varies depending on the type of material constituting the adhesive layer 3. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can modify the material constituting the adhesive layer 3.
(method (1) for producing laminate)
A method for producing a laminate according to claim 3 of the present invention is a method for producing a laminate in which a support for transmitting light, an adhesive layer, and a semiconductor substrate are sequentially laminated, the method comprising: a step of applying the adhesive composition according to claim 1 onto the support or the semiconductor substrate to form an adhesive composition layer (hereinafter, also referred to as "adhesive composition layer forming step"); a step of placing the semiconductor substrate on the support via the adhesive composition layer (hereinafter, also referred to as a "semiconductor substrate placing step"); and a step of forming the adhesive layer by curing the adhesive composition layer through a polymerization reaction of the urethane resin (hereinafter, also referred to as "adhesive layer forming step").
Fig. 5 to 6 are schematic process diagrams for explaining one embodiment of the method for manufacturing a laminate according to the present embodiment.
Fig. 5A to 5B are views illustrating a manufacturing process of a laminate 100 'in which the support 1, the adhesive composition layer 3', and the semiconductor substrate 4 are sequentially laminated. Fig. 5A is a diagram illustrating an adhesive composition layer forming step. Fig. 5B is a diagram illustrating a semiconductor substrate mounting step.
Fig. 6 is a diagram illustrating an adhesive layer forming step. The adhesive layer 3 'in the laminate 100' is thermally cured to form the adhesive layer 3, thereby obtaining the laminate 100.
[ adhesive composition layer Forming Process ]
The method for producing a laminate according to the present embodiment includes an adhesive composition layer forming step. The adhesive composition layer forming step is a step of applying an adhesive composition on a support or a semiconductor substrate to form an adhesive composition layer.
In fig. 5A, an adhesive composition layer 3' is formed on a support 1 using an adhesive composition.
The method for forming the adhesive composition layer 3' on the support 1 is not particularly limited, and examples thereof include spin coating, dipping, roll coating, spray coating, slit coating, and the like.
The adhesive composition layer may be formed on the semiconductor substrate 4 by the same method.
After the adhesive composition layer is formed, a baking treatment may be performed. The baking temperature condition is set to a temperature lower than the heating temperature in the adhesive layer forming step described later. The baking conditions may vary depending on the type of the curable component contained in the adhesive composition, and examples thereof include 1 to 10 minutes at a temperature of 70 to 100 ℃.
[ semiconductor substrate mounting Process ]
The method for manufacturing a laminate according to the present embodiment includes a semiconductor substrate mounting step. The semiconductor substrate mounting step is a step of mounting the semiconductor substrate on the support via the adhesive composition layer. This can yield a laminate 100'.
In fig. 5(c), the semiconductor substrate 4 is placed on the support 1 via the adhesive composition layer 3' formed on the support 1.
The method for placing the semiconductor substrate 4 on the support 1 through the adhesive composition layer 3' is not particularly limited, and a method generally used as a method for disposing a semiconductor substrate at a predetermined position can be employed.
[ adhesive layer Forming Process ]
The method for manufacturing a laminate according to the present embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of forming an adhesive layer by curing the adhesive composition layer. This can yield the laminate 100.
In fig. 6, the adhesive layer 3 is formed by curing the adhesive composition layer 3'.
The curing reaction of the adhesive composition layer can be carried out by an appropriate method selected depending on the kind of the curing component.
When the curing component is the component (a), the curing reaction can be carried out by heating. The heating temperature may be set to a temperature at which the crosslinking reaction of the component (I) and the component (O) is initiated or higher. For example, when the component (I) contains a blocked polyisocyanate, the heating temperature may be set to a temperature not lower than the dissociation temperature of the thermally dissociative blocking agent for blocking the isocyanate group in the blocked polyisocyanate. The heating temperature may vary depending on the type of the thermally releasable sealing agent, and examples thereof include 80 ℃ or more, 100 ℃ or more, 130 ℃ or more, and 150 ℃ or more. The upper limit of the heating temperature is not particularly limited, and from the viewpoint of energy consumption, for example, 350 ℃ or lower, 300 ℃ or lower, or 250 ℃ or lower, and the like can be mentioned. Examples of the heating temperature range include 80 to 350 ℃, 100 to 300 ℃, 130 to 300 ℃, or 150 to 300 ℃.
