JP6802348B1 - Adhesive composition, laminate, method for manufacturing laminate, and method for manufacturing electronic components - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition which does not require a separation layer, has high heat resistance, and can easily remove an adhesive layer, a laminate produced by using the adhesive composition, a method for producing the laminate, and an adhesive composition. Provided is a method for manufacturing an electronic part using an object. SOLUTION: In a laminated body 100, an adhesive composition used for forming an adhesive layer 3 for temporarily adhering a semiconductor substrate 4 or an electronic device and a support 1 transmitting light is a light absorber, poly. It contains isocyanates and polyols or light absorbers, urethane resins containing polymerizable carbon-carbon double bonds and polymerization initiators. [Selection diagram] Fig. 1

Description

The present invention relates to an adhesive composition, a laminate, a method for producing a laminate, and a method for producing an electronic component.

The semiconductor package (electronic component) including the semiconductor element has various forms depending on the corresponding size, and includes, for example, WLP (Wafer Level Package), PLP (Panel Level Package) and the like.
Examples of semiconductor package technology include fan-in type technology and fan-out type technology. As a semiconductor package using fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package) or the like in which terminals at the end of a bare chip are rearranged in a chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) or the like in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, fan-out type technology has been applied to fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel, and further high integration in semiconductor packages has been achieved. It is attracting attention as a method that can realize thinning and miniaturization.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the element to be incorporated. However, if the thickness of the substrate is reduced, the strength of the substrate is reduced, and the substrate is liable to be damaged during the manufacture of the semiconductor package. On the other hand, there is known a technique of temporarily adhering a substrate to a support using an adhesive, processing the substrate, and then separating the substrate from the support.

As the adhesive used for temporary bonding between the substrate and the support, a thermoplastic adhesive is often used because the adhesive layer can be easily removed with a solvent or the like. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high boiling point solvent, and a low boiling point solvent.

International Publication No. 2016/05/2315

By the way, in semiconductor package manufacturing, high temperature treatment such as thin film formation, firing, and die bonding may be performed. If the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer decreases during high-temperature treatment, and there is a concern that the substrate may be misaligned or the substrate may sink. On the other hand, when the heat resistance of the adhesive is increased, the applicability to the substrate or the support tends to decrease.
When a thermosetting adhesive is used to bond the support and the substrate, problems such as misalignment and sinking do not occur during high temperature treatment. However, it is difficult to remove the adhesive layer with a solvent or the like, and even when the separation layer is provided, it is difficult to remove the adhesive layer adhering to the substrate after separating the support and the substrate due to deterioration of the separation layer.
Further, in the conventional adhesive, a separation layer is usually required in order to separate the support and the substrate after processing the substrate. Therefore, it is necessary to separately form the separation layer and the adhesive layer, which is complicated.

The present invention has been made in view of the above circumstances, and is produced by using an adhesive composition that does not require a separation layer, has high heat resistance, and is easy to remove the adhesive layer, and the adhesive composition. An object of the present invention is to provide a laminate, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support that transmits light, and (a) light. An adhesive composition containing an absorbent, a polyisocyanate, and a polyol, or (b) a light absorber, a urethane resin containing a polymerizable carbon-carbon double bond, and a polymerization initiator.

A 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 laminated in this order, and the adhesive layer is the adhesive according to the first aspect. It is a laminate, which is a cured product of the composition.

A third aspect of the present invention is a method for producing a laminated body in which a support that transmits light, an adhesive layer, and a semiconductor substrate are laminated in this order, and the first aspect is applied to the support or the semiconductor substrate. The step of applying the adhesive composition to form the adhesive composition layer, the step of placing the semiconductor substrate on the support via the adhesive composition layer, and the step of placing the adhesive composition on the support. This is a method for producing a laminated body, which comprises a step of curing the layer to form the adhesive layer.

A fourth aspect of the present invention comprises a member made of a metal or a semiconductor after obtaining the laminate by the method for producing a laminate according to the third aspect, and a resin for sealing or insulating the member. This is a method for producing a laminate in which a light-transmitting support, an adhesive layer, and an electronic device are laminated in this order, further comprising an electronic device forming step for forming the electronic device, which is a composite of the above.

In a fifth aspect of the present invention, after a laminate is obtained by the method for producing a laminate according to the fourth aspect, the adhesive layer is irradiated with light via the support to alter the adhesive layer. A step of separating the electronic device from the support and a step of removing the adhesive layer adhering to the electronic device by decomposing the urethane bond in the adhesive layer with an acid or an alkali. It is a manufacturing method of an electronic part having.

According to the present invention, an adhesive composition that does not require a separation layer, has high heat resistance, and is easy to remove the adhesive layer, a laminate produced using the adhesive composition, and a method for producing the laminate. , And a method for manufacturing an electronic component using the adhesive composition.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process diagram explaining one Embodiment of the manufacturing method of the laminated body 100'in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. FIG. 5A is a diagram for explaining an adhesive composition layer forming step, and FIG. 5B is a diagram for explaining a semiconductor substrate mounting step. It is a figure explaining the adhesive layer forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 120. FIG. 7A is a diagram for explaining a sealing process, FIG. 7B is a diagram for explaining a grinding process, and FIG. 7C is a diagram for explaining a wiring layer forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a semiconductor package (electronic component) from a laminated body 120. 8 (a) is a diagram showing the laminated body 200, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining an adhesive layer removing step.

