TW202134384A - Adhesive agent composition, layered body, method for producing layered body, and method for producing electronic component - Google Patents

Abstract

This adhesive agent composition is used to form an adhesive layer for temporarily bonding a semiconductor substrate or an electronic device with a light-transmissive support body, the adhesive agent composition containing: (a) a light absorber, a polyisocyanate and a polyol; or (b) a light absorber, a urethane resin having a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.

Description

Adhesive composition, laminate, method for manufacturing laminate, and method for manufacturing electronic parts

The present invention relates to an adhesive composition, a laminate, a method of manufacturing a laminate, and a method of manufacturing electronic parts. This case is based on a special application filed in Japan on December 27, 2019 No. 2019-238291 and Special Application No. 2020-110426 filed in Japan on June 26, 2020, claim priority and use its content here.

Semiconductor packages (electronic parts) containing semiconductor elements have various forms according to corresponding sizes, such as WLP (Wafer Level Package), PLP (Panel Level Package), etc. The technology of semiconductor packaging can include fan-in technology and fan-out technology. With the fan-in technology of semiconductor packaging, there is known a fan-in WLP (Fan-in Wafer Level Package) in which the terminals at the end of the bare chip are rearranged in the chip area. By fan-out technology of semiconductor packaging, fan-out WLP (Fan-out Wafer Level Package) and the like in which the terminal is relocated outside the chip area are known.

In recent years, especially fan-out technology, as fan-out PLP (Fan-out Panel Level Package), which is applied to arrange semiconductor elements on the panel and packaged, can be implemented in semiconductor packaging. Methods such as high integration, thinning, and miniaturization are attracting attention.

In order to achieve the miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled device. However, if the thickness of the substrate is reduced, its strength is reduced, and the substrate is likely to be damaged during semiconductor package manufacturing. In this regard, the technique of temporarily bonding the substrate to the support using an adhesive, and separating the substrate and the support after processing the substrate.

As the adhesive for temporary bonding between the substrate and the support, the adhesive layer is easily removed by a solvent or the like, so thermoplastic adhesives are often used. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high-boiling point solvent, and a low-boiling point solvent. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2016/052315

[The problem to be solved by the invention]

However, semiconductor packaging manufacturing requires high-temperature processing such as film formation, firing, and die bonding. When the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer will decrease during high-temperature processing, and there may be doubts about the positional deviation of the substrate or the concealment of the substrate. In addition, when the heat resistance of the adhesive is increased, the coatability to the substrate or support tends to decrease. When a thermosetting adhesive is used for bonding between the support and the substrate, problems such as positional deviation or concealment will not occur during high-temperature processing. However, it is not easy to remove the adhesive layer by a solvent or the like. Even when the separation layer is provided, it is difficult to remove the adhesive layer attached to the substrate after the support and the substrate are separated due to the deterioration of the separation layer. In addition, conventional adhesives usually require a separation layer in order to separate the support and the substrate after the substrate is processed. Therefore, it is necessary to form a separation layer and to form an adhesive layer separately, and the operation is complicated.

The present invention has been accomplished in view of the foregoing. The subject of the present invention is to provide an adhesive composition that does not require a separation layer, has high heat resistance, and is easy to remove the adhesive layer, a laminate manufactured using the adhesive composition, and the The manufacturing method of the laminated body and the manufacturing method of the electronic part using the adhesive composition. [Means to solve the problem]

In order to solve the above-mentioned problems, the present invention adopts the following configuration. That is, the first aspect of the present invention is an adhesive composition that forms an adhesive composition for temporarily bonding a semiconductor substrate or an electronic device to a light-transmitting support, and it contains (a) light Absorbents, polyisocyanates, and polyols, or (b) light absorbers, urethane resins containing polymerizable carbon-carbon unsaturated bonds, and polymerization initiators.

The second aspect of the present invention is a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device are sequentially laminated, and the adhesive layer is the adhesive composition of the first aspect. The hardened body of the object.

The third aspect of the present invention is a method of manufacturing a laminated body, which is a method of manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated, which has the following steps: The step of applying the adhesive composition of the first aspect to the support or semiconductor substrate to form an adhesive composition layer is to place the semiconductor substrate on the support via the adhesive composition layer The step is to harden the adhesive composition layer to form the adhesive layer.

The fourth aspect of the present invention is a method for manufacturing a laminated body, which is a method for manufacturing a laminated body having a light-transmitting support, an adhesive layer, and an electronic device sequentially laminated, wherein the third aspect is laminated The manufacturing method of the body has the step of forming an electronic device after obtaining the laminated body. The electronic device is a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the member.

The fifth aspect of the present invention is a method of manufacturing an electronic component. After the multilayer body is obtained by the above-mentioned fourth aspect of the multilayer body manufacturing method, the method further has the following steps: The step of irradiating light on the adhesive layer through the support body to change the quality of the adhesive layer and separate the electronic device and the support body by separating the urethane bond in the adhesive layer with acid or The step of alkali decomposition to remove the adhesive layer attached to the electronic device. [Effects of the invention]

According to the present invention, it is possible to provide an adhesive composition that does not require a separation layer, has high heat resistance, and is easy to remove the adhesive layer, a laminate manufactured using the adhesive composition, a method of manufacturing the laminate, and the adhesive The manufacturing method of electronic parts of the agent composition.

In this specification and the scope of the patent application, "aliphatic" is a relative concept to aromatics, and is defined as a group or compound that does not have aromaticity. "Alkyl" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise stated. The same applies to the alkyl group in the alkoxy group. The "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise stated. The "halogenated alkyl group" is a group in which part or all of the hydrogen atoms of the 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. "Fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of the hydrogen atoms of an alkyl group or an alkylene group are substituted with fluorine atoms. "Structural unit ( structural unit ) " refers to the monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer). The description of "substitutable group" or "substitutable group" includes both the case where the hydrogen atom (-H) is substituted by a monovalent group and the case where the methylene group (-CH ₂ -) is substituted by a divalent group By. "Exposure" includes the entire concept of radiation exposure.

The so-called "structural unit derived from hydroxystyrene" means a structural unit formed by breaking the ethylenic double bond of hydroxystyrene. The so-called "structural unit derived from a hydroxystyrene derivative" means a structural unit formed by the cleavage of the ethylenic double bond of the hydroxystyrene derivative. The so-called "hydroxystyrene derivative" means a hydrogen atom at the α-position of hydroxystyrene is substituted with other substituents such as an alkyl group and a halogenated alkyl group, and the concept including these derivatives. Examples of their derivatives include those in which the hydrogen atom of the hydroxystyrene at the alpha position can be replaced by a substituent, and the hydrogen atom of the hydroxyl group in which the hydrogen atom at the alpha position can be replaced by a substituent. The benzene ring of styrene has a substituent other than a hydroxyl group bonded thereto. In addition, when the α-position (carbon atom at the α-position) is not specifically stated, it refers to the carbon atom to which the benzene ring is bonded. Examples of the substituent that replaces the hydrogen atom at the α-position of the hydroxystyrene include the same as those exemplified as the α-position substituent in the α-substituted acrylate.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group. Specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl) Propyl, n-butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl) and the like. In addition, the halogenated alkyl group as the substituent at the α-position specifically includes a group in which part or all of the hydrogen atoms of the aforementioned "alkyl group as the substituent at the α-position" are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. In addition, specific examples of the hydroxyalkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the aforementioned "alkyl group as the substituent at the α-position" are substituted with hydroxy groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, most preferably 1.

In this specification and the scope of the patent application, there are asymmetric carbons in the structure represented by the chemical formula, and there may be enantiomers or diastereomers. At this time, a chemical formula represents their isomers. These isomers can be used alone or as a mixture.

(Adhesive composition) The adhesive composition of the first 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 light-transmitting support, and is characterized by containing (a) a light absorber and a polyisocyanate , And polyols, or (b) light absorbers, urethane resins containing polymerizable carbon-carbon unsaturated bonds, and polymerization initiators.

＜Object to be temporarily connected＞ The adhesive composition of this embodiment is used to form an adhesive layer for temporarily bonding a semiconductor substrate or an electronic device and a support. In this specification, "temporarily joined" means that the joining object is temporarily joined (for example, between arbitrary operation steps). More specifically, a semiconductor substrate or an electronic device is temporarily attached to a support body for thinning of the device, transportation of the semiconductor substrate, mounting of the semiconductor substrate, etc., and is fixed (temporarily attached) to the support body. This step ends. After that, the self-supporting body is separated.

≪Semiconductor substrate≫ The semiconductor substrate using the adhesive composition of this embodiment is not particularly limited, and it may be a substrate generally used as a semiconductor substrate. The semiconductor substrate (bare die) is provided for steps such as thinning and mounting while being supported by the support. For example, structures such as integrated circuits and metal bumps can be mounted on the semiconductor substrate. The semiconductor substrate typically includes a silicon wafer substrate, but it is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, and the like.

≪Electronic device≫ In this specification, "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited, and may be a device in which various mechanical structures or circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the aforementioned member. The electronic device may be a rewiring layer described later and/or a semiconductor element or other element encapsulated or insulated by an encapsulating material or an insulating material, and may have a single-layer or multi-layer structure.

≪Support body≫ The support is a member that supports a semiconductor substrate or an electronic device. As described later, the support base is composed of a member that has light-transmitting properties and supports a semiconductor substrate.

The adhesive composition of this embodiment contains any one of the following components (a) or (b). (a) Light absorbers, polyisocyanates, and polyols. (b) A light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. Hereinafter, for convenience, the adhesive composition containing the aforementioned component (a) is also referred to as "adhesive composition (a)". The adhesive composition containing the aforementioned component (b) is also referred to as "adhesive composition (b)".

The adhesive composition (a) and the adhesive composition (b) are both curable adhesive compositions, which are cured by forming a cross-linked structure by heating or the like. Therefore, an adhesive composition layer is formed between a semiconductor substrate or an electronic device (hereinafter collectively referred to as a "semiconductor substrate, etc.") and a support, and by curing, an adhesive layer that temporarily bonds the semiconductor substrate or the like to the support can be formed. In addition, the adhesive layer formed by the adhesive composition (a) or the adhesive composition (b) contains a light absorber. Therefore, when light is irradiated to the adhesive layer through the light-transmitting support, the light absorber in the adhesive layer absorbs the light, and the adhesive layer is deteriorated. Thereby, it can be separated into a semiconductor substrate or device temporarily bonded via the aforementioned bonding layer and a support body through which light is transmitted. In addition, since the adhesive layer formed by the adhesive composition (a) or the adhesive composition (b) contains a urethane resin, the urethane bond can be decomposed by acid or alkali. Decompose and then layer. Thereby, after separation from the light-transmitting support, the residue adhering to the semiconductor substrate or the adhesive layer of the device can be removed.

＜Adhesive composition (a)＞ The adhesive composition (a) contains a light absorber, a polyisocyanate, and a polyol. The adhesive composition (a) is heated to crosslink the urethane bond of the polyisocyanate and the polyol. Thereby, the adhesive composition layer is cured, and an adhesive layer for temporarily bonding the support, the semiconductor substrate, etc., is formed. In addition, when light such as laser light is irradiated to the adhesive layer, the light absorber absorbs the light, and the adhesive layer is deteriorated. Thereby, the support body and the semiconductor substrate, etc. can be separated. In addition, residues attached to the adhesive layer of the semiconductor substrate and the like can be removed by decomposing the urethane bond by acid or alkali.

≪Light absorber: (B) component≫ The adhesive composition (a) contains a light absorber (hereinafter also referred to as "(B) component"). Since the adhesive composition (a) contains the component (B), it can be irradiated with light to change the quality of the adhesive layer.

When the component (B) is a substance having light absorption energy, it is not particularly limited. The component (B) is based on the wavelength of the irradiated light when the support is separated from the semiconductor substrate, etc., and one that can absorb light of that wavelength can be used. For example, the component (B) can absorb light in the wavelength region of 300~800nm. The component (B) is preferably one that can absorb the wavelength range of 400 to 700. It is more preferable to absorb light in the wavelength region of 450 to 600 nm, and more preferably to absorb light in the wavelength region of 500 to 550 nm. (B) Component includes, for example, pigments and dyes.

·pigment The pigment can be an organic pigment or an inorganic pigment. The pigment may be any of a black pigment and a colored pigment.

Examples of black organic pigments include perylene black (perylene-based black pigment), lignin black, aniline black, and nigrosine black. Black inorganic pigments include, for example, carbon black (lamp black, acetylene black, thermal black, channel black, furnace black, etc.), chromium oxide, iron oxide, titanium black, acid titanium nitride, titanium nitride, strontium titanate, Chromium oxide, and cerium oxide, etc.

Examples of color pigments include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colourists). Specifically, the following color index (CI) is attached. Numberers, etc.

CI Pigment Yellow 1 (Hereinafter, "CI Pigment Yellow" is also described only by numbers), 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; CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is also described only by numbers), 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, "C.I. Pigment Violet" is also described only by numbers), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, "CI Pigment Red" is also described only by numbers), 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, 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, "C.I. Pigment Blue" is also described only by numbers), 2, 15, 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 diameter of the pigment can be appropriately set, for example, the volume average particle diameter is 10 nm or more and 1000 nm or less, preferably 10 nm or more and 500 nm or less, and more preferably 10 nm or more and 300 nm or less. The volume average particle size can be obtained by the dynamic light scattering method.

A pigment may be used individually by 1 type, and may use 2 or more types together. In addition, plural pigments that absorb light in different wavelength regions may be used in combination. For example, a black pigment may be used in combination with one or more color pigments.

·dye Examples of dyes include azo dyes (monoazo and polyazo dyes, metal complex salt azo dyes, pyrazolone azo dyes, stilbene azo dyes, thiazole azo dyes), anthraquinone dyes (anthracene Quinone derivatives, anthrone derivatives), indigoid dyes (indigo derivatives, thioindigo derivatives), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthones) Ton dyes, acridine dyes), quinone imine dyes ( Quinoneimine dye) (azine dye, oxazine dye, thiazine dye), methine dye (cyan dye, azomethine dye), quinoneimine dye, nitroso dye, Benzoquinone and naphthoquinone dyes, naphthimide dyes, and perylene dyes, etc.