The heating time is not particularly limited as long as it is a time sufficient to thermally cure the component (I) and the component (O). The heating time may be set to, for example, 15 minutes or more, 30 minutes or more, 45 minutes or more, or the like. The upper limit of the heating time is not particularly limited, and may be set to, for example, 120 minutes or less, 100 minutes or less, 80 minutes or less, or 60 minutes or less, from the viewpoint of the operation efficiency and the like. The heating time is, for example, 15 to 120 minutes, 30 to 120 minutes, or 45 to 120 minutes.
When the curing component is the component (b) and the component (P1) contains a methacryloyl group or an acryloyl group, the curing reaction can be carried out by heating. Examples of the heating temperature include 80 to 350 ℃, 100 to 300 ℃, 130 to 300 ℃, or 150 to 300 ℃. The heating time is not particularly limited as long as it is a time sufficient to polymerize and cure the (P1) component. The heating time is, for example, preferably 30 to 180 minutes, more preferably 45 to 120 minutes, and still more preferably 60 to 120 minutes. The curing reaction can be carried out, for example, under a nitrogen atmosphere.
By this step, the components (I) and (O) or the component (P1) in the adhesive composition layer 3 'are crosslinked and cured to form the adhesive layer 3 as a cured product of the adhesive composition layer 3'. Thereby, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, the laminate 100 can be obtained.
When the curing component is the component (B) and the component (B1) is contained as the component (B), the component (P1) and the component (B1) in the adhesive composition layer 3 'are crosslinked and cured to form the adhesive layer 3 as a cured product of the adhesive composition layer 3'. Thereby, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, the laminate 100 can be obtained.
[ optional procedure ]
The method for producing a laminate according to the present embodiment may include other steps in addition to the above steps. Examples of the other steps include various mechanical and chemical treatments (thin film treatment such as polishing and Chemical Mechanical Polishing (CMP), high-temperature and vacuum treatment such as Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD), treatment using chemicals such as organic solvents, acidic treatment solutions, and alkaline treatment solutions, plating treatment, irradiation with active light, heating and cooling treatment), and the like.
(method (2) for producing laminate)
A method for producing a laminate according to claim 4 of the present invention is characterized by further comprising an electronic device forming step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member, after obtaining the laminate by the method for producing a laminate according to claim 3.
The laminate obtained by the method for producing a laminate of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are sequentially laminated. This laminate can be obtained by subjecting the laminate obtained by the method for producing a laminate according to embodiment 3 to an electronic device forming step.
[ electronic device Forming Process ]
The method for manufacturing a laminate according to the present embodiment includes an electronic device forming step. The electronic device forming step is a step of forming an electronic device that is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
The electronic device forming process may include any one of a sealing process, a grinding process, and a wiring layer forming process. In one embodiment, the electronic device forming step includes a substrate fixing step and a sealing step. In this case, the electronic device forming step may further include a grinding step and a wiring layer forming step.
About the sealing process
The sealing step is a step of sealing the substrate fixed to the support body with a sealing material.
In fig. 7A, a laminate 110 is obtained, and the entire semiconductor substrate 4 temporarily bonded to the support 1 via the adhesive layer 3 is sealed by the sealing material layer 5 to form the laminate 110.
In the sealing step, a sealing material heated to 130 to 170 ℃, for example, is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity state, and is compression molded to produce a laminate 110 in which the sealing material layer 5 is provided on the adhesive layer 3.
In this case, the temperature is, for example, 130 to 170 ℃.
The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500N/cm2。
The sealing material layer 5 is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3, not on each of the semiconductor substrates 4.