In the present specification and claims, "aliphatic" is defined as a concept relative to aromatics and means groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" shall include linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is 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.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of hydrogen atoms of the alkyl group or the alkylene group is substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent" or "may have a substituent", the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH ₂ ) is substituted. Includes both cases where −) is replaced with a divalent group.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from hydroxystyrene” means a structural unit formed by cleaving the ethylenic double bond of hydroxystyrene. The “constituent unit derived from the hydroxystyrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the hydroxystyrene derivative.
The "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. Derivatives thereof include those in which the hydrogen atom at the α-position may be substituted with a substituent, and the hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than the hydroxyl group is bonded to the benzene ring of a good hydroxystyrene. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Further, as the hydroxyalkyl group as the substituent at the α-position, a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a hydroxyl group can be specifically mentioned. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

In the present specification and claims, there are some structures represented by chemical formulas in which an asymmetric carbon is present and an enantiomer or a diastereomer may be present. The case is represented by one formula to represent those isomers. These isomers may be used alone or as a mixture.

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support that transmits light.
It is characterized by containing (a) a light absorber, a polyisocyanate, and a polyol, or (b) a light absorber, a urethane resin containing a polymerizable carbon-carbon double bond, and a polymerization initiator.

<Target of temporary adhesion>
The adhesive composition according to this embodiment is used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support. As used herein, "temporary bonding" means that the objects to be bonded are temporarily bonded (for example, during an arbitrary work process). More specifically, the semiconductor substrate or the electronic device is temporarily adhered to the support and fixed on the support for the purpose of thinning the device, transporting the semiconductor substrate, mounting on the semiconductor substrate, and the like (provisional). Adhesion), separated from the support after the process is complete.

≪Semiconductor substrate≫
The semiconductor substrate to which the adhesive composition according to the present embodiment is applied is not particularly limited, and may be generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by a support. Structures such as integrated circuits and metal bumps may be mounted on the semiconductor substrate.
The semiconductor substrate is typically a silicon wafer substrate, but is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

≪Electronic device≫
As used herein, the term "electronic device" means a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited, and various mechanical structures and circuits may be formed on the surface of the semiconductor substrate. The electronic device may preferably be a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer described later and / or a semiconductor element or other element sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure. obtain.

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

The adhesive composition of the present embodiment contains any of the following components (a) or (b).
(A) Light absorber, polyisocyanate, and polyol.
(B) A light absorber, a urethane resin containing a polymerizable carbon-carbon double bond, and a polymerization initiator.
Hereinafter, for convenience, the adhesive composition containing the component (a) is referred to as "adhesive composition (a)", and the adhesive composition containing the component (b) is referred to as "adhesive composition (b)". Also called.

Both the adhesive composition (a) and the adhesive composition (b) are curable adhesive compositions, and are cured by forming a crosslinked structure by heating or the like. Therefore, by forming an adhesive composition layer between the semiconductor substrate or electronic device (hereinafter collectively referred to as "semiconductor substrate or the like") and the support and curing the adhesive composition layer, the semiconductor substrate or the like and the support are temporarily separated. An adhesive layer to be bonded can be formed.
On the other hand, the adhesive layer formed by the adhesive composition (a) or the adhesive composition (b) contains a light absorber. Therefore, when the adhesive layer is irradiated with light through a support that transmits light, the adhesive layer light absorber absorbs the light and the adhesive layer is denatured. As a result, the semiconductor substrate or device temporarily bonded via the adhesive layer and the support that transmits light can be separated.
Further, since the adhesive layer formed by the adhesive composition (a) or the adhesive composition (b) contains a urethane resin, the adhesive layer can be decomposed by decomposing the urethane bond with an acid or an alkali. it can. Thereby, after separating from the support that transmits light, the residue of the adhesive layer adhering to the semiconductor substrate or the device can be removed.

<Adhesive composition (a)>
The adhesive composition (a) contains a light absorber, a polyisocyanate, and a polyol. In the adhesive composition (a), the polyisocyanate and the polyol are urethane-bonded and crosslinked by heating. As a result, the adhesive composition layer is cured to form an adhesive layer for temporarily adhering the support, the semiconductor substrate, and the like. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light and the adhesive layer is denatured. As a result, the support and the semiconductor substrate or the like can be separated. Further, the residue of the adhesive layer adhering to the semiconductor substrate or the like can be removed by decomposing the urethane bond with an acid or an alkali.

≪Light absorber: (B) component≫
The adhesive composition (a) contains a light absorber (hereinafter, also referred to as “component (B)”). When the adhesive composition (a) contains the component (B), the adhesive layer can be altered by irradiating with light.

The component (B) is not particularly limited as long as it is a substance having a light absorbing ability. As the component (B), a component capable of absorbing light having a wavelength of light that is irradiated when the support and the semiconductor substrate or the like are separated can be used. For example, as the component (B), a component capable of absorbing light in the wavelength range of 300 to 800 nm can be used. The component (B) preferably has a light in the wavelength range of 400 to 700, more preferably can absorb light in the wavelength range of 450 to 600 nm, and can absorb light in the wavelength range of 500 to 550 nm. Is more preferable.
Examples of the component (B) include pigments and dyes.