As the dye, commercially available dyes can also be used. Examples of commercially available dyes include PC-5857 (manufactured by Orient Industrial Co., Ltd.).

A dye may be used individually by 1 type, and may use 2 or more types together. In addition, multiple dyes that absorb light in different wavelength regions can be used in combination.

(B) A component may be used individually by 1 type, and may use 2 or more types together. The content of the component (B) in the adhesive composition (a) is relative to the total mass (100 mass%) of the adhesive composition (a), preferably 1-20 mass%, more preferably 2-15 mass %, more preferably 3-15% by mass. When the content of the component (B) is more than the above lower limit, the light absorption efficiency in the adhesive layer is improved, and the deterioration of the adhesive layer is good. (B) When the content of the component is below the above upper limit, it becomes easy to balance with other components. In addition, the content of the component (B) in the adhesive composition (a) is relative to the total mass (100% by mass) of the adhesive composition (a), and may be 5% by mass or more or 10% by mass or more .

≪Polyisocyanate compound: (I) component≫ The adhesive composition (a) contains a polyisocyanate compound (hereinafter also referred to as "(I) component"). In this specification, "polyisocyanate compound" refers to a compound having two or more isocyanate groups (-N=C=O) (polyisocyanate) or a compound having two or more blocked isocyanate groups (blocked poly Isocyanate). The polyisocyanate is not particularly limited, and ordinary users can use the urethane resin for the production without particular limitation. A compound in which the isocyanate group of the blocked polyisocyanate-based polyisocyanate is blocked by the reaction with a blocking agent and is inactivated. The blocked polyisocyanate used as the component (I) preferably has an isocyanate group blocked by a thermally dissociable blocking agent. Examples of the thermally dissociable blocking agent include blocking agents such as oximes, diketones, phenols, and caprolactam. In the blocked polyisocyanate obtained by the thermally dissociable blocking agent, the isocyanate group is inactive at room temperature, and the thermally dissociable blocking agent is dissociated by heating to regenerate the isocyanate group.

Specific examples of polyisocyanates include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates such as isocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated phenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc.; and Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, toluidine diisocyanate, p-diisocyanate Aromatic diisocyanates such as phenyl diisocyanate and naphthylene diisocyanate; and these biuret, isocyanurate, trimethylolpropane adducts, etc. A polyisocyanate may be used individually by 1 type, and may use 2 or more types together.

Commercially available polyisocyanates can also be used. Commercially available polyisocyanates include duranate (registered trademark) 24A-100, duranate22A-75P, duranateTPA-100, duranateTKA-100, duranateP301-75E, duranate21S-75E, duranateMFA-75B, duranateMHG-80B, duranateTUL-100, duranateTLA-100, duranateTSA-100, duranateTSS-100, duranateTSE100, duranateE402-80B, duranateE405-70B, duranateAS700-100, duranateD101, duranateD201, and duranateA201H (the above are trade names, manufactured by Asahi Kasei Chemicals), etc. These products may be used alone or in combination of two or more.

Examples of the blocked isocyanate include compounds in which the isocyanate group of the polyisocyanate described above is protected by reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, that is, it is added to isocyanate groups and is stable at room temperature, but when heated to a dissociation temperature or higher, it is free to form isocyanate groups. Limited use of known compounds. Specific examples of the blocking agent include, for example, internal amide compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; methyl ethyl ketoxime, methyl ethyl ketoxime, and methyl ethyl ketoxime. Oxime compounds such as methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamidoxime, acetone oxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, etc.; Monocyclic phenol compounds such as phenol, cresol, catechol, nitrophenol; polycyclic phenol compounds such as 1-naphthol; methanol, ethanol, isopropanol, tert-butanol, trimethylolpropane, 2 -Alcohol compounds such as ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.; alkyl malonate, dialkyl malonate, and acetic acid Active methylene compounds such as alkyl esters and acetone. The blocking agent may be used singly or in combination of two or more kinds.

The blocked polyisocyanate can be produced by reacting polyisocyanate with a blocking agent. The reaction of polyisocyanate and blocking agent, for example, in a solvent without active hydrogen (1,4-dioxane, cellosolve acetate, etc.), under heating at about 50 to 100 ℃, and when necessary It is carried out in the presence of a blocking catalyst. The use ratio of the polyisocyanate and the blocking agent is not particularly limited. Based on the equivalent ratio of the isocyanate group in the polyisocyanate to the blocking agent, it is preferably 0.95:1.0 to 1.1:1.0, and more preferably 1:1.05 to 1.15. Known substances can be used as the blocking catalyst, for example, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide; hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc. ; These weak organic acid salts of acetate, caprylate, myristate, benzoate, etc.; and alkali metal salts of alkyl carboxylic acids such as acetic acid, caproic acid, caprylic acid, and myristic acid; etc. One type of blocking catalyst may be used alone, or two or more types may be used in combination.

A commercially available one can be used for the blocked polyisocyanate. Commercially available blocked polyisocyanates include, for example, Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (the above are trade names, manufactured by Asahi Kasei Co., Ltd.), etc.

The component (I) is preferably a blocked polyisocyanate in which an isocyanate group is blocked by a thermally dissociable blocking agent.

(I) A component may be used individually by 1 type, and may use 2 or more types together. The content of component (I) in the adhesive composition (a) is relative to the total mass (100% by mass) of the adhesive composition (a), preferably 5-50% by mass, more preferably 10-40% by mass %, and more preferably 20-40% by mass. When the content of the component (I) is greater than or equal to the above lower limit, the curability of the adhesive composition (a) becomes good. (I) When the content of the component is below the above upper limit, it is easy to balance with other components.

≪Polyol: (O) component≫ The adhesive composition (a) contains a polyol (hereinafter also referred to as "(O) component"). Polyols are compounds having two or more hydroxyl groups (-OH). Polyols are not particularly limited, and those generally used for the production of urethane resins can be used without any particular limitations. (O) The component may be an aliphatic polyol or an aromatic polyol. The component (O) may be a low molecular polyol (for example, less than a molecular weight of 500), or a high molecular polyol (for example, a molecular weight of 500 or more).

Specific examples of low-molecular polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5 -Pentylene glycol, 1,6-hexanediol, neopentyl glycol, alkanediol with carbon number 7-22, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5- Pentylene glycol, 2-ethyl-2-butyl-1,3-propanediol, C17-20 alkane-1,2-diol, 1,3-cyclohexanedimethanol, 1,4-ring Hexane dimethanol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol , Dihydric alcohols such as bisphenol A; Trihydric alcohols such as glycerol and trimethylolpropane; Tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; Xylitol, etc. Alcohols; hexavalent alcohols such as sorbitol, mannitol, alliitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, etc.; Heptahydric alcohol; and octahydric alcohols such as sucrose; etc.

Polymer polyols include, for example, phenol resins, resins containing hydroxystyrene skeletons, polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, and polycarbonate polyols. Alcohols, polyhydroxyalkanes, polyurethane polyols, vegetable oil-based polyols, etc. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.

[Phenolic resin] The phenol resin may be a Novolac type phenol resin or a Resol type phenol resin. Novolac-type phenol resins can be obtained by addition condensation of aromatic compounds having phenolic hydroxyl groups (hereinafter referred to as "phenols") and aldehydes under an acid catalyst. Resol type phenol resin can be obtained by addition condensation of phenols and aldehydes under an alkali catalyst.

The aforementioned phenols include, for example, phenol; cresols such as m-cresol, p-cresol, and o-cresol; 2,3-xylenol, 2,5-xylenol, 3,5-diphenol Xylenols such as cresol and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3, 5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butylphenol Alkylphenols such as -5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m- Alkoxyphenols such as propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol, etc. Isopropenyl phenols; aryl phenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9- Bis(4-hydroxy-3,5-dimethylphenyl) pyridium, 9,9-bis(4-hydroxy-3-methylphenyl) pyridium, 1,1-bis(4-hydroxy-3-methyl) (Phenyl) cyclohexane and other polyhydroxyphenols, etc.

The aforementioned aldehydes include, for example, formaldehyde, polyformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde , M-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzene Formaldehyde, cinnamaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenylbenzaldehyde, etc.

The acid catalyst in the addition condensation reaction is not particularly limited, and for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used. The alkali catalyst in the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium carbonate, hexamethylenetetramine, etc. 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 structural units derived from hydroxystyrene or hydroxystyrene derivatives include structural units represented by the following general formula (a10-1).

。 [式中，R為氫原子、碳數1~5之烷基或碳數1~5之鹵化烷基。Ya^x1 為單鍵或2價之連結基。Wa^x1 為(n_ax1 +1)價之芳香族烴基。n_ax1 為1~3之整數]。

. [In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons. Ya ^x1 is a single bond or a bivalent linking base. Wa ^x1 is an aromatic hydrocarbon group of (n _ax1 +1) valence. n _ax1 is an integer from 1 to 3].

In the aforementioned formula (a10-1), R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons. The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched chain alkyl group having 1 to 5 carbon atoms. Specifically, methyl, ethyl, propyl, and isopropyl are exemplified , N-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbon atoms of R is a group obtained by substituting part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms by halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group with a carbon number of 1 to 5 or a fluorinated alkyl group with a carbon number of 1 to 5. For ease of industrial acquisition, a hydrogen atom or a methyl group is most preferred.

In the aforementioned formula (a10-1), Ya ^x1 is a single bond or a divalent linking group. The ^{divalent linking group in Ya x1} includes, for example, a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

･Divalent hydrocarbon group that ^{may have a substituent: When Ya x1} is a divalent hydrocarbon group that may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

･･ ^{The aliphatic hydrocarbon group in Ya x1} This aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. The aliphatic hydrocarbon group may be saturated or unsaturated, and in general, it is preferably saturated. The aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

･･･Straight-chain or branched aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has a carbon number of 1~10, more preferably a carbon number of 1~6, and even more preferably a carbon number of 1~ 4. The best carbon number is 1~3. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkylene group. Specifically, methylidene [-CH ₂ -], ethylidene [-(CH ₂ ) ₂ -], propylene Group [-(CH ₂ ) ₃ -], butylene [-(CH ₂ ) ₄ -], pentylene [-(CH ₂ ) ₅ -] and the like. The branched aliphatic hydrocarbon group preferably has a carbon number of 2-10, more preferably a carbon number of 3-6, still more preferably a carbon number of 3 or 4, and most preferably a carbon number of 3. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -and other alkylene groups;- CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -and other alkyl ethylene groups; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -and other alkyl ethylene groups; -CH(CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, such as alkylene, etc., such as alkylene, etc. The alkyl group in the alkylene alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The aforementioned linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

･･･Aliphatic hydrocarbon group containing a ring in the structure The aliphatic hydrocarbon group containing a ring in the structure includes a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, the aforementioned ring The aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the aforementioned cyclic aliphatic hydrocarbon group is between the linear or branched aliphatic hydrocarbon group. The base and so on. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has a carbon number of 3-20, more preferably a carbon number of 3-12. 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 two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane. The polycycloalkane is preferably one having 7 to 12 carbon atoms. Specifically, adamantane, Norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

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 halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group of the aforementioned 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, and a tert-butyl group. The alkoxy group of the aforementioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy , Tert-butoxy, preferably methoxy and ethoxy. The halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group as the substituent includes a group obtained by substituting a part or all of the hydrogen atoms of the alkyl group with the halogen atom. The cyclic aliphatic hydrocarbon group may also be that a part of the carbon atoms forming the ring structure is substituted by a substituent containing a heteroatom. The substituents containing heteroatoms are preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

･･ ^{Aromatic hydrocarbon group in Ya x1} The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. When the aromatic ring is a cyclic conjugated system having 4n+2 π electrons, it is not particularly limited, and it may be a monocyclic type or a polycyclic type. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, particularly preferably 6-12. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, etc.; aromatic heterocycles in which a part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted by heteroatoms, and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. The aromatic hydrocarbon group, specifically, includes a group obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); aromatics containing two or more aromatic rings Group compounds (for example, biphenyl, pyruvate, etc.) obtained by removing two hydrogen atoms; hydrogen of a group (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring One of the atoms is substituted by alkylene (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. The aryl group in the arylalkyl group is obtained by removing one more hydrogen atom) and so on. The carbon number of the alkylene group to which the aforementioned aryl or heteroaryl group is bonded is preferably 1 to 4, more preferably 1 to 2 carbons, and particularly preferably 1 carbon.

The aforementioned aromatic hydrocarbon group is that the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, when the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be substituted by a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group of the aforementioned 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, and a tert-butyl group.　 The aforementioned alkoxy group, halogen atom, and halogenated alkyl group as substituents can be exemplified as substituents that replace the hydrogen atom of the aforementioned cyclic aliphatic hydrocarbon group.

･Divalent linking group ^{containing heteroatoms: When Ya x1} is a divalent linking group containing heteroatoms, the linking group is preferred, such as -O-, -C(=O)-O-, -C (=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can be substituted by alkyl, acyl, etc. substituents), - S -, - S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 - C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m" -Y ²² -, ^{-Y 21} -OC(=O)- Y ²² -or -Y ²¹ -S(=O) ₂ -OY ²² -represents a group [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group that may have a substituent, O is an oxygen atom, and m" is 0~3 integer] etc. The aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- When, the H may be substituted by substituents such as alkyl and acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has a carbon number of 1-10, more preferably 1-8, and particularly preferably 1-5. General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -(Y ²¹ -C(=O )-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² -or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ²² are independently possible A substituted divalent hydrocarbon group. The divalent hydrocarbon group includes the same ones as those listed in the description of the divalent linking group (divalent hydrocarbon group that may have a substituent). Y ^{21 is} preferably a linear aliphatic group The hydrocarbyl group is more preferably a straight-chain alkylene group, and more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably a methylidene group or an ethylidene group. Y ^{22 is} preferably a straight-chain alkylene group. Or a branched aliphatic hydrocarbon group, more preferably a methylidene group, an ethylidene group or an alkylidene group. The alkyl group in the alkylidene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms , More preferably a straight-chain alkyl group with 1 to 3 carbon atoms, most preferably a methyl group. In the group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -, m" It is preferably an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 1. In other words, the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -represents The base is particularly preferably the base represented by the formula -Y ²¹ -C(=O)-OY ²² -. Wherein, preferably the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - represents a group of. In this formula, a'is preferably an integer of 1-10, an integer of 1-8, more preferably an integer of 1-5, still more preferably 1 or 2, and most preferably 1. b'is preferably an integer from 1 to 10, an integer from 1 to 8, more preferably an integer from 1 to 5, still more preferably 1 or 2, and most preferably 1.