Concerning the grinding process
The grinding step is a step of grinding the sealing material portion (the sealing material layer 5) in the sealing body so as to expose a part of the semiconductor substrate after the sealing step.
For example, as shown in fig. 7B, grinding of the seal material portion is performed in the following manner: the sealing material layer 5 is shaved to a thickness substantially equal to that of the semiconductor substrate 4.
Formation of interconnection layer
The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step.
In fig. 7C, a wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5. This can obtain the laminate 120. In the stacked body 120, the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 constitute an electronic component 456.
As a method of forming the wiring layer 6, for example, the following method can be given.
First, silicon oxide (SiO) is formed on the sealing material layer 5x) And a dielectric layer of photosensitive resin. The dielectric layer formed of silicon oxide can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like. The dielectric layer formed of a photosensitive resin can be formed by applying a photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roll coating, spray coating, or slit coating.
Next, a wiring is formed of a conductor such as a metal on the dielectric layer. As a method of forming the wiring, for example, a known semiconductor process such as a photolithography process such as photolithography (resist lithography) and an etching process can be used. Examples of such a lithography process include a lithography process using a positive resist material and a lithography process using a negative resist material.
In the method for manufacturing a laminate according to the present embodiment, formation of bumps or mounting of elements may be further performed on the wiring layer 6. The mounting of the components on the wiring layer 6 may be performed using, for example, a mounter or the like.
(method (3) of producing a laminate)
A method for producing a laminate according to claim 5 of the present invention is a method for producing a laminate in which a support, an adhesive layer, and an electronic device are sequentially laminated, the method comprising: a step of applying the adhesive composition according to the above-mentioned 1 to the support to form a layer of the adhesive composition (adhesive composition layer forming step); an electronic component forming step of forming an electronic component on the adhesive composition layer, the electronic component being a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member (electronic component forming step); and a step (adhesive layer forming step) of curing the adhesive composition layer to form an adhesive layer.
Similarly to the production method according to the above-described 4 th aspect, the laminate obtained by the production method of a laminate according to the present embodiment is a laminate in which a support, an adhesive layer, and an electronic component are sequentially laminated.
In the production method of the present embodiment, the adhesive composition layer forming step may be performed in the same manner as the adhesive composition layer forming step in the production method of the laminate according to embodiment 3.
In the manufacturing method of the present embodiment, the electronic device forming step is performed after the adhesive composition layer forming step. As the electronic device forming process, a wiring layer forming process may be included. The electronic device forming step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, and the like. In addition, the electronic device forming step may be a step of placing a sealing body (which is formed by sealing the semiconductor substrate with a sealing material) on the support through the adhesive composition layer.
The adhesive layer forming step may be performed in the same manner as the adhesive layer forming step in the method for manufacturing a laminate according to embodiment 3.
After the adhesive layer forming step, an electronic device forming step may be further performed as necessary. The electronic device forming step may include, for example, a semiconductor substrate mounting step, a sealing step, a grinding step, and the like.
According to the method of manufacturing a laminate according to any of the above-described aspects 3 to 5, since the support and the semiconductor substrate or the electronic device are temporarily bonded via the adhesive layer having high heat resistance, a laminate in which the support, the adhesive layer, and the semiconductor substrate or the electronic device are sequentially laminated can be stably manufactured. The laminate is produced in a process based on a fan-out type technique in which terminals provided on a semiconductor substrate are mounted on a wiring layer extending outside a chip region.
(method for manufacturing electronic Components)
A method for manufacturing an electronic component according to claim 6 of the present invention is characterized in that, after a laminate is obtained by the method for manufacturing a laminate according to any one of the above-described 3 to 5, the method includes: a step of irradiating the adhesive layer with light through the support to modify the adhesive layer, thereby separating the electronic component from the support (hereinafter, also referred to as a "separation step"); and a step of removing the adhesive layer by decomposing the urethane bond in the adhesive layer with an acid or an alkali (hereinafter, also referred to as "adhesive layer removal step").