-Pigment The pigment may be an organic pigment or an inorganic pigment. The pigment may be either a black pigment or a color coloring pigment.

Examples of the black organic pigment include perylene black (perylene-based black pigment), cyanine black, aniline black, lactam black and the like. Examples of the black inorganic pigment include carbon black (lamp black, acetylene black, thermal black, channel black, furnace black, etc.), chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, strontium titanate, and oxidation. Examples include chrome and ceria.

Examples of the color coloring pigment include compounds classified as Pigments in the Color Index (CI; The Society of Dyers and Colorists), specifically, the following Color Index (C). .I.) Numbered items and the like can be mentioned.

C. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described), 3,11,12,13,14,15,16,17,20,24,31,53,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119. , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;
C. I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described), 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, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is described) 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, "CI Pigment Blue" is the same and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37;
C. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28;
C. I. Pigment Black 1, Pigment Black 7.

The particle size of the pigment can be appropriately set, and for example, the volume average particle size 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 a dynamic light scattering method.

As the pigment, one type may be used alone, or two or more types may be used in combination. Further, a plurality of pigments that absorb light in different wavelength ranges may be used in combination. For example, a black pigment and one or more color coloring pigments may be used in combination.

-Dyes Examples of dyes include azo dyes (monoazo and polyazo dyes, metal complex salt azo dyes, pyrazolone azo dyes, stillben azo dyes, thiazole azo dyes), anthraquinone dyes (anthraquinone derivatives, anthron derivatives), and indigoid dyes (indigoid derivatives, Thioindigoid derivatives), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes), quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes), methine dyes (cyanine dyes, azomethine dyes), quinoline dyes. , Nitroso dyes, benzoquinones and naphthoquinone dyes, naphthalimide dyes, perinone dyes and the like.

As the dye, a commercially available dye may be used. Examples of commercially available dyes include PC-5857 (manufactured by Orient Industry Co., Ltd.) and the like.

As the dye, one type may be used alone, or two or more types may be used in combination. Further, a plurality of dyes that absorb light in different wavelength ranges may be used in combination.

As the component (B), one type may be used alone, or two or more types may be used in combination.
The content of the component (B) in the adhesive composition (a) is preferably 1 to 20% by mass, preferably 2 to 15% by mass, based on the total mass (100% by mass) of the adhesive composition (a). More preferably, 3 to 15% by mass is further preferable. When the content of the component (B) is at least the above lower limit value, the light absorption efficiency in the adhesive layer is improved, and the deterioration of the adhesive layer is improved. When the content of the component (B) is not more than the above upper limit value, it becomes easy to balance with other components.
Further, the content of the component (B) in the adhesive composition (a) may be 5% by mass or more with respect to the total mass (100% by mass) of the adhesive composition (a) by 10% by mass. It may be% or more.

<< Polyisocyanate compound: Component (I) >>
The adhesive composition (a) contains a polyisocyanate compound (hereinafter, also referred to as “component (I)”). As used herein, the term "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 those generally used for producing urethane resins can be used without particular limitation.
Blocked polyisocyanate is a compound in which the isocyanate group of polyisocyanate is blocked by a reaction with a blocking agent and inactivated. The blocked polyisocyanate used as the component (I) is preferably one in which the isocyanate group is blocked by a heat-dissociating blocking agent. Examples of the heat dissociable blocking agent include blocking agents such as oximes, diketones, phenols and caprolactams. Blocked polyisocyanates with a heat-dissociating blocking agent have inactive isocyanate groups at room temperature, and when heated, the heat-dissociating blocking agent dissociates and regenerates the isocyanate groups.

Specific examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexanediisocyanate, hydrogenated xylylene diisocyanate, and water. Alicyclic diisocyanates such as supplemented tolylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, Aromatic diisocyanates such as trizine diisocyanate, p-phenylenediocyanate, and naphthylene diisocyanate; and adducts of these biurets, isocyanurates, and trimethylolpropane can be mentioned. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

As the polyisocyanate, a commercially available one may be used. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, and Duranate MHG. -80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H. (The above is the product name, the name manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like. 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 as described above is protected by a reaction with a blocking agent. The blocking agent is not particularly limited and is known as long as it is a thermally dissociable blocking agent, that is, a compound that is stable at room temperature but is liberated when heated to a dissociation temperature or higher to generate an isocyanate group. Those can be used without particular limitation.
Specific examples of the blocking agent include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam and propiolactam; methylethylketooxime, methylisoamylketooxime, methylisobutylketooxime, formamideoxime, acetamideoxime, Oxime compounds such as acetooxime, diacetylmonooxime, benzophenone oxime, cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, nitrophenol; polycyclic phenol compounds such as 1-naphthol; methyl alcohol, ethyl alcohol, isopropyl alcohol Alcohol compounds such as tert-butyl alcohol, trimethylolpropane, 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; malonic acid alkyl ester, malonic acid dialkyl ester, acet Active oxime compounds such as acetic acid alkyl ester and acetylacetone; and the like. As the blocking agent, one type may be used alone, or two or more types may be used in combination.