Ya ^{x1 is} preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), -C(=O)-NH-, linear or branched alkylene The base, or a combination of these, is particularly preferably a single bond.

In the aforementioned formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group of (n _ax1 +1) valence. The aromatic hydrocarbon group in Wa ^x1 _{may be a group obtained by removing (n ax1} +1) hydrogen atoms from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, particularly preferably 6-12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles substituted with heteroatoms as part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

In the aforementioned formula (a10-1), n _{ax1 is} preferably an integer of 1 to 3, 1 or 2, and more preferably 1.

Specific examples of the structural unit represented by the aforementioned general formula (a10-1) are shown below. In the following formula, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

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] Polycarbonate polyols can be exemplified by adding ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 -Pentylene glycol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Polycarbonate polycarbonate obtained from one or more of ethylene glycol such as dimethanol, bisphenol A, or hydrogenated bisphenol A, and dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. alcohol.

Among them, the polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).

[式中，Rp¹ 及Rp² 各自獨立為2價烴基。np為2以上之整數]。

[In the formula, Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. np is an integer of 2 or more].

In the aforementioned general formula (PC-1), Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. The aforementioned divalent hydrocarbon group is an aromatic hydrocarbon group, but may be an aliphatic hydrocarbon group. Examples of the aforementioned divalent hydrocarbon group include the same ones as those exemplified ^{in Ya x1 of the general formula (a10-1).} The ^{divalent hydrocarbon group in Rp 1} and Rp ² is preferably an aliphatic hydrocarbon group, and more preferably a linear or branched alkylene group. The aforementioned divalent hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 3 to 8, and still more preferably a carbon number of 4 to 6. Specific examples of Rp ¹ and Rp ² include -(CH ₂ ) ₆ -or -(CH ₂ ) ₅ -.

The weight average molecular weight (Mw) of the polycarbonate polyol is preferably 500-5000, more preferably 500-3000, still more preferably 500-2000, particularly preferably 500-1000.

[Other polyols] Polyester polyols include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or their dialkyl esters or their mixtures, and, for example, ethyl Glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane Polyethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol and other glycols or polyester polyols obtained by the reaction of their mixtures, or polycaprolactone, polyvalerolactone , Poly(β-methyl-γ-valerolactone) and other lactones are polyester polyols obtained by ring-opening polymerization.

Polyether polyols include, for example, ethylene oxide compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, such as water, ethylene glycol, propylene glycol, trimethylolpropane, and propylene oxide. Polyether polyols obtained by polymerization with low-weight polyols such as triols as initiators.

Polyether ester polyols include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or their dialkyl esters or their mixtures The polyether ester polyol obtained by the reaction of the above-mentioned polyether polyol.

Polyester amide polyol. In the above-mentioned esterification reaction, for example, aliphatic diamine having an amine group such as ethylene diamine, propylene diamine, hexamethylene diamine, etc., is used together as a raw material to obtain a polyester amide polyol. .

Acrylic polyols can be exemplified by combining hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc. or their corresponding methacrylic acid derivatives with, for example, acrylic acid, Polyesteramide polyol obtained by copolymerizing methacrylic acid or its ester.

Examples of the polyhydroxyalkane include liquid rubber obtained by copolymerizing butadiene or butadiene with acrylamide.

Polyurethane polyols are polyols having more than one urethane bond in one molecule. Examples include polyether polyols, polyester polyols, and polyether esters with a number average molecular weight of 200 to 20,000. A polyurethane polyol obtained by reacting a polyol and the like with a polyisocyanate preferably has an NCO/OH of less than 1, more preferably 0.9 or less.

The vegetable oil-based polyol includes castor oil, castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol. Among them, the vegetable oil-based polyol is preferably castor oil-modified polyol, more preferably castor oil-modified diol.

Among the above, the component (O) is preferably a phenol resin or a resin containing a hydroxystyrene skeleton, more preferably a novolak resin or a resin containing a hydroxystyrene skeleton, and still more preferably a hydroxystyrene or a hydroxystyrene derivative The polymer of the material is particularly preferably polyhydroxystyrene resin.

(O) A component may be used individually by 1 type, and may use 2 or more types together. The content of the (O) component in the adhesive composition (a) is relative to the total mass (100 mass%) of the adhesive composition (a), preferably 50 to 90 mass%, more preferably 50 to 85 mass %, and more preferably 60-85% by mass. When the content of the component (O) is at least the above lower limit, the curability of the adhesive composition (a) becomes good. (I) When the content of the component is below the above upper limit, it becomes easy to balance with other components.

The hydroxyl group in the component (O) contained in the adhesive composition (a) The molar ratio (NCO/OH) of (-OH) to the isocyanate group (-NCO) in component (I) 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 (I) component and the (O) component is preferably in the range of ((I):(O))=1:10~10:1, more preferably 2:8~8:2, and more preferably 2:8~5:5.

＜Adhesive composition (b)＞ The adhesive composition (b) contains a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. The adhesive composition (b) is heated or the like to polymerize and crosslink a urethane resin containing a polymerizable carbon-carbon unsaturated bond. Thereby, the adhesive composition layer is cured, and an adhesive layer for temporarily bonding the support, the semiconductor substrate, etc., is formed. In addition, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light, and the adhesive layer is deteriorated. Thereby, the support body and the semiconductor substrate, etc. can be separated. In addition, the residue attached to the adhesive layer of the semiconductor substrate or the like can be removed by decomposing the urethane bond with acid or alkali.

≪Light absorber: (B) component≫ The adhesive composition (b) contains a light absorber ((B) component). As the (B) component, the same thing as the said adhesive composition (a) is mentioned. In addition, the (B) component may contain a compound (B1) that absorbs at least a part of light in the range of 300 to 800 nm in wavelength and contains a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "(B1) component").

･(B1) Ingredients (B1) The component is a compound that absorbs at least a part of light in the range of 300 to 800 nm in wavelength and contains a polymerizable carbon-carbon unsaturated bond. In addition, the component (B1) is a compound that does not correspond to the component (P1) described later.

The component (B1) contains a polymerizable carbon-carbon unsaturated bond, so it reacts with the urethane resin (P1) (hereinafter also referred to as "(P1) component") containing a polymerizable carbon-carbon unsaturated bond described later It is cured to form an adhesive layer together with the component (P1). Thereby, the semiconductor substrate or electronic device and the support body can be temporarily bonded. In addition, the component (B1) absorbs at least a part of the light in the range of 300 to 800 nm. Therefore, by irradiating the light in the range of 300 to 800 nm to the adhesive layer, the component (B1) absorbs the light and generates heat. Thereby, the adhesive layer can be deteriorated.

The component (B1) acts as a light absorber that absorbs light with a wavelength of 300 to 800 nm. (B1) The component absorbs light in the wavelength range of 300 to 800 nm, and can be converted into thermal energy that can change the quality of the adhesive layer. The component (B1) is preferably one that can absorb light in the wavelength range of 300 to 700, more preferably one that can absorb light in the wavelength range of 300 to 600 nm, and even more preferably one that can absorb light in the wavelength range of 300 to 550 nm , Especially preferred are those that can absorb light in the wavelength range of 300~400nm. The component (B1) preferably has an absorption peak in the aforementioned wavelength range. (B1) The component depends on the wavelength of the light used when separating the support from the semiconductor substrate, etc., and one that can absorb light of that wavelength can be used. The component (B1) includes, for example, a component that absorbs light with a wavelength of 355 nm and converts it into thermal energy, which can change the quality of the adhesive layer.

The polymerizable carbon-carbon unsaturated bond contained in the compound (B1) is not particularly limited, but is preferably radical polymerizable. The polymerizable carbon-carbon unsaturated bond includes, for example, a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. The polymerizable carbon-carbon double bond includes, for example, a vinyl group, a methacryl group, and an acrylic group, but it is not limited to these. The polymerizable carbon-carbon triple bond includes, for example, an ethynyl group and a propargyl group, but it is not limited to these.

Examples of the compound (B1) include those represented by the following general formula (b1).

[式中，W為包含聚合性碳-碳不飽和鍵之1價基；Y為單鍵、或選自由-O-、-CO-、-COO-、及-CONH-所構成群組之2價之連結基；n為1~6之整數；X係具有其結構中具有芳香族性之縮合環骨架、二苯甲酮骨架、二苯甲醯基甲烷骨架、二苯甲醯基苯骨架、或苯并三唑骨架之n價的原子團。n為2以上時，複數存在之W及Y彼此可相同或相異]。

[In the formula, W is a monovalent group containing a polymerizable carbon-carbon unsaturated bond; Y is a single bond, or 2 selected from the group consisting of -O-, -CO-, -COO-, and -CONH- Valence linking group; n is an integer from 1 to 6; X has an aromatic condensed ring skeleton, a benzophenone skeleton, a benzophenacylmethane skeleton, a benzophenacylbenzene skeleton, Or the n-valent atomic group of the benzotriazole skeleton. When n is 2 or more, W and Y in plural may be the same or different from each other].

In the general formula (b1), W is a polymerizable group-containing group containing a polymerizable carbon-carbon unsaturated bond. The polymerizable carbon-carbon unsaturated bond contained in W includes, for example, a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. Examples of W include alkenyl and alkynyl. The aforementioned alkenyl group preferably has a carbon number of 2-10, more preferably a carbon number of 2-6, and still more preferably a carbon number of 2 or 3. Specific examples of the alkenyl group include, for example, a vinyl group and an isopropenyl group. The aforementioned alkynyl group preferably has 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms. Specific examples of the alkynyl group include, for example, an ethynyl group and a 1-propynyl group.

In the general formula (b1), Y is a single bond, or selected from -O-, -CO-, -COO-, and -CONH- constitute a group of divalent linking bases. 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, particularly preferably 1. When n is 2 or more, W in plural numbers may be the same or different from each other, but the same is preferred. When n is 2 or more, the plural Ys may be the same or different from each other, but the same is preferred.

In the general formula (b1), X has an aromatic condensed ring skeleton, a benzophenone skeleton, a benzophenone skeleton, a benzophenacylbenzene skeleton, or a benzotriazole skeleton in its structure. The n-valent atomic group.

[N-valent atomic group with aromatic condensed ring skeleton] The aromatic condensed ring skeleton system includes a condensed ring having at least one aromatic ring. The aforementioned aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings in the condensed ring is preferably 2-10, more preferably 2-6, still more preferably 2-4, particularly preferably 2 or 3. The condensed ring may be composed of only an aromatic ring or may be a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, but it is preferably a condensed ring composed of only an aromatic ring. Specific examples of the condensed ring include naphthalene, anthracene, phenanthrene, and pyrene. Among these, anthracene or phenanthrene is preferred.

Examples of X containing a condensed ring skeleton having aromaticity include those represented by the following general formula (Xa-1) or (Xa-2). X represented by the general formula (Xa-1) is an atomic group with an anthracene skeleton, and X represented by the general formula (Xa-2) is an atomic group with a phenanthrene skeleton.

[式中，L^a1 及L^a2 各自獨立表示單鍵或2價之連結基，R^a1 及R^a2 各自獨立表示取代基。n係與前述式(b1)中之n相同者。m表示0~9之整數，m+n≦10。n為2以上時，複數存在之L^a1 及L^a2 彼此可相同或相異。m為2以上時，複數存在之R^a1 及R^a2 彼此可相同或相異。*為通式(b1)中與Y鍵結的鍵結鍵]。

[In the formula, ^La1 and ^La2 each independently represent a single bond or a divalent linking group, and ^Ra1 and ^Ra2 each independently represent a substituent. n is the same as n in the aforementioned formula (b1). m represents an integer of 0-9, m+n≦10. n is 2 or more, L ^a1 and L ^a2 may be the same or presence of a plurality of different from each other. When m is 2 or more, ^Ra1 and ^Ra2 existing in plural may be the same or different from each other. * Is the bonding bond to Y in the general formula (b1)].

In the general formulas (Xa-1) and (Xa-2), ^La1 and ^La2 each independently represent a single bond or a divalent linking group. The aforementioned divalent linking group includes a hydrocarbon group which may have a substituent. The aforementioned hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aforementioned aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aforementioned aliphatic hydrocarbon group may be linear or branched, or may contain a ring in the structure. The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, and still more preferably a carbon number of 1 to 3. The branched aliphatic hydrocarbon group preferably has a carbon number of 2-10, more preferably a carbon number of 2-6, and still more preferably a carbon number of 2 or 3. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group may have a substituent. The aforementioned substituent may be one that replaces a hydrogen atom, or one that replaces a methylidene group (-CH ₂ -) in the carbon chain. Examples of the substituent substituting the hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, etc., and a hydroxyl group or an amino group is preferred. _{Examples of the substituents that replace the methylidene (-CH 2} -) in the carbon chain include -O-, -CO-, -NH-, -COO-, -CONH-, and the like.

The aforementioned aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the aforementioned aromatic hydrocarbon group may be monocyclic or polycyclic. The aforementioned aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained 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 to which an aromatic ring and an aliphatic hydrocarbon group are connected. The aforementioned aromatic hydrocarbon group may have a substituent. The aforementioned substituent may be substituted for the hydrogen atom of the aromatic ring, or substituted for the carbon atom of the ring constituting the aromatic ring with a hetero atom. Examples of the substituent substituting the hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, etc., and a hydroxyl group or an amino group is preferred. The heteroatom substituted for the ring of the aromatic ring includes a nitrogen atom, an oxygen atom, a sulfur atom, etc., and a nitrogen atom is preferred.