Fig. 8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 8A is a diagram illustrating the laminate 120, fig. 8B is a diagram illustrating a separation step, and fig. 8C is a diagram illustrating an adhesive removal step.
[ separation Process ]
The separation step is as follows: the electronic component 456 is separated from the support 1 by irradiating light (arrow) to the adhesive layer 3 through the support 1 to modify the adhesive layer 3.
As shown in fig. 8A, in the separation step, the adhesive layer 3 is modified by irradiating light (arrows) to the adhesive layer 3 through the support 1 that transmits light.
The wavelength of the light used in the separation step may be selected according to the wavelength of the light that can be absorbed by the component (B) contained in the adhesive layer 3. For example, light having a wavelength of 300 to 800nm can be used.
The type of light to be irradiated may be appropriately selected depending on the permeability of the support 1, and examples thereof include YAG laser, ruby laser, glass laser, and YVO4Solid laser such as laser, LD laser, and fiber laser, liquid laser such as dye laser, and CO2A gas laser such as a laser beam, an excimer laser, an Ar laser, or a He — Ne laser, a laser such as a semiconductor laser or a free electron laser, or a non-laser. This makes it possible to modify the adhesive layer 3 to easily separate the support 1 from the electronic component 456.
When the laser is irradiated, the following conditions may be mentioned as examples of the laser irradiation conditions.
The average output value of the laser beam is preferably 1.0W or more and 5.0W or less, and more preferably 3.0W or more and 4.0W or less. The repetition frequency of the laser is preferably 20kHz to 60kHz, and more preferably 30kHz to 50 kHz. The scanning speed of the laser is preferably 100mm/s to 10000 mm/s.
After the adhesive layer 3 is modified by irradiating light (arrows) to the adhesive layer 3, the support 1 is separated from the electronic component 456 as shown in fig. 8B.
For example, the support 1 is separated from the electronic component 456 by applying a force in a direction in which the support 1 and the electronic component 456 are separated from each other. Specifically, in a state where one of the support 1 and the electronic component 456 side (the wiring layer 6) is fixed to the table, the other is lifted up while being sucked and held by a separation plate provided with a suction pad (a bellows pad or the like), whereby the support 1 can be separated from the electronic component 456.
The force applied to the laminate 200 may be appropriately adjusted depending on the size of the laminate 200, and is not particularly limited, and for example, in the case of a laminate having a diameter of about 300mm, the support 1 and the electronic component 456 may be appropriately separated by applying a force of about 0.1 to 5kgf (0.98 to 49N).
[ adhesive layer removing step ]
The method for manufacturing an electronic component according to the present embodiment includes an adhesive layer removing step. The adhesive layer removing step is a step of removing the adhesive layer by decomposing a urethane bond in the adhesive layer with an acid or an alkali.
In fig. 8B, after the separation process, the adhesive layer 3 is attached to the electronic component 456. In this step, the adhesive layer 3 is decomposed using an acid or an alkali, and the adhesive layer 3 is removed to obtain the electronic component 50.
In this step, the urethane bond in the adhesive layer 3 is decomposed by an acid or an alkali. The adhesive layer 3 contains a urethane resin formed by copolymerization of the above-mentioned component (I) and component (O), or a crosslinked urethane resin formed by polymerization of the above-mentioned component (P1). These polyurethane resins are decomposed by treatment with an acid or an alkali, which cleaves the urethane bond. This can decompose the adhesive layer 3 and remove the residue of the adhesive layer 3 adhering to the electronic component 456.
The acid or base used in the present step is not particularly limited as long as it can decompose the urethane bond. Examples of the acid capable of decomposing the urethane bond include, but are not limited to, hydrochloric acid, sulfuric acid, and nitric acid. Examples of the base capable of decomposing a urethane bond include inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine, but not limited thereto.
The acid or the base may be dissolved in a solvent and used in the form of a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, and examples thereof include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, and propylene glycol.