Blocked polyisocyanate can be produced by reacting polyisocyanate with a blocking agent. The reaction between the polyisocyanate and the blocking agent is carried out, for example, in a solvent having no active hydrogen (1.4 dioxane, cellosolve acetate, etc.) under heating at about 50 to 100 ° C., and if necessary, the presence of a blocking catalyst. It is done below. The ratio of the polyisocyanate to the blocking agent is not particularly limited, but the equivalent ratio of the isocyanate group to the blocking agent in the polyisocyanate is preferably 0.95: 1.0 to 1.1: 1.0. , More preferably 1: 1.05 to 1.15. Known blocking catalysts can be used, for example, metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate, potassium methylate; tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium. Hydrooxides; organic weak salts such as these acetates, octylates, myristates, benzoates; and alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octyl acid, myristic acid; etc. Be done. As the blocking catalyst, one type may be used alone, or two or more types may be used in combination.

Commercially available block polyisocyanate may be used. Examples of commercially available blocked polyisocyanates include Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (hereinafter, trade names). , Asahi Kasei Corporation), etc.

As the component (I), blocked polyisocyanate in which the isocyanate group is blocked by a heat dissociative blocking agent is preferable.

As the component (I), one type may be used alone, or two or more types may be used in combination.
The content of the component (I) in the adhesive composition (a) is preferably 5 to 50% by mass, preferably 10 to 40% by mass, based on the total mass (100% by mass) of the adhesive composition (a). More preferably, 20 to 40% by mass is further preferable. When the content of the component (I) is at least the above lower limit value, the curability of the adhesive composition (a) becomes good. When the content of the component (I) is not more than the above upper limit value, it becomes easy to balance with other components.

<< polyol: component (O) >>
The adhesive composition (a) contains a polyol (hereinafter, also referred to as “component (O)”). A polyol is a compound having two or more hydroxy groups (-OH). The polyol is not particularly limited, and those generally used in the production of urethane resin can be used without particular limitation. The component (O) may be an aliphatic polyol or an aromatic polyol. The component (O) may be a low molecular weight polyol (for example, a molecular weight of less than 500) or a high molecular weight polyol (for example, a molecular weight of 500 or more).

Specific examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, and 1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, 7-22 carbon atoms alcandiol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl -1,3-Propanediol, Alcan-1,2-diol having 17 to 20 carbon atoms, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanediol, Bisphenol hydride A, Dihydric alcohols such as 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetramethylolmethane (pentamethylolmethane) Erislitol), tetrahydric alcohols such as diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, aritol, iditol, darsitol, altritor, inositol, dipentaerythritol; Octohydric alcohols such as sucrose; and the like.

Examples of the polymer polyol include a phenol resin, a resin containing a hydroxystyrene skeleton, a polyester polyol, a polyether polyol, a polyether ester polyol, a polyesteramide polyol, an acrylic polyol, a polycarbonate polyol, a polyhydroxylalkane, a polyurethane polyol, and a vegetable oil type. Examples include polyols. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.

[Phenolic resin]
The phenol resin may be a novolak type phenol resin or a resol type phenol resin. The novolak-type phenolic resin can be obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and aldehydes under an acid catalyst. The resole-type phenolic resin can be obtained by addition-condensing phenols and aldehydes under an alkaline catalyst.

Examples of the phenols include phenols; cresols such as m-cresol, p-cresol, o-cresol; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2 Alkylphenols such as −tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol , P-propoxyphenols, m-propoxyphenols and other alkoxyphenols; o-isopropenylphenols, p-isopropenylphenols, 2-methyl-4-isopropenylphenols, 2-ethyl-4-isopropenylphenols and other isopropenylphenols. Propenylphenols; arylphenols such as phenylphenols; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9, Examples thereof include polyhydroxyphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p. -Hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, katsura aldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenyl Benzaldehyde and the like can be mentioned.

The acid catalyst at the time of the addition condensation reaction is not particularly limited, and for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used. The alkali catalyst at the time of the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, hexamethylenetetramine and the like are used.

[Resin containing hydroxystyrene skeleton]
The resin containing a hydroxystyrene skeleton is not particularly limited as long as it has a structural unit derived from hydroxystyrene or a hydroxystyrene derivative. Specific examples of the structural unit derived from the hydroxystyrene or the hydroxystyrene derivative include the structural unit represented by the following general formula (a10-1).

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^ｘ１は、単結合又は２価の連結基である。Ｗａ^ｘ１は、（ｎ_ａｘ１＋１）価の芳香族炭化水素基である。ｎ_ａｘ１は、１〜３の整数である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or divalent linking group. Wa ^x1 is a (n _ax1 + 1) valent aromatic hydrocarbon group. n _ax1 is an integer of 1 to 3. ]

In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-. Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The alkyl halide group having 1 to 5 carbon atoms of R is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.
As the divalent linking group in Ya ^x1 , for example, a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom are preferable.

A divalent hydrocarbon group that may have a substituent:
When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

· · Aliphatic hydrocarbon group in Ya ^x1 The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Numbers 1 to 4 are more preferable, and carbon numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ). Alkylmethylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc.;- 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 - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The 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, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which the group hydrocarbon group is intervening in the middle of the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. The methoxy group and the ethoxy group are most preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

Aromatic hydrocarbon group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the carbon number does not include the carbon number of the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. A group in which one is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc. A group obtained by removing one more atom) and the like. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon number.