In general formulas (Xa-1) and (Xa-2), R ^a1 and R ^a2 each independently represent a substituent. R ^a1 and R ^a2 include, for example, an alkyl group, a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, a nitrile group, a nitrile alkyl group, an alicyclic group, and the like. The aforementioned alkyl group, alkoxy group, and nitrile alkyl group preferably have 1 to 5 carbon atoms, and more preferably have 1 to 3 carbon atoms. The aforementioned alicyclic group preferably has 1 to 6 carbon atoms. The nitrile alkyl group includes, for example, a malononitrile group. The alicyclic group may be an alicyclic hydrocarbon ring or an alicyclic heterocyclic ring. Examples of the alicyclic heterocyclic ring include those containing a sulfur atom, a nitrogen atom, or an oxygen atom. Specific examples of the alicyclic heterocycle include dithiolane.

In general formulas (Xa-1) and (Xa-2), m represents an integer of 0-9. m is preferably 0-6, more preferably 0-5, still more preferably 0-3, particularly preferably 0-2. In general formulas (Xa-1) and (Xa-2), n is the same as n in the aforementioned formula (b1). m and n have a relationship of m+n≦10.

[N-valent atomic group with benzophenone skeleton] Examples of X having a benzophenone skeleton include those represented by the following general formula (Xb).

[式中，L^b1 及L^b2 各自獨立表示單鍵或2價之連結基，R^b1 及R^b2 各自獨立表示取代基。p及q各自獨立表示0~5之整數，p+q=n。n係與前述式(b1)中之n相同者。m1及m2各自獨立表示0~5之整數，m1+p≦5、m2+q≦5。p為2以上時，複數存在之L^b1 彼此可相同或相異。q為2以上時，複數存在之L^b2 彼此可相同或相異。m1為2以上時，複數存在之R^b1 彼此可相同或相異。m2為2以上時，複數存在之R^b2 彼此可相同或相異。*係鍵結於通式(b1)中之Y的鍵結鍵]。

[In the formula, L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group, and R ^b1 and R ^b2 each independently represent a substituent. p and q each independently represent an integer from 0 to 5, and p+q=n. n is the same as n in the aforementioned formula (b1). m1 and m2 each independently represent an integer from 0 to 5, m1+p≦5, m2+q≦5. When p is 2 or more, L ^b1 existing in plural may be the same or different from each other. When q is 2 or more, L ^b2 existing in plural may be the same or different from each other. When m1 is 2 or more, the plural R ^b1 may be the same or different from each other. When m2 is 2 or more, R ^b2 existing in plural may be the same or different from each other. *It is the bonding bond of Y in the general formula (b1)].

In the general formula (Xb), L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group. Of the divalent linking group, and include (Xa-1) and (Xa-2) in the preceding formula L ^a1 and L are the same as those enumerated ^A2. L ^b1 and L ^{b2 are} preferably a single bond or an aliphatic hydrocarbon group that may have a substituent, and more preferably a single bond or an alkyl group that may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a _{part of the methylidene group (-CH 2} -) constituting the carbon chain is -O-, -CO-, -NH-, -COO-, -CONH- Substituted alkyl.

In the general formula (Xb), R ^b1 and R ^b2 each independently represent a substituent. Examples of R ^b1 and R ^b2 are the same as those exemplified in ^{R a1} and R ^a2 in the aforementioned formulas (Xa-1) and (Xa-2).

In the general formula (Xb), p and q each independently represent an integer of 0 to 5, and p+q=n. The aforementioned n is the same as n in the aforementioned formula (b1). In the general formula (Xb), m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5, m2+q≦5. m1 and m2 are preferably 0-3, more preferably 0-2, and still more preferably 0 or 1.

[N-valent atomic group with the framework of dibenzoylmethane] Examples of X having a dityl methane skeleton include those represented by the following general formula (Xc).

[式中，L^c1 及L^c2 各自獨立表示單鍵或2價之連結基，R^c1 及R^c2 各自獨立表示取代基。p及q各自獨立表示0~5之整數，p+q=n。n係與前述式(b1)中之n相同者。m1及m2各自獨立表示0~5之整數，m1+p≦5、m2+q≦5。p為2以上時，複數存在之L^c1 彼此可相同或相異。q為2以上時，複數存在之L^c2 彼此可相同或相異。m1為2以上時，複數存在之R^c1 彼此可相同或相異。m2為2以上時，複數存在之R^c2 彼此可相同或相異。*係鍵結於通式(b1)中之Y的鍵結鍵]。

[In the formula, L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group, and R ^c1 and R ^c2 each independently represent a substituent. p and q each independently represent an integer from 0 to 5, and p+q=n. n is the same as n in the aforementioned formula (b1). m1 and m2 each independently represent an integer from 0 to 5, m1+p≦5, m2+q≦5. When p is 2 or more, L ^c1 existing in plural may be the same or different from each other. When q is 2 or more, L ^c2 existing in plural may be the same or different from each other. When m1 is 2 or more, R ^c1 existing in plural may be the same or different from each other. When m2 is 2 or more, R ^c2 existing in plural may be the same or different from each other. *It is the bonding bond of Y in the general formula (b1)].

In the general formula (Xc), L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group. Of the divalent linking group, and include (Xa-1) and (Xa-2) in the preceding formula L ^a1 and L are the same as those enumerated ^A2. L ^c1 and L ^{c2 are} preferably a single bond or an aliphatic hydrocarbon group that may have a substituent, and more preferably a single bond or an alkyl group that may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a _{part of the methylidene group (-CH 2} -) constituting the carbon chain is -O-, -CO-, -NH-, -COO-, -CONH- Substituted alkyl.

In the general formula (Xc), R ^c1 and R ^c2 each independently represent a substituent. R ^c1 and R ^c2 may be the same as those exemplified in ^{R a1} and R ^a2 in the aforementioned formulas (Xa-1) and (Xa-2).

In the general formula (Xc), p and q each independently represent an integer of 0 to 5, and p+q=n. The aforementioned n is the same as n in the aforementioned formula (b1). In the general formula (Xc), m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5, m2+q≦5. m1 and m2 are preferably 0-3, more preferably 0-2, and still more preferably 0 or 1.

[N-valent atomic group with dibenzylbenzene skeleton] Examples of X having a ditylbenzene skeleton include those represented by the following general formula (Xd).

[式中，L^d1 、L^d2 及L^d3 各自獨立表示單鍵或2價之連結基，R^d1 、R^d2 及R^d3 各自獨立表示取代基。p及q各自獨立表示0~5之整數，r表示0~4之整數，p+q+r=n。n係與前述式(b1)中之n相同者。m1及m2各自獨立表示0~5之整數，m3表示1~4之整數，m1+p≦5、m2+q≦5、m3+r=4。p為2以上時，複數存在之L^d1 彼此可相同或相異。q為2以上時，複數存在之L^d2 彼此可相同或相異。r為2以上時，複數存在之L^d3 彼此可相同或相異。m1為2以上時，複數存在之R^d1 彼此可相同或相異。m2為2以上時，複數存在之R^d2 彼此可相同或相異。m3為2以上時，複數存在之R^d3 彼此可相同或相異。*係鍵結於通式(b1)中之Y的鍵結鍵]。

[In the formula, L ^d1, L ^d2 and L ^d3 each independently represent the single bond or a divalent linking group, R ^d1, R ^d2 and R ^d3 each independently represent a substituent. p and q each independently represent an integer from 0 to 5, r represents an integer from 0 to 4, and p+q+r=n. n is the same as n in the aforementioned formula (b1). m1 and m2 each independently represent an integer from 0 to 5, m3 represents an integer from 1 to 4, m1+p≦5, m2+q≦5, m3+r=4. When p is 2 or more, L ^d1 existing in plural may be the same or different from each other. When q is 2 or more, L ^d2 existing in plural may be the same or different from each other. When r is 2 or more, L ^{d3 in} plurals may be the same or different from each other. When m1 is 2 or more, the plural R ^d1 may be the same or different from each other. When m2 is 2 or more, the plural R ^d2 may be the same or different from each other. When m3 is 2 or more, the plural R ^d3 may be the same or different from each other. *It is the bonding bond of Y in the general formula (b1)].

In the general formula (Xd), L ^d1 , L ^d2 and L ^d3 each independently represent a single bond or a divalent linking group. Of the divalent linking group, and include (Xa-1) and (Xa-2) in the preceding formula L ^a1 and L are the same as those enumerated ^A2. L ^d1 , L ^d2 and L ^{d3 are} preferably a single bond or an aliphatic hydrocarbon group that may have a substituent, and preferably a single bond or an alkyl group that may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a _{part of the methylidene group (-CH 2} -) constituting the carbon chain is -O-, -CO-, -NH-, -COO-, -CONH- Substituted alkyl.

In the general formula ^{(Xd), R d1, R} d2 and R ^d3 each independently represent a substituent. R ^d1 , R ^d2 and R ^d3 may be the same as those exemplified in ^{R a1} and R ^a2 in the aforementioned formulas (Xa-1) and (Xa-2).

In the general formula (Xd), p and q each independently represent an integer from 0 to 5, r represents an integer from 0 to 4, and p+q+r=n. The aforementioned n is the same as n in the aforementioned formula (b1). In the general formula (Xd), m1 and m2 each independently represent an integer from 0 to 5, m3 represents an integer from 1 to 4, m1+p≦5, m2+q≦5, m3+r=4. m1, m2, and m3 are preferably 0-3, more preferably 0-2, and still more preferably 0 or 1.

[N-valent atomic group with benzotriazole skeleton] Examples of X having a benzotriazole skeleton include those represented by the following general formula (Xe).

[式中，L^e 表示單鍵或2價之連結基，R^e 表示取代基。n係與前述式(b1)中之n相同者。m表示0~4之整數，m+n≦5。n為2以上時，複數存在之L^e 彼此可相同或相異。m為2以上時，複數存在之R^e 彼此可相同或相異。*係鍵結於通式(b1)中之Y的鍵結鍵]。

[In the formula, L ^e represents the single bond or a divalent linking group, R ^e represents a substituent. n is the same as n in the aforementioned formula (b1). m represents an integer from 0 to 4, m+n≦5. n is 2 or more, the presence of a plurality of L ^e may be the same or different from each other. m is 2 or greater, the plurality of R ^e may be the same or different from each other. *It is the bonding bond of Y in the general formula (b1)].

In the general formula (Xe), ^Le represents a single bond or a divalent linking group. Of the divalent linking group, and include (Xa-1) and (Xa-2) in the preceding formula L ^a1 and L are the same as those enumerated ^{A2. Le is} preferably a single bond or a hydrocarbon group that may have a substituent, preferably a single bond, an alkyl group that may have a substituent, or a group in which one 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, and more preferably have 1 to 3 carbon atoms.

In the general formula (Xe), R ^e represents a substituent. R ^e may be the same as those exemplified in ^{R a1} and R ^a2 in the aforementioned formulas (Xa-1) and (Xa-2).

In the general formula (Xe), m represents an integer of 0-4. m is preferably 0-3, more preferably 0-2, and still more preferably 0 or 1. In the general formula (Xe), n is the same as n in the aforementioned formula (b1). At this time, n is an integer from 1 to 5. m and n have a relationship of m+n≦5.

The compound (B1) is preferably a compound represented by the following general formula (b1-1) or (b1-2).

[式中，R¹¹ 、R¹² 、及R¹³ 各自獨立為氫原子或碳原子數1~3之烷基；Y¹ 為單鍵、或選自由-O-、-CO-、-COO-、及 -CONH-所構成群組之2價之連結基，n¹ 為1~6之整數；X¹ 係其結構中含有具有芳香族性之縮合環骨架、二苯甲酮骨架、二苯甲醯基甲烷骨架、二苯甲醯基苯骨架、或苯并三唑骨架之n¹ 價之原子團。n¹ 為2以上時，複數存在之R¹¹ 、R¹² 、及R¹³ 及Y¹ 彼此可相同或相異]。

[In the formula, R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms; Y ¹ is a single bond, or selected from -O-, -CO-, -COO-, And the divalent linking group of the group formed by -CONH-, n ¹ is an integer of 1 to 6; X ¹ is the structure containing aromatic condensed ring skeleton, benzophenone skeleton, and benzophenone ^{N 1} valence atomic group of methane skeleton, dibenzylbenzene skeleton, or benzotriazole skeleton. When n ¹ is 2 or more, R ¹¹ , R ¹² , and R ¹³ and Y ¹ that exist in plural may be the same or different from each other].

[式中，R²¹ 為氫原子或碳原子數1~3之烷基；Y² 為單鍵、或選自由-O-、-CO-、-COO-、及-CONH-所構成群組之2價之連結基；n² 為1~6之整數；X² 係其結構中含有具有縮合環骨架、二苯甲酮骨架、二苯甲醯基甲烷骨架、二苯甲醯基苯骨架、或苯并三唑骨架之n² 價之原子團。n² 為2以上時，複數存在之R²¹ 及Y² 彼此可相同或相異]。

[In the formula, R ²¹ is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms; Y ² is a single bond, or selected from the group consisting of -O-, -CO-, -COO-, and -CONH- A bivalent linking group; n ² is an integer of 1 to 6; X ² is a structure containing a condensed ring skeleton, a benzophenone skeleton, a benzophenacylmethane skeleton, a benzophenacylbenzene skeleton, or The n ^2- valent atomic group of the benzotriazole skeleton. When n ² is 2 or more, R ²¹ and Y ² present in plural may be the same or different from each other].

In the general formula (b1-1), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ and R ¹² are each independently 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. R ^{13 is} preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.

In the general formula (b1-1), Y ¹ is the same as Y in the aforementioned general formula (b1). In the general formula (b1-1), X ¹ is the same as X in the aforementioned general formula (b1).

In the general formula (b1-1), n ¹ is the same as n in the aforementioned general formula (b1). When n ¹ is 2 or more, R ¹¹ , R ¹² , and R ¹³ present in plural may be the same or different from each other. When n ¹ is 2 or more, Y ¹ present in plural may be the same or different from each other. When n ¹ is 2 or more, X ¹ existing in plural may be the same or different from each other.