The treatment liquid for removing the adhesive may contain known additives such as a surfactant in addition to the above components.
The content of the acid or the base in the treatment solution is not particularly limited, and examples thereof include 1 to 50% by mass. The content of the polar solvent in the treatment liquid is 50 to 99% by mass.
The treatment liquid for removing the adhesive layer may be a commercially available alkaline treatment liquid or an acidic treatment liquid. Examples of commercially available processing liquids include ST-120 and ST-121 (both manufactured by Tokyo Kogyo Co., Ltd.).
When the treatment liquid containing an acid or an alkali as described above is brought into contact with the adhesive layer 3, urethane bonds in the adhesive layer 3 are decomposed, and the adhesive layer 3 can be removed.
In the method for manufacturing an electronic component according to the present embodiment, after the adhesive layer removing step, the electronic component 50 may be further subjected to a process such as solder ball formation, dicing, or oxide film formation.
According to the method for producing an electronic component of the present embodiment, an adhesive composition containing (a) a light absorber, a polyisocyanate, and a polyol, or an adhesive composition containing (b) a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator is used, and the adhesive composition is cured to temporarily bond a semiconductor substrate or the like to a support. Therefore, an adhesive layer having high heat resistance (which can withstand high-temperature treatment in an electronic device formation process or the like) can be formed.
Further, since the adhesive composition contains a light absorbing agent, the adhesive layer is modified by irradiation with light, and the adhesive strength is reduced. Therefore, even if the separation layer is not present, the temporarily bonded semiconductor substrate and the like can be easily separated from the support.
Further, by decomposing the urethane bond in the adhesive layer with an acid or an alkali, the residue of the adhesive layer adhering to the semiconductor substrate or the like separated from the support can be easily removed.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
< example for Synthesis of polyurethane resin (component (P1) >)
To a flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, Propylene Glycol Monomethyl Ether Acetate (PGMEA), 36 parts of castor oil-modified diol, 17 parts of polycarbonate diol (mw1,000), 18 parts of pentaerythritol diacrylate, 1 part of neopentyl glycol and an inhibitor were added, and the mixture was uniformly mixed under a nitrogen stream. Subsequently, 7 parts of diphenylmethane diisocyanate (MDI) and 21 parts of hydrogenated xylylene diisocyanate (H6XDI) were charged into a dropping funnel and dropped at a constant rate over 30 minutes. After completion of the dropwise addition, aging was carried out for 30 minutes. Then adding a bismuth catalyst, heating to 65 ℃, and curing for 4-5 hours. Subsequently, 2HEA (2-hydroxyethyl acrylate) was added and the reaction was aged for 1 hour, and the reaction was terminated at the time when the isocyanate group (NCO) disappeared. The weight-average molecular weight (Mw) of the resulting polyurethane resin (P1) -1 was 20,000. The C ═ C equivalent (molecular weight of the polyurethane resin per 1 equivalent of the polymerizable carbon-carbon double bond) of the polyurethane resin (P1) -1 was 600g/eq.
The polycarbonate diol (mw1,000) used for the synthesis of the polyurethane resin (P1) -1 is a polycarbonate diol (R ═ CH) represented by the following formula (PC-1-1)2)6-、-(CH2)5-)。
[ chemical formula 19]
Figure BDA0003647599760000621
< preparation of adhesive composition (1) >)
(examples 1 to 6, comparative example 1)
The components shown in table 1 were mixed to prepare adhesive compositions of respective examples. More specifically, it was prepared as follows. First, component (P1), component (a), component (Ad), and component (S) were mixed in the blending amounts shown in table 1. Next, component (B) was added so as to have the ratio shown in table 1, and the mixture was mixed so that the entire composition became uniform.
[ Table 1]
Figure BDA0003647599760000631
In table 1, the abbreviations each have the following meanings. [] The numerical values in (b) are amounts (parts by mass) to be blended. The numerical value of wt% in (c) is a ratio (% by mass) of the pigment solid content to the total mass (100% by mass) of the adhesive composition.