In the aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, halogen atom and alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-Divalent linking group containing heteroatom:
When Ya ^x1 is a divalent linking group containing a hetero atom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC. (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group or an acyl group. _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - ^{C (= O) -O -,} - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y 22 -, - Y 21 -O-C ( = O) ^{-Y 22} - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} have independently substituent It is also a good divalent hydrocarbon group, where O is an oxygen atom and m "is an integer from 0 to 3. ] Etc. can be mentioned.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). )-, The H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 - _{^{C (= O) -O] m}} "-Y 22 -, - Y 21 -O-C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - in, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group is mentioned in the description as the divalent linking group. (A divalent hydrocarbon group that may have a substituent) is mentioned.
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by group is particularly preferred among them, the formula _{-. (CH 2) a '} -C (= O) -O- (CH 2) b' -. in the group represented by the formula in the formula, a 'is from 1 to 10 Is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b'is an integer of 1 to 10 and of 1 to 8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

As Ya ^x1 , a single bond, an ester bond [-C (= O) -O-], an ether bond (-O-), -C (= O) -NH-, a linear or branched alkylene group. , Or a combination thereof, and a single bond is particularly preferable.

In the formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group having a ( _nax1 + 1) valence.
Examples of the aromatic hydrocarbon group in Wa ^x1 include a group obtained by removing (n _ax1 + 1) hydrogen atoms from the 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 may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

In the above formula (a10-1), n _ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

A specific example of the structural unit represented by the general formula (a10-1) is shown below.
In the formula below, 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]
Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One or more of diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, etc. Examples thereof include a polycarbonate polyol obtained by reacting the glycol of dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgen and the like.

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

［式中、Ｒｐ^１及びＲｐ^２は、それぞれ独立に、２価の炭化水素基である。ｎｐは、２以上の整数である。］

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

In the general formula (PC-1), Rp ¹ and Rp ² are independently divalent hydrocarbon groups. The divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to those mentioned in Ya ^x1 in the general formula (a10-1). As the divalent hydrocarbon group in Rp ¹ and Rp ² , an aliphatic hydrocarbon group is preferable, and a linear or branched alkylene group is more preferable. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. 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 to 5000, more preferably 500 to 3000, further preferably 500 to 2000, and particularly preferably 500 to 1000.

[Other polyols]
Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, dialkyl esters thereof, or mixtures thereof, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, and neo. Glycos such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol or Examples thereof include polyester polyols obtained by reacting a mixture thereof with polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone). ..

As the polyether polyol, for example, an oxylan compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran is polymerized using a low-volume polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerin as an initiator. Examples thereof include the obtained polyether polyol.

The polyether ester polyol is obtained by reacting, for example, a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebatic acid, a dialkyl ester thereof, or a mixture thereof with the above-mentioned polyether polyol. Examples include polyether ester polyols.

Examples of the polyesteramide polyol include a polyesteramide polyol obtained by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, and hexamethylenediamine as a raw material in the esterification reaction.

Examples of the acrylic polyol include hydroxyethyl acrylate containing one or more hydroxyl groups in one molecule, hydroxyprople acrylate, acrylic hydroxybutyl and the like, or corresponding methacrylic acid derivatives thereof, and for example, acrylic acid, methacrylic acid or Examples thereof include a polyesteramide polyol obtained by copolymerizing with the ester.

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

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule. For example, a polyether polyol having a number average molecular weight of 200 to 20,000, a polyester polyol, a polyether ester polyol, or the like, and a polyisocyanate are used. , Preferably a polyurethane polyol obtained by reacting with an NCO / OH of less than 1, more preferably 0.9 or less.

Examples of the vegetable oil-based polyol include castor oil, castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol. Among them, as the vegetable oil-based polyol, castor oil-modified polyol is preferable, and castor oil-modified diol is more preferable.

Among the above, as the component (O), a phenol resin or a resin containing a hydroxystyrene skeleton is preferable, a novolak resin or a resin containing a hydroxystyrene skeleton is more preferable, and a polymer of hydroxystyrene or a hydroxystyrene derivative is further preferable. Polyhydroxystyrene resin is particularly preferable.

As the component (O), one type may be used alone, or two or more types may be used in combination.
The content of the component (O) in the adhesive composition (a) is preferably 50 to 90% by mass, preferably 50 to 85% by mass, based on the total mass (100% by mass) of the adhesive composition (a). More preferably, 60 to 85% by mass is further preferable. When the content of the component (O) is at least the above lower limit value, the curability of the adhesive composition (a) becomes good. When the content of the component (I) is not more than the above upper limit value, it becomes easy to balance with other components.

The molar ratio (NCO / OH) of the hydroxy group (-OH) in the component (O) to the isocyanate group (-NCO) in the component (I) contained in the adhesive composition (a) is 0.1 to 1. It is preferably 0.3 to 0.7, and more preferably 0.3 to 0.7.
The mass ratio of the contents of the component (I) and the component (O) in the adhesive composition (a) may be in the range of ((I) :( O)) = 1:10 to 10: 1. It is preferably 2: 8 to 8: 2, more preferably 2: 8 to 5: 5, and even more preferably 2: 8 to 5: 5.