In the general formula (b1-2), R ²¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^{21 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.

In the general formula (b1-2), Y ² is the same as Y in the aforementioned general formula (b1). In the general formula (b1-2), X ² is the same as X in the aforementioned general formula (b1).

In the general formula (b1-2), n ² is the same as n in the aforementioned general formula (b1). When n ² is 2 or more, the plural R ²¹ may be the same or different from each other. When n ² is 2 or more, Y ² present in plural may be the same or different from each other. When n ² is 2 or more, X ² existing in plural may be the same or different from each other.

Specific examples of the compound (B1) containing a condensed ring skeleton having aromaticity are shown below, but are not limited to these.

The specific example of the compound (B1) containing a benzophenone skeleton is shown below, but it is not limited to these.

The specific example of the compound (B1) containing a dityl methane skeleton is shown below, but it is not limited to these.

The specific example of the compound (B1) containing a ditylbenzene skeleton is shown below, but it is not limited to these.

The specific example of the compound (B1) containing a benzotriazole skeleton is shown below, but it is not limited to these.

(B1) A component may be used individually by 1 type, and may use 2 or more types together. The content of the (B1) component in the adhesive composition is relative to 100 parts by mass of the polyurethane resin (P1) described below, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, may be 10 parts by mass or more, or 15 parts by mass or more. (B1) The upper limit of the content of the component is not particularly limited, but it is, for example, 30 parts by mass or less, or 20 parts by mass or less with respect to 100 parts by mass of the polyurethane resin (P1) described below. (B1) The range of the content of the component is relative to 100 parts by mass of the polyurethane resin (P1) described below, preferably 1-30 parts by mass, more preferably 3-20 parts by mass, and still more preferably 5~ 15 parts by mass. (B1) When the content of the component is more than the above lower limit, the light absorption efficiency in the adhesive layer increases, and the deterioration of the adhesive layer becomes good. (B1) When the content of the component is below the above upper limit, it becomes easy to balance with other components.

(B) A component may be used individually by 1 type, and may use 2 or more types together. The content of the component (B) in the adhesive composition (b) is relative to the total mass (100 mass%) of the adhesive composition (b), preferably 1-20 mass%, more preferably 2-15 mass %, more preferably 3-15% by mass. When the content of the component (B) is more than the above lower limit, the light absorption efficiency in the adhesive layer increases, and the deterioration of the adhesive layer becomes good. (B) When the content of the component is below the above upper limit, it becomes easy to balance with other components. In addition, the content of the component (B) in the adhesive composition (b) is relative to the total mass (100% by mass) of the adhesive composition (b). It may be 5% by mass or more, or it may be 10% by mass or more.

≪Urethane resin containing polymerizable carbon-carbon unsaturated bonds: (P1) component≫ The adhesive composition (b) contains a urethane resin containing a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "(P1) component"). (P1) The component is polymerized and hardened by polymerizable carbon-carbon unsaturated bonds to form an adhesive layer. Thereby, the semiconductor substrate or electronic device and the support body can be temporarily bonded. In addition, the urethane bond in component (P1) has the property of being decomposed by acid or alkali. Therefore, the aforementioned adhesive layer can be easily removed with a treatment solution containing acid or alkali.

(P1) The polymerizable carbon-carbon unsaturated bond contained in the component is not particularly limited, but it 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, preferably a polymerizable carbon-carbon double bond. The polymerizable carbon-carbon double bond includes, for example, a methacryl group and an acryl group. (P1) The polymerizable carbon-carbon unsaturated bond contained in the component may be one type or two or more types. (P1) The equivalent of the polymerizable carbon-carbon unsaturated bond contained in the component is preferably 200~2000g/eq. or more, more preferably 300~1500g/eq. or more, and more preferably 400~1200g/eq. Above, 500~1000g/eq. is particularly preferred. When the polymerizable carbon-carbon unsaturated bond equivalent is more than the lower limit of the aforementioned preferable range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. When the polymerizable carbon-carbon unsaturated bond equivalent is less than the upper limit of the aforementioned preferable range, the adhesive layer does not become too hard, and the detergency is good. The aforementioned equivalent number is the molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon unsaturated bond.

(P1) The weight average molecular weight (Mw) of the component is preferably 5,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 12,000 to 30,000, particularly preferably 13,000 to 25,000.

The component (P1) can be synthesized by a polymerization addition 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). At least one of the component (I) and the component (O) preferably contains a polymerizable carbon-carbon unsaturated bond.

･Polyisocyanate compound: (I) component (P1) The component (I) used for the synthesis of the component may be the same as those exemplified in the above-mentioned adhesive composition (a) (I) component. (I) A component may be used individually by 1 type, and may use 2 or more types together. For example, a mixture of aliphatic diisocyanate and aromatic diisocyanate can be used as the component (I). The aforementioned aliphatic diisocyanate is preferably hydrogenated xylene diisocyanate. The aforementioned aromatic diisocyanate is preferably 4,4-diphenylmethane diisocyanate.

･Polyol: (O) component (P1) The component (O) used in the synthesis of component includes polyols containing polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "(O1) component") and other polyols (hereinafter also referred to as Is "(O2) ingredient").

･･Polyol containing polymerizable carbon-carbon unsaturated bond ((O1) component) (O1) As a component, the polyhydric alcohol containing at least 1 sort(s) selected from the group which consists of a methacryl group and an acrylic group is mentioned. (O1) The polymerizable carbon-carbon unsaturated bond possessed by the component may be one or two or more.

The component (O1) includes, for example, esters of trivalent or higher polyhydric alcohols and methacrylic acid, acrylic acid, or derivatives thereof. The aforementioned trivalent or higher polyol is preferably a trivalent or higher low molecular polyol. The aforementioned low-molecular polyols with three or more valences include triols such as glycerol and trimethylolpropane; tetraols such as tetramethylolmethane (pentaerythritol) and diglycerol; xylitol, etc. The pentahydric alcohol; sorbitol, mannitol, allinitol, iditol, dulcitol, altritol, inositol, dipentaerythritol and other hexahydric alcohols; sorbitol And other heptahydric alcohols; and octahydric alcohols such as sucrose; etc.

(O1) Specific examples of the component include glycerol mono(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate , Diglycerol di(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate ) Acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, etc. "(Meth)acrylate" refers to the concept of methacrylate and acrylate, and refers to methacrylate or acrylate.

(O1) A component may be used individually by 1 type, and may use 2 or more types together. Among them, the component (O1) is preferably a diol containing a methacryl group or an acryl group, and more preferably glycerol mono(meth)acrylate or pentaerythritol di(meth)acrylate.

･･Other polyols ((O2) ingredients) The (O2) component is a polyhydric alcohol other than the above (O1) component. The component (O2) is not particularly limited, and may be an aliphatic polyol or an aromatic polyol. The (O2) component may be a low-molecular polyol (for example, less than a molecular weight of 500), or a high-molecular polyol (for example, a molecular weight of 500 or more).

Examples of the low-molecular-weight polyol include those listed in the description of the (O) component in the above-mentioned adhesive composition (a). The low-molecular-weight polyol is preferably a diol (diol). When low-molecular polyol is used as component (O2), the ratio of low-molecular polyol relative to component (O1) (low-molecular polyol/(O1) component (mass ratio)) is preferably 0.01 to 0.1, more preferably 0.03~0.08.

Examples of the polymer polyol include those listed in the description of the (O) component in the above-mentioned adhesive composition (a) (but excluding those corresponding to the (O1) component). The polymer polyol is preferably a polycarbonate polyol and a vegetable oil-based polyol. The polycarbonate polyol is preferably an aliphatic polycarbonate polyol, and more preferably an aliphatic polycarbonate diol. The vegetable oil-based polyol is preferably castor oil-modified polyol, more preferably castor oil-modified diol. When polycarbonate polyol is used as component (O2), the ratio of polycarbonate polyol relative to component (O1) (polycarbonate polyol/component (O1) (mass ratio)) is preferably 0.1 to 5. It is more preferably 0.3~3, and still more preferably 0.4~3. When vegetable oil polyol is used as component (O2), the ratio of vegetable oil polyol relative to component (O1) (vegetable oil polyol/(O1) component (mass ratio)) is preferably 0.1 to 5, more preferably 0.3~3, more preferably 0.4~2.5.

(O2) A component may be used individually by 1 type, and may use 2 or more types together. Among the above, the component (O2) is preferably a polycarbonate polyol and a low-molecular polyol from the viewpoint 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, castor oil-modified polyol can be used as the component (O2).

The component (O) is preferably a combination of the component (O1) and the component (O2) from the viewpoint of adjusting the viscosity of the adhesive composition (b) and the heat resistance of the adhesive layer. The aforementioned (O2) component is preferably a low-molecular-weight polyol, a polycarbonate polyol, or a castor oil-modified polyol, or a combination thereof. Specific examples of component (O2) combined with component (O1) include a combination of polycarbonate polyol, castor oil modified polyol, and low-molecular polyol; polycarbonate polyol, and castor oil modified polyol Combinations of alcohols; and polycarbonate polyols, etc. The mass ratio of (O1) component to (O2) component is preferably (O1):(O2) = 1:5~5:1, more preferably 1:4~2:1, and even more preferably 1:4 ~1:1, especially 1:4~1:2. By setting the mass ratio of the (O1) component to the (O2) component within the aforementioned range, the elastic modulus and heat resistance of the adhesive layer can be improved.

The component (P1) can be synthesized by mixing the component (I) and the component (O) and copolymerizing it in accordance with a known synthesis method of urethane resin. The copolymerization of the component (I) and the component (O) is preferably carried out in the presence of a known urethane catalyst such as a bismuth catalyst. In addition, in order to avoid polymerization of polymerizable carbon-carbon unsaturated bonds in component (O1), a polymerization inhibitor may be added to the reaction system.

(P1) The ratio (mass ratio) of (I) component and (O) component for the synthesis of component is preferably, for example (I):(O)=10:90~60:40, more preferably 20:80 ~50:50, and more preferably 25:75~45:55. (I) The molar ratio (NCO/OH) of the isocyanate group (-NCO) in the component to the hydroxyl group (-OH) in the (O) component (NCO/OH), preferably 60:40~40:60, more preferably 55: 45:~45:55.

(P1) A component may be used individually by 1 type, and may use 2 or more types together. When the content of the component (P1) in the adhesive composition (b) is a concentration that can be applied to a support or the like, it is not particularly limited. The content of the component (P1) in the adhesive composition (b) is relative to the total mass (100% by mass) of the adhesive composition (b), preferably 10-60% by mass, more preferably 20-60% by mass %, more preferably 30-60% by mass.

<Polymerization initiator: (A) component> The adhesive composition (b) contains a polymerization initiator (hereinafter also referred to as (A) component). The polymerization initiator has the function of accelerating the polymerization reaction. (A) The component includes a thermal polymerization initiator, a photopolymerization initiator, and the like.

Examples of thermal polymerization initiators include peroxides and azo polymerization initiators.

The peroxide in the thermal polymerization initiator includes, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, and the like. Such peroxides, specifically, include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl cumene peroxide, propylene peroxide, and benzyl peroxide. BPO, 2-chlorobenzyl peroxide, 3-chlorobenzyl peroxide, 4-chlorobenzyl peroxide, 2,4-dichlorobenzyl peroxide, 4-bromomethyl peroxide Benzyl benzoate, laurel peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, peroxy Tert-butyl triphenylacetate, tert-butyl hydroperoxide, tert-butyl peroxyformate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, per Tert-butyl 4-methoxyacetate, tert-butyl per N-(3-tolyl)carbamate, etc.

For the aforementioned peroxides, for example, the product name "Percumyl (registered trademark)", product name "Perbutyl (registered trademark)", product name "Peroyl (registered trademark)" and product name "Perocta ( Registered trademark)" and other commercial products.

The azo polymerization initiator in the thermal polymerization initiator includes, for example, 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1' -Azo(methylethyl)diacetate, 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane) nitrate , 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methyl propionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis Dimethyl isobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sulfonate sodium), 2-(4-methylphenylazo)-2-methylmalononitrile 4,4'-Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis-2-methyl Valeronitrile, 4,4'-azobis-4-cyanovaleric acid dimethyl ester, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobicyclo Capronitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanonitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1' -Azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'- Azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazobisphenylmethane, phenyl Azotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4,4'- Azobis-4-cyanovalerate), poly(tetraethylene glycol-2,2'-azobisisobutyrate), etc.

The photopolymerization initiator includes, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1-[4-(2-hydroxyethoxy) Phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-( 4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4 -Dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole -3-yl)-1-(o-acetyloxime), 2,4,6-trimethylbenzyldiphenylphosphine oxide, 4-benzyl-4'-methyldimethyl Disulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate , 4-Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl Acetal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzylbenzoic acid methyl, 2,4-diethylthioxanthene Ketone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylsulfide Xanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone Quinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorobenzene Yl)-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, 4,4'-bisdimethylaminodimer Benzophenone (i.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzophenone Ketones, 3,3-Dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzidine, benzine methyl ether, benzine ethyl ether, benzine isopropyl ether, benzene Phenyl-n-butyl ether, benzyl isobutyl ether, benzyl-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p -Dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, pt- Butyl dichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzo ring Heptanone, pentyl-4-dimethylaminobenzoate, 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) Yl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-di Ethylamino-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-triazine Chloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)benzene Vinylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, etc.

As the aforementioned photopolymerization initiator, for example, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", Commercial products such as "IRGACURE 907" (all product names, manufactured by BASF) and "NCI-831" (product names, manufactured by ADEKA Co., Ltd.).

(A) A component may be used individually by 1 type, and may be used in combination of 2 or more types. (A) The component is preferably a thermal polymerization initiator, and more preferably a peroxide. The usage amount of component (A) can be adjusted according to the usage amount of component (P1). The content of the polymerization initiator in the adhesive composition (b) is relative to 100 parts by mass of the component (P1), preferably 0.1-10 parts by mass, more preferably 0.5-5 parts by mass.