(P1) -1: the polyurethane resin (P1) -1 synthesized in the above synthesis example.
(A) -1: peroxide (Percumyl (registered trademark) D, japan oil and fat co.
(Ad) -1: polyester-modified polydimethylsiloxane (BYK-310 (trade name), BYK Chemie).
(S) -1: PGMEA (propylene glycol monomethyl ether acetate).
(B) -1: carbon black (acrylic resin dispersion volume average particle diameter of 150nm or less).
(B) -2: perylene black pigments (volume average particle size 150 nm).
< evaluation >
Measurement of light transmittance
The adhesive compositions of the respective examples were applied to bare glass supports by spin coating. The adhesive layers were cured by heating at 180 ℃ for 1 hour in an oven under a nitrogen atmosphere to form adhesive layers having the film thicknesses shown in table 2. The adhesive layer was evaluated for transmittance of light having a wavelength of 532nm by irradiating the adhesive layer with light having a wavelength of 380 to 780nm using a spectroscopic analyzer UV-3600 (manufactured by Shimadzu corporation). The results are shown in Table 2.
[ Table 2]
Figure BDA0003647599760000641
From the results shown in Table 2, it was confirmed that the adhesive layers formed using the adhesive compositions of examples 1 to 6 had significantly reduced light transmittance and absorbed light having a wavelength of 532 nm.
Evaluation of cleaning Property
The adhesive composition of example 6 was applied to a glass support (size diameter 30cm, thickness 700 μm) by spin coating. The resulting mixture was heated at 180 ℃ for 1 hour in an oven under a nitrogen atmosphere to cure the mixture, thereby forming an adhesive layer (film thickness: 18 μm). The treatment liquid for a support on which the adhesive layer had been formed (treatment liquid obtained by diluting tetramethylammonium hydroxide (TMAH) at a concentration of 2 mass% with respect to a mixed solvent of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and Propylene Glycol (PG) (NMP: DMS: PG: 10: 78: 12 (mass ratio)) was treated at 50 ℃, and the time until complete dissolution was measured. The dissolution rate of the adhesive layer was calculated from the dissolution time with respect to the film thickness. When the dissolution rate is 50nm/sec or more, it is judged that the cleaning property is good.
The dissolution rate of the adhesive layer was 70 nm/sec. Therefore, it was confirmed that the adhesive layer formed using the adhesive composition of example 6 was excellent in cleaning property.
< preparation of adhesive composition (2) >)
(examples 7 to 9, comparative example 2)
The components shown in table 3 were mixed to prepare adhesive compositions of respective examples.
[ Table 3]
Figure BDA0003647599760000651
In table 3, the abbreviations each have the following meanings. [] The numerical values in (b) are amounts (parts by mass) to be blended.
(P1) -1: the polyurethane resin (P1) -1 synthesized in the above synthesis example.
(A) -1: peroxide (Percumyl (registered trademark) D, Nippon fat Co., Ltd.).
(Ad) -1: polyester-modified polydimethylsiloxane (BYK-310 (trade name), BYK Chemie).
(S) -1: PGMEA (propylene glycol monomethyl ether acetate).
(B1) -1: the following compound (B1-1).
[ chemical formula 20]
Figure BDA0003647599760000652
< evaluation >
Measurement of light transmittance
The adhesive compositions of the respective examples were applied to bare glass supports by spin coating. The adhesive layers were cured by heating at 180 ℃ for 1 hour in an oven under a nitrogen atmosphere to form adhesive layers having the film thicknesses shown in table 2. The adhesive layer was irradiated with light having a wavelength of 300 to 800nm using a spectroscopic analyzer UV-3600 (manufactured by Shimadzu corporation), and the transmittance of light having a wavelength of 355nm was measured. The results are shown in table 4 below.
[ Table 4]
Figure BDA0003647599760000661
From the results shown in table 4, it was confirmed that the adhesive layers formed using the adhesive compositions of examples 7 to 9 had a low level of light transmittance at the measurement wavelength and absorbed light in the wavelength range.