<Adhesive composition (b)>
The adhesive composition (b) contains a light absorber, a urethane resin containing a polymerizable carbon-carbon double bond, and a polymerization initiator. In the adhesive composition (b), a urethane resin containing a polymerizable carbon-carbon double bond is polymerized and crosslinked by heating or the like. As a result, the adhesive composition layer is cured to form an adhesive layer for temporarily adhering the support, the semiconductor substrate, and the like. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light and the adhesive layer is denatured. As a result, the support and the semiconductor substrate or the like can be separated. Further, the residue of the adhesive layer adhering to the semiconductor substrate or the like can be removed by decomposing the urethane bond with an acid or an alkali.

≪Light absorber: (B) component≫
The adhesive composition (b) contains a light absorber (component (B)). Examples of the component (B) include the same components as those of the adhesive composition (a).
As the component (B), one type may be used alone, or two or more types may be used in combination.
The content of the component (B) in the adhesive composition (b) is preferably 1 to 20% by mass, preferably 2 to 15% by mass, based on the total mass (100% by mass) of the adhesive composition (b). More preferably, 3 to 15% by mass is further preferable. When the content of the component (B) is at least the above lower limit value, the light absorption efficiency in the adhesive layer is improved, and the deterioration of the adhesive layer is improved. When the content of the component (B) is not more than the above upper limit value, it becomes easy to balance with other components.
Further, the content of the component (B) in the adhesive composition (b) may be 5% by mass or more with respect to the total mass (100% by mass) of the adhesive composition (b) by 10% by mass. It may be% or more.

<< Urethane resin containing polymerizable carbon-carbon double bond: (P1) component >>
The adhesive composition (b) contains a urethane resin containing a polymerizable carbon-carbon double bond (hereinafter, also referred to as “(P1) component”). The polymerizable carbon-carbon double bond contained in the component (P1) is not particularly limited, but is preferably radically polymerizable. Examples of the polymerizable carbon-carbon double bond include a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon double bond contained in the component (P1) may be one type or two or more types.
The equivalent of the polymerizable carbon-carbon double bond contained in the component (P1) is 200 to 2000 g / eq. The above is preferable, and 300 to 1500 g / eq. The above is more preferable, and 400 to 1200 g / eq. The above is more preferable, and 500 to 1000 g / eq. Is particularly preferable. When the polymerizable carbon-carbon double bond equivalent is at least the lower limit of the preferable range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. When the polymerizable carbon-carbon double bond equivalent is not more than the upper limit of the above-mentioned preferable range, the adhesive layer does not become too hard and the detergency is improved. The equivalent number is the molecular weight of the urethane resin per equivalent of the polymerizable carbon-carbon double bond.

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

The component (P1) can be synthesized by a polymerization addition reaction of a polyisocyanate compound (component (I)) and a polyol (component (O)). It is preferable that at least one of the component (I) and the component (O) contains a polymerizable carbon-carbon double bond.

-Polyisocyanate compound: The component (I) used for the synthesis of the component (P1) includes the same components as those listed as the component (I) in the adhesive composition (a).
As the component (I), one type may be used alone, or two or more types may be used in combination. For example, as the component (I), a mixture of an aliphatic diisocyanate and an aromatic diisocyanate can be used. As the aliphatic diisocyanate, hydrogenated xylene diisocyanate is preferable. As the aromatic diisocyanate, 4,4-diphenylmethane diisocyanate is preferable.

-Polycarbonate: The component (O) used for the synthesis of the component (P1) includes a polyol containing a polymerizable carbon-carbon double bond (hereinafter, also referred to as "component (O1)") and other polyols. (Hereinafter, also referred to as "(O2) component").

-Polymer containing a polymerizable carbon-carbon double bond ((O1) component)
Examples of the component (O1) include polyols containing at least one selected from the group consisting of methacryloyl groups and acryloyl groups. The polymerizable carbon-carbon double bond contained in the component (O1) may be one or two or more.

Examples of the component (O1) include esters of trivalent or higher valent polyols and methacrylic acid, acrylic acid or derivatives thereof. As the trivalent or higher valent polyol, a trivalent or higher low molecular weight polyol is preferable. Examples of the trihydric or higher low molecular weight polyols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; sorbitol, mannitol and alitol. , Hexal alcohols such as iditol, darsitol, altritor, inositol, dipentaerythritol; heptahydric alcohols such as persetol; and octahydric alcohols such as sucrose; and the like.

Specific examples of the component (O1) include glycerin mono (meth) acrylate, diglycerin tri (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, diglycerin di (meth) acrylate, and dipentaerythritol. Di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) Examples include acrylate.
"(Meta) acrylate" is a concept that includes methacrylate and acrylate, and means methacrylate or acrylate.

As the component (O1), one type may be used alone, or two or more types may be used in combination.
Among them, the component (O1) is preferably a diol containing a methacryloyl group or an acryloyl group, and more preferably glycerin mono (meth) acrylate or pentaerythritol di (meth) acrylate.