＜Optional ingredients＞ In addition to the above-mentioned components, the adhesive composition (a) and the adhesive composition (b) may contain optional components within a range that does not impair the effects of the present invention. The optional components are not particularly limited, and examples thereof include polymerization inhibitors, solvent components, plasticizers, adhesive additives, stabilizers, colorants, surfactants, and the like.

≪Polymerization inhibitor≫ The polymerization inhibitor refers to a component that has the function of preventing free radical polymerization caused by heat or light. The polymerization inhibitor system shows high reactivity to free radicals.

The polymerization inhibitor is preferably one having a phenol skeleton. For example, this polymerization inhibitor can use hindered phenol antioxidants, including pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone , Pentylquinone, pentyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylene)bis(2-methylphenol) ), 4,4'-(1-methylethylene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)- 1-methylethyl)phenyl]ethylene]bisphenol, 4,4',4"-ethylene tris (2-methylphenol), 4,4',4"-ethylene triphenol , 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2 '-Methylene bis(4-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 4,4'-sulfur Substituted bis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propanol Oxy)-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-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetra[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (trade name IRGANOX1010, manufactured by BASF Corporation), tris(3,5-di-tert-butylhydroxybenzyl) Isocyanurate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the like.

A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the polymerization inhibitor can be appropriately determined according to the type of resin component, the purpose of the adhesive composition and the use environment.

≪Surface active agent≫ Surfactants include, for example, fluorine-based surfactants and silicone-based surfactants.

Examples of fluorine-based surfactants include BM-1000, BM-1100 (all manufactured by BM Chmie), MegafacF142D, MegafacF172, MegafacF173, MegafacF183 (all manufactured by DIC), FluoradFC-135, FluoradFC-170C, FluoradFC- 430, FluoradFC-431 (all manufactured by Sumitomo 3M), SurflonS-112, SurflonS-113, SurflonS-131, SurflonS-141, SurflonS-145 (all manufactured by Asahi Glass), SH-28PA, SH-190, SH -193, SZ-6032, SF-8428 (all manufactured by Toray Silicone) and other commercially available fluorine-based surfactants.

Polysiloxane-based surfactants include, for example, unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, and alkyl-modified surfactants. Silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants, etc. A commercially available product can be used for the silicone-based surfactant. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Toray Dow Corning Corporation), Topika K1000, Topika K2000, Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), and XL-121 (polyether modified). Polysiloxane-based surfactant, manufactured by Clariant Corporation), BYK-310 (polyester-modified silicone-based surfactant, manufactured by BYK-Chemie), etc.

A surfactant may be used individually by 1 type, and may be used in combination of 2 or more types. The surfactant is preferably a silicone-based surfactant, more preferably a polyester-modified silicone-based surfactant. When the adhesive composition (a) contains a surfactant, the content of the surfactant is relative to the total mass (100 parts by mass) of the components (I) and (O), preferably 0.01 to 1 part by mass, more preferably It is 0.5 to 0.5 parts by mass. When the adhesive composition (b) contains a surfactant, the content of the surfactant is relative to 100 parts by mass of the component (P1), preferably 0.01 to 1 part by mass, more preferably 0.5 to 0.5 part by mass.

≪Solvent composition≫ Examples of the solvent component include hydrocarbon solvents, petroleum-based solvents, and other solvents other than the aforementioned solvents. Hereinafter, a combination of hydrocarbon solvents and petroleum-based solvents is referred to as "(S1) component". Solvent components other than (S1) components are called "(S2) components".

Examples of the hydrocarbon solvent include linear, branched, or cyclic hydrocarbons. Examples of hydrocarbon solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, and tridecane; isooctane, isonon Branched chain hydrocarbons such as alkanes and isododecane; p-menthane, o-menthane, m-menthane, diphenyl menthane, 1,4-terpene diol, 1,8-terpene diol , Campane, norbornane, pinane, thujane, carane, longleafene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, cyclooctane and other alicyclic hydrocarbons; toluene, xylene, indene, pentalene , Indane, tetrahydroindene, naphthalene, tetralin, decaline and other aromatic hydrocarbons.

Petroleum-based solvents refer to solvents purified from heavy oil, and examples thereof include white kerosene, paraffinic solvents, and isoparaffinic solvents.

(S2) As a component, the terpene solvent which has an oxygen atom, a carbonyl group, an acetoxy group, etc. which are a polar group can be mentioned. For example, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, Terpinen-1-ol, terpinen-4-ol, dihydrorosinol acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, Ionone, thujone, camphor, etc.

In addition, as the component (S2), lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentanone, and methyl isoamyl ketone can be cited , 2-heptanone and other ketones; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and other polyhydric alcohols; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetic acid Ester, or compounds with ester linkages such as dipropylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monoalkyl ethers such as the above polyols or the above compounds with ester linkage Derivatives of polyols such as phenyl ethers and other compounds having ether bonds (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); dioxane Cyclic ethers; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate Esters such as anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether and other aromatic organic solvents.

A solvent component may be used individually by 1 type, and may be used in combination of 2 or more types. The solvent component is preferably one that is inactive to the above-mentioned (B) component, (I) component, and (O) component, or the above-mentioned (B) component and (P1) component. Preferable solvent components include, for example, ester-based solvents, ketone-based solvents, aromatic hydrocarbon-based solvents, PGMEA, PGME, and mixed solvents thereof.

The adhesive composition (a) can be prepared by adding appropriate optional components to the above-mentioned (B) component, (I) component, and (O) component, and mixing them.

Adhesive composition (b) can be prepared by dissolving (B) component, (P1) component, and (A) component, and if necessary, optional components in a solvent component, and mixing them. The content of the solvent component in the adhesive composition (b) can be appropriately adjusted according to the thickness of the adhesive composition layer. The content of the solvent component, for example, is preferably in the range of 40 to 90% by mass relative to the total mass (100% by mass) of the adhesive composition. That is, the solid content of the adhesive composition of the present embodiment (the total amount of the formulated components after excluding the solvent component) concentration is preferably in the range of 10 to 80% by mass. When the content of the solvent component is within the aforementioned preferable range, viscosity adjustment becomes easy.

When a polymerization initiator is used, the polymerization initiator can be blended by a conventional method before using the adhesive composition. The polymerization initiator or polymerization inhibitor may be blended in the form of being dissolved in the solution of the above-mentioned (S2) component in advance. The amount of (S2) component used can be appropriately adjusted according to the type of polymerization initiator or polymerization inhibitor. For example, relative to 100 parts by mass of (S1) component, preferably 1-50 parts by mass, more preferably 5 ~30 parts by mass. (S2) When the usage amount of the component is within the aforementioned preferable range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.

According to the adhesive composition of the present embodiment, in order to temporarily bond the semiconductor substrate or the like to the support, the adhesive composition layer may be formed between the semiconductor substrate or the like and the support to be cured. This forms an adhesive layer that temporarily bonds the semiconductor substrate and the like to the support. The adhesive layer is hardened by the cross-linking structure, so it has high heat resistance, and the elastic modulus will not decrease even at high temperatures (for example, above 200°C). Therefore, during the processing of semiconductor substrates or electronic devices, there will be no defects such as positional deviation or sinking during high-temperature processing. In addition, when the aforementioned 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 deteriorated. Thereby, the adhesive force of the adhesive layer is reduced, and the semiconductor substrate and the like can be separated from the support. Therefore, no separation layer is required. In addition, since the aforementioned adhesive layer contains a urethane resin, the urethane bond can be decomposed by acid or alkali to decompose the adhesive layer. Therefore, even if the residue of the adhesive layer adheres to the semiconductor substrate or the like separated from the support, it can be cleaned by acid or alkali, and the residue of the adhesive layer can be easily removed.

(Layered body) The laminated body of the second aspect of the present invention is characterized by a laminated body laminated in the order of a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device, and the adhesive layer is the adhesive composition of the first aspect The hardened body.

Fig. 1 shows an embodiment of the laminate of the second aspect. The laminated body 100 shown in FIG. 1 includes a support 1 through which light passes, an adhesive layer 3 and a semiconductor substrate 4. In the laminated body 100, the supporting body 1, the adhesive layer 3, and the semiconductor substrate 4 are laminated in the order.

Fig. 2 shows another embodiment of the laminate of the second aspect. The laminated body 200 shown in FIG. 2 has an electronic device 456 composed of a semiconductor substrate 4, an encapsulating material layer 5, and a wiring layer 6 laminated on the adhesive layer 3 and has the same structure as the laminated body 100.

Fig. 3 shows another embodiment of the laminate of the second aspect. The laminate 300 shown in FIG. 3 has the same structure as the laminate 100 except that the electronic device is composed of the wiring layer 6.

Fig. 4 shows another embodiment of the laminate of the second aspect. The laminated body 400 shown in FIG. 4 has an electronic device 645 composed of the wiring layer 6, the semiconductor substrate 4, and the encapsulating material layer 5 laminated on the adhesive layer 3, and has the same structure as the laminated body 100.

＜Support body＞ The support system supports the semiconductor substrate or the components of the electronic device. The support has the characteristic of light transmission. The support system is attached to the semiconductor substrate or electronic device through the adhesive layer. Therefore, as a support, it is better to have the necessary strength in order to prevent damage or deformation of the semiconductor substrate when the device is thinned, the semiconductor substrate is transported, and the semiconductor substrate is mounted. As the material of the support, for example, glass, silicon, acrylic resin, etc. can be used. The shape of the support includes, for example, a rectangle, a circle, etc., but it is not limited to these. As the support body, in order to achieve higher density integration or increase production efficiency, a large-scale panel with a rectangular shape when viewed from the top can be used by increasing the size of the circular support body.

＜Adhesive layer＞ The subsequent layer is provided for temporarily attaching the semiconductor substrate or the electronic device to the support. The adhesive layer is a cured body of the adhesive composition of the first embodiment described above. The curing of the adhesive composition of the first embodiment can be performed by heating the adhesive composition. The thickness of the subsequent layer is, for example, preferably in the range of 1 μm or more and 200 μm or less, and more preferably in the range of 5 μm or more and 150 μm or less.

The adhesive layer is a cured body of the adhesive composition as described above, but the material (cured body) constituting the adhesive layer preferably satisfies the following characteristics. That is, when the complex modulus of elasticity of the hardened body is measured under the following conditions, the complex modulus of elasticity at 200°C is preferably 1.0×10 ⁴ Pa or more, more preferably 5.0×10 ⁴ Pa or more, and still more preferably 1.0×10 ⁵ Pa or more. In addition, the complex modulus of elasticity at 200°C is more preferably 1.0×10 ⁶ Pa or more, still more preferably 5.0×10 ⁶ Pa or more, and particularly ^{preferably 1.0×10 7} Pa or more. The upper limit of the complex modulus of elasticity at 200°C is, for example, 1.0×10 ¹⁰ Pa or less. In addition, when the complex modulus of elasticity of the hardened body is measured under the following conditions, the complex modulus of elasticity at 250°C is preferably 5.0×10 ⁶ Pa or more, and more preferably 1.0×10 ⁷ Pa or more. The upper limit of the complex modulus of elasticity at 250°C is, for example, 1.0×10 ¹⁰ Pa or less.

The complex elastic modulus of the hardened body can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition was coated on a PET film with a release agent, heated at 180°C for 1 hour in an oven in a nitrogen environment, to form a test piece with a thickness of 50 μm, and then peeled off from the PET film. The latter test piece (size 5 mm×40 mm, thickness 50 μm) can be measured using the above-mentioned measuring device. The measurement condition adopts the stretching condition with a frequency of 1 Hz, and the temperature rises from the starting temperature of 50°C to 300°C and the temperature rise rate is 5°C/min.

＜Semiconductor substrate or electronic device＞ The semiconductor substrate or the electronic device is temporarily attached to the support via the adhesive layer.

≪Semiconductor substrate≫ The semiconductor substrate is not particularly limited, and, for example, the same as those exemplified in the above-mentioned "(adhesive composition)". The semiconductor substrate may be a semiconductor element or another element, and may have a single-layer or multiple-layer structure.

≪Electronic device≫ The electronic device is not particularly limited, and for example, the same as those exemplified in the above-mentioned "(adhesive composition)". The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the aforementioned member. Specifically, the electronic device includes at least one of an encapsulating material layer and a wiring layer, and may further include a semiconductor substrate. In the laminated body 200 shown in FIG. 2, the electronic device 456 is composed of a semiconductor substrate 4, an encapsulating material layer 5, and a wiring layer 6. In the laminated body 300 shown in FIG. 3, the electronic device 6 is constituted by the wiring layer 6. In the laminated body 400 shown in FIG. 4, the electronic device 645 is composed of the wiring layer 6, the semiconductor substrate 4 and the packaging material layer 5.

[Packaging material layer] The packaging material layer is provided for packaging the semiconductor substrate, and is formed by using the packaging material. As the packaging material, a member that can insulate or encapsulate a member made of metal or semiconductor is used. As the packaging material, for example, a resin composition can be used. The packaging material layer 5 is not provided on each semiconductor substrate 4, but it is better to set the semiconductor substrate 4 on the adhesive layer 3 to cover all of it. The resin used for the encapsulating material is not particularly limited as long as it can encapsulate and/or insulate metals or semiconductors, and examples thereof include epoxy resins and silicone resins. In addition to resin, the packaging material may also contain other ingredients such as fillers. Examples of the filler include spherical silica particles.

≪Wiring layer≫ The wiring layer is also called RDL (Redistribution Layer). The wiring body that constitutes the thin film of the wiring connected to the substrate can have a single-layer or multi-layer structure. The wiring layer can use conductors (for example, metals such as aluminum, copper, titanium, nickel, gold, silver, etc.) between _{dielectrics (silicon oxide (SiO x ), photosensitive resins such as photosensitive epoxy, etc.)} -Tin alloy and other alloys) forming wiring, but not limited to this.

In addition, in the laminated body of FIGS. 1 to 4, the support 1 and the adhesive layer 3 are adjacent, but it is not limited to this, and another layer may be further formed between the support 1 and the adhesive layer 3. In this case, the other layers may be made of materials that transmit light. Thereby, without preventing light from being incident on the adhesive layer 3, it is possible to appropriately add a layer that imparts preferable properties to the layered body 100 to 400. Depending on the type of material constituting the adhesive layer 3, the wavelength of light that can be used is different. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can change the material constituting the adhesive layer 3.