Evaluation of laser reactivity
An adhesive layer was formed from the adhesive compositions of example 9 and comparative example 2 under the same conditions as in the above-described "measurement of light transmittance". The adhesive layer was irradiated with 355nm laser light using Talon (registered trademark) 355-12 manufactured by Spectra Physics. The adhesive layer was observed to confirm the indentation. The results are shown in Table 5 together with the transmittance at 355 nm.
[ Table 5]
Figure BDA0003647599760000662
From the results shown in Table 5, it was confirmed that the adhesive layer formed using the adhesive composition of example 9 had a laser reactivity of 355 nm. On the other hand, in the adhesive layer formed using the adhesive composition of comparative example 2, no laser reactivity was observed.
Description of the reference numerals
1 support body
3 adhesive layer
3' adhesive composition layer
4 semiconductor substrate
5 sealing Material layer
6 wiring layer
20 laminated body
50 electronic component
100 laminated body
100' laminate
110 laminated body
120 laminated body
200 laminated body
300 laminated body
400 laminated body
456 electronic device
645 electronic device

Claims (10)

1. An adhesive composition for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support which transmits light, the adhesive composition comprising:
(a) light absorbers, polyisocyanates, and polyols; or
(b) A light absorber, a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.
2. The adhesive composition according to claim 1, wherein the adhesive composition contains the component (b),
the light absorber contains a compound (B1) which absorbs at least a part of light in a wavelength range of 300 to 800nm and contains a polymerizable carbon-carbon unsaturated bond (wherein the compound belonging to the polyurethane resin is not included).
3. The adhesive composition according to claim 2, wherein the compound (B1) is represented by the following general formula (B1),
[ chemical formula 1]
Figure FDA0003647599750000011
Wherein W is a 1-valent group containing a polymerizable carbon-carbon unsaturated bond; y is a single bond, or a 2-valent linking group selected from the group consisting of-O-, -CO-, -COO-, and-CONH-; n is an integer of 1-6; x is an n-valent atomic group having an aromatic condensed ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton in its structure; when n is 2 or more, a plurality of W and Y may be the same or different.
4. The adhesive composition according to any one of claims 1 to 3, wherein the adhesive composition contains the component (b),
the polyurethane resin is a reaction product of a polyol and a polyisocyanate,
at least one of the polyol and the polyisocyanate includes the polymerizable carbon-carbon unsaturated bond.
5. The adhesive composition according to any one of claims 1 to 4, wherein the adhesive composition contains the component (b),
as the polymerization initiator, a thermal polymerization initiator is included.
6. The adhesive composition according to any one of claims 1 to 5, wherein a composite body of a member made of a metal or a semiconductor and a resin sealing or insulating the member, which is the electronic device, is laminated on the support via the adhesive layer.
7. A laminate comprising a support for transmitting light, an adhesive layer, and a semiconductor substrate or an electronic device laminated in this order,
the adhesive layer is a cured product of the adhesive composition according to any one of claims 1 to 6.
8. A method for producing a laminate comprising a support for transmitting light, an adhesive layer, and a semiconductor substrate laminated in this order, the method comprising:
a step of applying the adhesive composition according to any one of claims 1 to 6 on the support or the semiconductor substrate to form an adhesive composition layer;
a step of placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween; and
and curing the adhesive composition layer to form the adhesive layer.
9. A method for producing a laminate comprising a support for transmitting light, an adhesive layer, and an electronic device laminated in this order, wherein the method for producing a laminate according to claim 8 further comprises a step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member.
10. A method for producing an electronic component, comprising the steps of, after obtaining a laminate by the method for producing a laminate according to claim 8:
irradiating the adhesive layer with light through the support to modify the adhesive layer, thereby separating the electronic device from the support; and
and a step of removing the adhesive layer attached to the electronic component by decomposing a urethane bond in the adhesive layer with an acid or an alkali.
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