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

Examples of the low-molecular-weight polyol include those similar to those mentioned in the description of the component (O) in the adhesive composition (a). As the low molecular weight polyol, a divalent alcohol (diol) is preferable.
When a low molecular weight polyol is used as the component (O2), the ratio of the low molecular weight polyol to the component (O1) (low molecular weight polyol / component (O1) component (mass ratio)) is preferably 0.01 to 0.1, and is 0. More preferably .03 to 0.08.

Examples of the polymer polyol include those similar to those mentioned in the description of the component (O) in the adhesive composition (a) (however, those corresponding to the component (O1) are excluded).
As the polymer polyol, a polycarbonate polyol and a vegetable oil-based polyol are preferable. As the polycarbonate polyol, an aliphatic polycarbonate polyol is preferable, and an aliphatic polycarbonate diol is more preferable. As the vegetable oil-based polyol, castor oil-modified polyol is preferable, and castor oil-modified diol is more preferable.
When a polycarbonate polyol is used as the component (O2), the ratio of the polycarbonate polyol to the component (O1) (polycarbonate polyol / component (O1) component (mass ratio)) is preferably 0.1 to 5, preferably 0.3 to 3. More preferably, 0.4 to 3 is further preferable.
When a vegetable oil-based polyol is used as the component (O2), the ratio of the vegetable oil-based polyol to the component (O1) (vegetable oil-based polyol / component (O1) component (mass ratio)) is preferably 0.1 to 5, preferably 0.3. ~ 3 is more preferable, and 0.4 to 2.5 is even more preferable.

As the component (O2), one type may be used alone, or two or more types may be used in combination.
Among the above, as the component (O2), a polycarbonate polyol and a low molecular weight polyol are preferable from the viewpoint of adjusting the viscosity of the adhesive composition (b) and the hardness of the adhesive layer. Further, from the viewpoint of increasing the heat resistance of the adhesive layer, castor oil-modified polyol may 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), the heat resistance of the adhesive layer, and the like. As the component (O2), a low molecular weight polyol, a polycarbonate polyol, a castor oil-modified polyol, or a combination thereof is preferable. Specific examples of the component (O2) to be combined with the component (O1) include a combination of a polycarbonate polyol, a castor oil-modified polyol, and a low-molecular-weight polyol; a combination of a polycarbonate polyol and a castor oil-modified polyol; and a polycarbonate polyol.
The mass ratio of the component (O1) to the component (O2) is preferably (O1) :( O2) = 1: 5 to 5: 1, more preferably 1: 4 to 2: 1, and 1: 4 to 1: 1 is more preferable, and 1: 4 to 1: 2 is particularly preferable. By setting the mass ratio of the component (O1) to the component (O2) within the above range, the elastic modulus, heat resistance, and the like of the adhesive layer can be improved.

The component (P1) can be synthesized by mixing the components (I) and (O) and copolymerizing them according to a known urethane resin synthesis method. The copolymerization of the component (I) and the component (O) is preferably carried out in the presence of a known urethane such as a bismuth catalyst or a catalyst. Further, in order to avoid the polymerization of the polymerizable carbon-carbon double bond in the component (O1), a polymerization inhibitor may be added to the reaction system.

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

As the component (P1), one type may be used alone, or two or more types may be used in combination.
The content of the component (P1) in the adhesive composition (b) is not particularly limited as long as it can be applied to a support or the like. The content of the component (P1) in the adhesive composition (b) is preferably 10 to 60% by mass, preferably 20 to 60% by mass, based on the total mass (100% by mass) of the adhesive composition (b). Is more preferable, and 30 to 60% by mass is further preferable.

<< Polymerization initiator: Component (A) >>
The adhesive composition (b) contains a polymerization initiator (hereinafter, also referred to as component (A)). The polymerization initiator is a component having a function of accelerating the polymerization reaction. Examples of the component (A) include a thermal polymerization initiator and a photopolymerization initiator.

Examples of the thermal polymerization initiator include peroxides and azo-based polymerization initiators.

Examples of the peroxide in the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters and the like. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), and 2-chlorobenzoyl peroxide. 3-Chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl -2-Methylpropyl-1-hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-perphenylacetate Examples thereof include butyl, tert-butyl peroxide, and tert-butyl peroxide N- (3-toluyl) carbamate.

Examples of the peroxide include the trade name "Park Mill (registered trademark)", the trade name "Perbutyl (registered trademark)", the trade name "Parloyl (registered trademark)" and the trade name "Perocta" manufactured by Nippon Oil & Fat Co., Ltd. Commercially available products such as "(registered trademark)" can be used.

Examples of the azo-based polymerization initiator in the thermal polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, and 1,1'-azo (methylethyl). Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyamide , 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2- Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodi Nitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis- Dimethyl 4-cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1' -Azobisisobutyoxynitrile, 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'-azobisisobutymen, 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitro Phynoazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2' -Azobisisobutyrate) and the like.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morphorinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone 1- [9-ethyl-6- (2-methylbenzoyl)) -9H-carbazole-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4 -Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-Benz anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumempaoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorofe) Nyl) -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'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethylmichillers) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin- t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt- Butyltrichloroacetophenone, pt-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acrydin, 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) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) -2-Methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxysti) Lil) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Examples include trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like. Be done.