(Manufacturing method of laminated body (1)) The manufacturing method of the laminated body of the third aspect of the present invention is a method of manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated, and is characterized by having the following steps: The step of coating the adhesive composition of the first aspect on a substrate to form an adhesive composition layer (hereinafter also referred to as "adhesive composition layer forming step"); through the adhesive composition layer, the semiconductor The step of placing the substrate on the support (hereinafter, also referred to as the "semiconductor substrate placing step"); and curing the adhesive composition layer by the polymerization reaction of the urethane resin to form the adhesive The step of layering (hereinafter, also referred to as "the next layer forming step").

Figs. 5 to 6 are schematic step diagrams for explaining one embodiment of the method of manufacturing the laminate of the present embodiment. 5A to 5B are diagrams illustrating the manufacturing steps of the 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 a step of forming an adhesive composition layer. FIG. 5B is a diagram illustrating the step of placing the semiconductor substrate. Fig. 6 is a diagram illustrating a step of forming a subsequent layer. The adhesive composition layer 3'in the laminated body 100' is thermally cured to form the adhesive layer 3, and the laminated body 100 is obtained.

[Adhesive composition layer forming step] The manufacturing method of the laminated body of this embodiment includes the step of forming an adhesive composition layer. The step of forming the adhesive composition layer is a step of applying the adhesive composition on the support or the semiconductor substrate to form the adhesive composition layer. In Fig. 5A, an adhesive composition is used to form an adhesive composition layer 3'on a support 1.

The method of forming the adhesive composition layer 3'on the support 12 is not particularly limited, and examples include methods such as spin coating, dipping, roll coating, spray coating, and slit coating. The same method can be used to form an adhesive composition layer on the semiconductor substrate 4.

After the adhesive composition layer is formed, a baking treatment can be performed. The baking temperature condition is a temperature lower than the heating temperature in the subsequent layer forming step described later. The baking conditions vary depending on the type of the hardening component contained in the adhesive composition, and examples thereof include 1 to 10 minutes at a temperature of 70 to 100°C.

[Semiconductor substrate placement step] The manufacturing method of the laminated body of this 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. In this way, a laminate 100' can be obtained. 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. As shown in FIG.

The method of mounting the semiconductor substrate 4 on the support 1 via the adhesive composition layer 3'is not particularly limited, and as a method of arranging the semiconductor substrate at a specific position, a commonly used method can be adopted.

[Next layer formation step] The manufacturing method of the laminated body of this embodiment includes the step of forming an adhesive layer. The subsequent layer forming step is a step of hardening the adhesive composition layer to form an adhesive layer. In this way, the layered body 100 can be obtained. 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 selecting an appropriate method according to the type of curing component.

When the hardening component is the above-mentioned (a) component, the hardening reaction can be carried out by heating. The heating temperature may be equal to or higher than the temperature at which the crosslinking reaction of the (I) component and (O) component starts. For example, when component (I) contains a blocked polyisocyanate, the heating temperature may be a temperature higher than the dissociation temperature of the thermally dissociable blocking agent that blocks isocyanate groups in the blocked polyisocyanate. The heating temperature can be changed depending on the type of the thermally dissociable end-capping agent, and examples thereof include 80°C or higher, 100°C or higher, 130°C or higher, or 150°C or higher. The upper limit of the heating temperature is not particularly limited, and from the viewpoint of energy consumption, for example, 350°C or lower, 300°C or lower, or 250°C or lower can be mentioned. Examples of the heating temperature range include 80 to 350°C, 100 to 300°C, 130 to 300°C, or 150 to 300°C. The heating time is not particularly limited as long as it is a time sufficient for thermal curing of the (I) component and (O) component. The heating time can be, for example, 15 minutes or more, 30 minutes or more, or 45 minutes or more. The upper limit of the heating time is not particularly limited, but from the viewpoint of work efficiency, for example, it may be 120 minutes or less, 100 minutes or less, 80 minutes or less, or 60 minutes or less. The range of the heating time includes, for example, 15 to 120 minutes, 30 to 120 minutes, or 45 to 120 minutes.

The hardening component is the above-mentioned (b) component, and when the (P1) component contains a methacryl group or an acryl group, the hardening reaction can be performed by heating. The heating temperature includes, for example, 80 to 350°C, 100 to 300°C, 130 to 300°C, or 150 to 300°C. The heating time is not particularly limited when it is sufficient time required for the polymerization and curing of the component (P1). 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 aforementioned hardening reaction can be carried out in a nitrogen environment, for example.

In this step, the (I) component and (O) component, or (P1) component in the adhesive composition layer 3'are cross-linked and hardened to form the adhesive layer 3 of the hardened body of the adhesive composition layer 3'. Thereby, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, a laminate 100 can be obtained.

In addition, when the curing component is the above-mentioned (b) component, and when the (B) component contains the (B1) component, the (P1) component and (B1) component in the adhesive composition layer 3'are cross-linked and cured to form an adhesive The adhesive layer 3 of the hardened body of the composition layer 3'. Thereby, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, a laminate 100 can be obtained.

[Any step] The manufacturing method of the laminated body of this embodiment may include other steps in addition to the above-mentioned steps. Other steps include, for example, various mechanical or chemical treatments (thin filming treatments such as polishing or chemical mechanical polishing (CMP), chemical vapor deposition (CVD) or physical vapor deposition (PVD), high temperature, vacuum treatment, etc.) Treatment with chemicals such as organic solvents, acidic treatment liquids or alkaline treatment liquids, electroplating treatments, active light irradiation, heating and cooling treatments, etc.).

(Manufacturing method of laminated body (2)) The fourth aspect of the method of manufacturing a laminate of the present invention is characterized in that after the laminate is obtained by the method of manufacturing the laminate of the third aspect, there is an electronic device forming step for forming an electronic device. The electronic device is A composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the aforementioned member.

The laminate system obtained by the method of manufacturing the laminate of this embodiment is a laminate in which the support, the adhesive layer, and the electronic device are laminated in the order. This laminated body can be obtained by performing an electronic device forming step with respect to the laminated body obtained by the manufacturing method of the laminated body of the said 3rd aspect.

[Electronic Device Formation Step] The manufacturing method of the laminated body of this embodiment includes the step of forming an electronic device. The electronic device forming step is a step of forming an electronic device that is a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the aforementioned member. The electronic device forming step may include any one of a packaging step, a grinding step, and a wiring layer forming step. In one embodiment, the electronic device forming step includes a substrate fixing step and a packaging step. At this time, the electronic device forming step may further include a grinding step and a wiring layer forming step.

･About the packaging procedure The packaging step is a step of packaging the substrate fixed on the support using a packaging material. In FIG. 7A, the entire semiconductor substrate 4 temporarily attached to the support 1 via the adhesive layer 3 and the laminated body 110 encapsulated by the encapsulating material layer 5 is obtained.

In the encapsulation step, for example, the encapsulation material heated to 130~170°C is supplied to the adhesive layer 3 while maintaining a high viscosity state while covering the semiconductor substrate 4, and is formed on the adhesive layer 3 by compression molding. There is a laminate 110 of the encapsulating material layer 5. At this time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N/cm ² .

The encapsulating material layer 5 is preferably provided in a manner to cover the entire semiconductor substrate 4 on the adhesive layer 3, rather than being provided on each semiconductor substrate 4.

･About the grinding step The grinding step is a step of grinding the packaging material part (the packaging material layer 5) in the package body by exposing a part of the semiconductor substrate after the aforementioned packaging step. For example, as shown in FIG. 7B, the grinding of the packaging material part is to cut the packaging material layer 5 to approximately the same thickness as the semiconductor substrate 4.

･About the wiring layer formation procedure 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 encapsulating material layer 5. As shown in FIG. Thereby, the laminated body 120 can be obtained. In the laminate 120, the semiconductor substrate 4, the encapsulating material layer 5, and the wiring layer 6 constitute an electronic device 456.

The method of forming the wiring layer 6 includes, for example, the following methods. First, a dielectric layer of silicon oxide (SiO _x ), photosensitive resin, or the like is formed on the sealing material layer 5. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like. The dielectric layer composed of photosensitive resin can be obtained by coating photosensitive resin on the sealing material layer 5 by, for example, spin coating, dipping, roll coating, spray coating, slit coating, etc. form.

Next, on the dielectric layer, wiring is formed with a conductor such as metal. As a method of forming wiring, for example, a known semiconductor manufacturing process method such as photolithography (resist lithography), etc., lithography processing, etching processing, and the like can be used. Such lithography processing includes, for example, lithography processing using a positive type resist material and lithography processing using a negative type resist material.

In the method of manufacturing the laminate of this embodiment, bumps or mounting components can be further formed on the wiring layer 6. The components are mounted on the wiring layer 6, for example, using a chip mounter or the like.

(Manufacturing method of laminate (3)) The manufacturing method of the laminate of the fifth aspect of the present invention is a method of manufacturing a laminate in which a support, an adhesive layer, and an electronic device are sequentially laminated, and is characterized by the following steps: coating the support on the support 1 aspect of the adhesive composition, the step of forming the layer of the aforementioned adhesive composition (adhesive composition layer forming step); the electronic device forming step of forming an electronic device on the aforementioned adhesive composition layer (the electronic device forming step ), the aforementioned electronic device is a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the aforementioned member; and, the step of hardening the aforementioned adhesive composition layer to form an adhesive layer (the step of forming an adhesive layer) .

The layered system obtained by the method of manufacturing the layered body of this embodiment is the same as the method of manufacturing of the aforementioned fourth aspect, in which a layered body of a support, an adhesive layer, and an electronic device is sequentially laminated.

In the manufacturing method of this embodiment, the step of forming the adhesive composition layer can be performed in the same manner as the manufacturing method of the laminate of the third aspect described above.

In the manufacturing method of this embodiment, after the adhesive composition layer forming step, the electronic device forming step is performed. This electronic device forming step may include a wiring layer forming step. The electronic device forming step may further include a semiconductor substrate mounting step, a packaging step, and a grinding step. In addition, the step of forming an electronic device may also be a step in which a package body encapsulated by a semiconductor substrate with a package material is placed on a support via an adhesive composition layer.

The subsequent layer forming step can be performed in the same manner as the subsequent layer forming step in the above-mentioned third aspect of the manufacturing method of the laminated body.

After the subsequent layer forming step, an electronic device forming step can be further performed if necessary. This electronic device forming step may include, for example, a semiconductor substrate mounting step, a packaging step, a grinding step, and the like.

According to the above-mentioned third to fifth aspect of the manufacturing method of the laminated body, the support body is temporarily bonded to the semiconductor substrate or the electronic device through the adhesive layer with high heat resistance. Therefore, the sequential laminated support body and the adhesive can be stably manufactured Layers, semiconductor substrates, or laminates of electronic devices. This laminate system is a laminate produced in a process based on a fan-out technology (terminals provided on a semiconductor substrate are mounted on a wiring layer that extends outside the wafer area).

(Method of manufacturing electronic parts) The manufacturing method of the electronic component of the sixth aspect of the present invention is characterized by having the following steps: after obtaining the laminated body by the method of manufacturing the laminated body of any one of the third to fifth aspects, passing the support body , The step of irradiating light on the adhesive layer to change the quality of the adhesive layer, separating the electronic device from the support (hereinafter also referred to as the "separation step") and bonding the urethane in the adhesive layer to acid Or the step of alkali decomposition and removal of the aforementioned adhesive layer (hereinafter also referred to as "adhesive layer removal step").

Fig. 8 is a schematic step diagram illustrating an embodiment of a method of manufacturing a semiconductor package (electronic component). FIG. 8A shows a view of the layered body 120, FIG. 8B is a diagram illustrating the separation step, and FIG. 8C is a diagram illustrating the adhesive removing step.

[Separation step] The separation step is a step of irradiating the adhesive layer 3 with light (arrow) through the support 1 to alter the quality of the adhesive layer 3 and separating the electronic device 456 and the support 1. As shown in FIG. 8A, in the separation step, the adhesive layer 3 is irradiated with light (arrow) through the support 1 through which the light passes, and the adhesive layer 3 is changed in quality.

The wavelength of the light used in the separation step may be selected according to the wavelength of the light absorbed by the component (B) contained in the adhesive layer 3. For example, light in the wavelength range of 300 to 800 nm can be used. The type of light to be irradiated can be appropriately selected according to the permeability of the support 1. For example, _{solid lasers such as YAG lasers, ruby lasers, glass lasers, YVO 4} lasers, LD lasers, and fiber lasers can be used. Lasers, pigment lasers and other liquid lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers, etc. laser. Thereby, the adhesive layer 3 is changed in quality, and the support 1 and the electronic device 456 can be easily separated from each other.

When irradiating laser light, one example of laser light irradiation conditions includes the following conditions. The average output value of the laser light 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 light is preferably above 20 kHz and below 60 kHz, more preferably above 30 kHz and below 50 kHz. The scanning speed of the laser light is preferably above 100 mm/s and below 10000 mm/s.

After the adhesive layer 3 is irradiated with light (arrow) to change the quality of the adhesive layer 3, the support 1 is separated from the electronic device 456 as shown in FIG. 8B. For example, by applying force in a direction in which the support 1 and the electronic device 456 are separated from each other, the support 1 and the electronic device 456 are separated. Specifically, in a state where one of the support 1 or the side of the electronic device 456 (wiring layer 6) is fixed to the stage, the other is held up while being sucked by a separation plate equipped with an adsorption pad such as a bellows pad, Thereby, the supporting base 1 and the electronic device 456 can be separated. The force applied to the laminated body 200 can be appropriately adjusted according to the size of the laminated body 200, etc., and is not particularly limited. For example, for a laminated body with a diameter of about 300 mm, a force of about 0.1 to 5 kgf (0.98 to 49 N) can be applied. The supporting body 1 can be appropriately separated from the electronic device 456.

[Next go to step] The manufacturing method of the electronic component of this embodiment has an adhesive layer removal step. The subsequent layer removal step is a step in which the urethane bond in the adhesive layer is decomposed by acid or alkali to remove the aforementioned adhesive layer. In FIG. 8B, after the separation step, the layer 3 is then attached to the electronic device 456. In this step, the adhesive layer 3 is separated by using an acid or 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 acid or alkali. The subsequent layer 3 contains a urethane resin formed by the copolymerization of the above-mentioned component (I) and (O), or a cross-linked urethane formed by the polymerization of the above-mentioned component (P1) Resin. For these urethane resins, the urethane bond is cut and decomposed by acid or alkali treatment. Thereby, the adhesive layer 3 is decomposed, and the residue attached to the adhesive layer 3 of the electronic device 456 can be removed.

The acid or base used in this step is not particularly limited as long as it can decompose the urethane bond. The acid that can decompose the urethane bond includes, for example, hydrochloric acid, sulfuric acid, nitric acid, etc., but is not limited to these. In addition, examples of bases capable of decomposing urethane bonds include inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine, but are not limited to these.

The aforementioned acid or alkali is dissolved in a solvent and can be used as a treatment liquid for adhesive layer removal. The aforementioned solvent is preferably a polar solvent, and examples thereof include dimethylsulfene (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, and propylene glycol. The aforementioned treatment liquid for adhesive removal may contain well-known additives such as surfactants in addition to the above-mentioned components. The content of the acid or alkali in the treatment liquid is not particularly limited, and it can be, for example, 1 to 50% by mass. In addition, the content of the polar solvent in the treatment liquid may be 50 to 99% by mass. The treatment liquid for subsequent layer removal can be a commercially available alkaline treatment liquid or acidic treatment liquid. Examples of commercially available treatment liquids include ST-120 and ST-121 (all manufactured by Tokyo Ohka Kogyo Co., Ltd.). The adhesive layer 3 is decomposed by the treatment liquid containing acid or alkali as described above, and the urethane bond in the adhesive layer 3 is decomposed, and the adhesive layer 3 can be removed.

In the method of manufacturing an electronic component of this embodiment, after the above-mentioned adhesive layer removal step, the electronic component 50 can be further processed to form a solder ball, cut, or form an oxide film.

According to the method of manufacturing electronic parts of this embodiment, urethane containing (a) light absorber, polyisocyanate, and polyol, or (b) light absorber, containing polymerizable carbon-carbon unsaturated bonds is used The adhesive composition of the ester resin and the polymerization initiator hardens the aforementioned adhesive composition to temporarily bond the semiconductor substrate and the like to the support. Therefore, it is possible to form an adhesive layer with high heat resistance that can withstand high-temperature processing in the steps of forming electronic devices and the like. In addition, the aforementioned adhesive composition contains a light absorber, and therefore, the adhesive layer is deteriorated by light irradiation, and the adhesive force is reduced. Therefore, even if there is no separation layer, it is possible to easily separate the temporarily bonded semiconductor substrate or the like from the support. In addition, the residue of the adhesive layer attached to the semiconductor substrate and the like separated from the support can be easily removed by decomposing the urethane bond in the adhesive layer by acid or alkali. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to these examples.

<Synthesis example of urethane resin ((P1) component)> Add propylene glycol monomethyl ether acetate (PGMEA), 36 parts of castor oil modified glycol, 17 parts of polycarbonate diol (Mw1,000), and pentaerythritol in a flask equipped with a stirrer, dropping funnel, condenser and thermometer. 18 parts of diacrylate, 1 part of neopentyl glycol and inhibitor are mixed uniformly under nitrogen flow. Next, 7 parts of diphenylmethane diisocyanate (MDI) and 21 parts of hydrogenated xylylene diisocyanate (H6XDI) were put into the dropping funnel and dropped at a constant speed over 30 minutes. After the dripping is over, mature for 30 minutes. Then, the bismuth catalyst is added, the temperature is raised to 65°C, and the maturation is 4 to 5 hours. Next, 2HEA (2-hydroxyethyl acrylate) was added and aged for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared. The weight average molecular weight (Mw) of the obtained urethane resin (P1)-1 was 20,000. The C=C equivalent of the urethane resin (P1)-1 (the molecular weight of the polymerizable carbon-carbon double bond per equivalent of the urethane resin) is 600g/eq.

The polycarbonate diol (Mw1,000) used in the synthesis of the above-mentioned urethane resin (P1)-1 is the polycarbonate diol represented by the following formula (PC-1-1) (R=-( CH ₂ ) ₆ -, -(CH ₂ ) ₅ -).

＜Preparation of adhesive composition (1)＞ (Examples 1 to 6, Comparative Example 1) The components shown in Table 1 were mixed to prepare the adhesive composition of each example. More specifically, it is modulated as follows. First, (P1) component, (A) component, (Ad) component, and (S) component were mixed by the compounding quantity described in Table 1. Next, the component (B) was added in the ratio described in Table 1, and the whole composition was uniformly mixed.

In Table 1, each abbreviation has the following meanings. The value in [] is the blending amount (parts by mass). In addition, the value of wt% in () is the ratio (mass%) of the pigment solid content relative to the total mass (100% by mass) of the adhesive composition. (P1)-1: The urethane resin (P1)-1 synthesized in the above synthesis example. (A)-1: peroxide (Percumyl (registered trademark) D, Nippon Oil & Fat Co., Ltd.). (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 dispersed volume average particle size 150 nm or less). (B)-2: Perylene-based black pigment (volume average particle diameter 150 nm).

＜Evaluation＞ ≪Measurement of light transmittance≫ The adhesive composition of each example was respectively coated on a bare glass support body by a spin coater method. It was cured by heating at 180°C for 1 hour in an oven in a nitrogen environment, and the adhesive layers each having the film thickness described in Table 2 were formed. For the aforementioned adhesive layer, using a spectroscopic analyzer UV-3600 (manufactured by Shimadzu Corporation), the transmittance of light with a wavelength of 532 nm was evaluated by irradiating light with a wavelength of 380 to 780 nm. The results are shown in Table 2.

From the results shown in Table 2, the light transmittance of the adhesive layer formed using the adhesive composition of Examples 1 to 6 was significantly reduced, and it was confirmed that light having a wavelength of 532 nm was absorbed.

≪Evaluation of Detergency≫ The adhesive composition of Example 6 was coated on a glass support (a size of 30 cm in diameter, and a thickness of 700 μm) by a spin coater method. It was cured by heating at 180°C for 1 hour in an oven in a nitrogen environment to form an adhesive layer (film thickness 18μm). After the bonding layer is formed, the support body is at 50 ℃, and the treatment liquid (tetramethyl ammonium hydroxide (TMAH) is compared with N-methylpyrrolidone (NMP), dimethyl sulfide (DMSO), propylene glycol (PG) The mixed solvent (NMP:DMS:PG =10:78:12 (mass ratio)), diluted with a concentration of 2% by mass), was used to determine the time to complete dissolution. From the dissolution time for the film thickness, calculate the dissolution rate of the adhesive layer. When the dissolution rate is 50 nm/sec or more, it is judged that the cleaning performance is good. The dissolution rate of the aforementioned adhesive layer is 70 nm/sec. Therefore, it was confirmed that the adhesive layer formed using the adhesive composition of Example 6 has good cleaning properties.

＜Preparation of adhesive composition (2)＞ (Examples 7-9, Comparative Example 2) The components shown in Table 3 were mixed to prepare the adhesive composition of each example.

In Table 3, each abbreviation has the following meanings. The value in [] is the blending amount (parts by mass). (P1)-1: Urethane resin (P1)-1 synthesized in the above synthesis example. (A)-1: peroxide (Percumyl (registered trademark) D, Nippon Oil & 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).

＜Evaluation＞ ≪Measurement of light transmittance≫ The adhesive composition of each example was respectively coated on the bare glass support body by the spin coater method. It was cured by heating at 180°C for 1 hour in an oven in a nitrogen environment, and the adhesive layers each having the film thickness described in Table 2 were formed. For the aforementioned adhesive layer, using a spectroscopic analyzer UV-3600 (manufactured by Shimadzu Corporation), by irradiating light with a wavelength of 300 to 800 nm, the transmittance of light at a wavelength of 355 nm was evaluated. The results are shown in Table 4 below.

From the results shown in Table 4, the adhesive layer formed using the adhesive compositions of Examples 7 to 9 has a low light transmittance measured at a wavelength, and it is confirmed that it absorbs light in this wavelength range.

≪Evaluation of laser reactivity≫ The adhesive layer was formed from the adhesive composition of Example 9 and Comparative Example 2 under the same conditions as the aforementioned "Measurement of Light Transmittance". For this adhesive layer, Talon (registered trademark) 355-12 manufactured by Spectra Physics was irradiated with 355 nm laser light. Observe the adhesive layer to confirm the marks. The results are shown in Table 5 together with the transmittance at 355 nm.

From the results shown in Table 5, it was confirmed that the adhesive layer formed using the adhesive composition of Example 9 has a laser reactivity of 355 nm. In addition, the adhesive layer formed using the adhesive composition of Comparative Example 2 could not confirm the laser reactivity.

1: Support 3: Next layer 3’: Adhesive composition layer 4: Semiconductor substrate 5: Packaging material layer 6: Wiring layer 20: Laminated body 50: Electronic parts 100: layered body 100’: Layered body 110: layered body 120: layered body 200: layered body 300: layered body 400: Laminated body 456: electronic device 645: electronic device

[Fig. 1] A schematic diagram showing an embodiment of a laminate using the present invention. [Fig. 2] A schematic diagram showing an embodiment of a laminate using the present invention. [Fig. 3] A schematic diagram showing an embodiment of a laminate using the present invention. [Fig. 4] A schematic diagram showing an embodiment of a laminate using the present invention. [Fig. 5A] Figs. 5A to 5B are schematic step diagrams illustrating an embodiment of a method of manufacturing a laminate 100' laminated in the order of a support, an adhesive composition layer, and a semiconductor substrate. Fig. 5A is a diagram illustrating a step of forming an adhesive composition layer. [Fig. 5B] Fig. 5B is a diagram illustrating a semiconductor substrate mounting step. [Fig. 6] A diagram explaining the subsequent layer formation step. [Fig. 7A] Figs. 7A to 7C are schematic step diagrams illustrating an embodiment of a method of manufacturing the laminate 120. Fig. 7A is a diagram illustrating the packaging step. [Fig. 7B] Fig. 7B is a diagram illustrating a grinding step. [Fig. 7C] Fig. 7C is a diagram illustrating a step of forming a wiring layer. [FIG. 8A] FIGS. 8A to 8C are schematic step diagrams illustrating an embodiment of a method of manufacturing a semiconductor package (electronic component) from the laminate 120. [FIG. FIG. 8A shows a view of the laminate 200. [Fig. 8B] Fig. 8B is a diagram illustrating the separation step. [Fig. 8C] Fig. 8C is a diagram illustrating a subsequent layer removal step.

Claims (10)

An adhesive composition, which is used to form an adhesive composition for temporarily adhering a semiconductor substrate or an electronic device and a light-transmitting support, which contains (a) Light absorbers, polyisocyanates, and polyols, or (b) A light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. Such as the adhesive composition of claim 1, wherein the aforementioned adhesive composition contains the aforementioned component (b), The aforementioned light absorber absorbs at least a part of light within a wavelength range of 300 to 800 nm, and contains a polymerizable carbon-carbon unsaturated bond-containing compound (B1) (but excluding those equivalent to the aforementioned urethane resin). Such as the adhesive composition of claim 2, wherein the aforementioned compound (B1) is represented by the following general formula (b1),

[In the formula, W is a monovalent group containing a polymerizable carbon-carbon unsaturated bond; Y is a single bond, or 2 selected from the group consisting of -O-, -CO-, -COO-, and -CONH- Valence linking group; n is an integer from 1 to 6; X is a condensed ring skeleton with aromaticity in its structure, benzophenone skeleton, benzophenone methane skeleton, benzophenone benzene skeleton, Or the n-valent atomic group of the benzotriazole skeleton. When n is 2 or more, W and Y, which exist in plural, may be the same or different from each other]. Such as the adhesive composition of claim 1, wherein the aforementioned adhesive composition contains the aforementioned component (b), The aforementioned urethane resin is a reaction product of polyol and polyisocyanate, At least one of the polyol and the polyisocyanate includes the polymerizable carbon-carbon unsaturated bond. Such as the adhesive composition of claim 1, wherein the aforementioned adhesive composition contains the aforementioned component (b), A thermal polymerization initiator is included as the aforementioned polymerization initiator. The adhesive composition of claim 1, wherein a composite of a member composed of a metal or a semiconductor as the electronic device and a resin encapsulating or insulating the member is laminated on the support through the adhesive layer. A laminated body is a laminated body in which a light-transmitting support body, an adhesive layer, and a semiconductor substrate or an electronic device are sequentially laminated, The aforementioned adhesive layer is a hardened body of the adhesive composition according to any one of claims 1 to 6. A method of manufacturing a laminated body, which is a method of manufacturing a laminated body in which a light-transmitting support body, an adhesive layer, and a semiconductor substrate are sequentially laminated, which has the following steps: The step of applying the adhesive composition according to any one of claims 1 to 6 to the aforementioned support or semiconductor substrate to form an adhesive composition layer, The step of placing the semiconductor substrate on the support via the adhesive composition layer, The step of hardening the adhesive composition layer to form the adhesive layer. A method of manufacturing a laminated body, which is a method of manufacturing a laminated body having a light-transmitting support, an adhesive layer, and an electronic device sequentially laminated, wherein the laminated body is obtained by the method of manufacturing a laminated body as in claim 8, There is further a step of forming an electronic device. The electronic device is a composite of a member made of metal or semiconductor and a resin that encapsulates or insulates the member. A method of manufacturing an electronic component, which is obtained by the method of manufacturing a layered body as in claim 8, and further has the following steps: The step of irradiating light on the adhesive layer through the support body to change the quality of the adhesive layer and separate the electronic device and the support body into the step, The step of removing the adhesive layer attached to the electronic device by decomposing the urethane bond in the adhesive layer with acid or alkali.

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