Examples of the photopolymerization initiator include "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade names, manufactured by BASF) and "NCI-831". Commercially available products such as (trade name, manufactured by ADEKA Corporation) can be used.

As the component (A), one type may be used alone, or two or more types may be used in combination. As the component (A), a thermal polymerization initiator is preferable, and a peroxide is more preferable. The amount of the component (A) used can be adjusted according to the amount of the component (P1) used. The content of the polymerization initiator in the adhesive composition (b) is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (P1). Is more preferable.

<Arbitrary ingredient>
The adhesive composition (a) and the adhesive composition (b) may contain an arbitrary component in addition to the above components as long as the effects of the present invention are not impaired. The optional component is not particularly limited, and examples thereof include a polymerization inhibitor, a solvent component, a plasticizer, an adhesion aid, a stabilizer, a colorant, and a surfactant.

≪Polymerization inhibitor≫
A polymerization inhibitor refers to a component having a function of preventing a radical polymerization reaction due to heat or light. Polymerization inhibitors are highly reactive with radicals.

As the polymerization inhibitor, those having a phenol skeleton are preferable. For example, a hindered phenolic antioxidant can be used as such a polymerization inhibitor, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone. , N-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol) ), 4,4'-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidentris (2-methylphenol) , 4,4', 4 "-ethylidentrisphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4- Methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl- 6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl-3- (3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), Examples thereof include tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like.

As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination.
The content of the polymerization inhibitor may be appropriately determined according to the type of resin component, the use of the adhesive composition, and the usage environment.

≪Surfactant≫
Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like.

Examples of the fluorine-based surfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183 (all manufactured by DIC), and Florard. FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S- Examples thereof include commercially available fluorine-based surfactants such as 145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.).

Examples of the silicone-based surfactant include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, and aralkyl-modified silicone-based surfactants. , And reactive silicone-based surfactants and the like. As the silicone-based surfactant, a commercially available one can be used. Specific examples of commercially available silicone-based surfactants include, for example, Paintad M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyester modification). Examples thereof include silicone-based surfactants (manufactured by Clariant AG) and BYK-310 (polyester-modified silicone-based surfactants manufactured by Big Chemie).

One type of surfactant may be used alone, or two or more types may be used in combination. As the surfactant, a silicone-based surfactant is preferable, and a polyester-modified silicone-based surfactant is more preferable. When the adhesive composition (a) contains a surfactant, the content of the surfactant is 0.01 to 1 with respect to the total mass (100 parts by mass) of the components (I) and (O). It is preferably parts by mass, more preferably 0.5 to 0.5 parts by mass. When the adhesive composition (b) contains a surfactant, the content of the surfactant is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (P1). More preferably, it is 5 to 0.5 parts by mass.

≪Solvent component≫
Examples of the solvent component include hydrocarbon solvents, petroleum-based solvents, and other solvents other than the above-mentioned solvents. Hereinafter, the hydrocarbon solvent and the petroleum-based solvent are also collectively referred to as “(S1) component”. A solvent component other than the component (S1) is also referred to as a “component (S2)”.

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. Examples of the hydrocarbon solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; and branched hydrocarbons such as isooctane, isononan, and isododecane; p. -Mentane, o-menthane, m-menthane, diphenylmentane, 1,4-terpinene, 1,8-terpinene, bornan, norbornan, pinan, tsujan, karan, longihoren, α-terpinene, β-terpinene, γ-terpinene, Alicyclic hydrocarbons such as α-pinene, β-pinene, α-tujon, β-tujon, cyclohexane, cycloheptane, cyclooctane; toluene, xylene, inden, pentalene, indan, tetrahydroinden, naphthalene, tetrahydronaphthalene (tetraline) ), Aromatic hydrocarbons such as decahydronaphthalene (decalin).

The petroleum-based solvent is a solvent refined from heavy oil, and examples thereof include white kerosene, paraffin-based solvent, and isoparaffin-based solvent.

Examples of the component (S2) include a terpene solvent having an oxygen atom, a carbonyl group, an acetoxy group or the like as a polar group, and examples thereof include geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol and α-terpineol. , Β-terpineol, γ-terpineol, terpine-1-ol, terpine-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carboxylic, yonon, tsuyon, camphor, etc. Can be mentioned.

In addition, as the component (S2), lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol. , Polyvalent alcohols such as propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyvalent alcohols or the esters. Derivatives of polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monoalkyl ether such as monobutyl ether, or compounds having an ether bond such as monophenyl ether (among these, propylene glycol) Monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, Esters such as methyl methoxypropionate and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol and butylphenyl ether can also be mentioned.

As the solvent component, one type may be used alone, or two or more types may be used in combination. As the solvent component, those which are inactive with respect to the above-mentioned (B) component, (I) component and (O) component, or the above-mentioned (B) component and (P1) component are preferable. Preferred solvent components include, for example, ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixed solvents thereof.

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

The adhesive composition (b) can be prepared by dissolving the component (B), the component (P1), and the component (A), and if necessary, an arbitrary component in a solvent component and mixing them.
The content of the solvent component in the adhesive composition (b) may be appropriately adjusted according to the thickness of the adhesive composition layer. The content of the solvent component is preferably in the range of 40 to 90% by mass with respect to the total mass (100% by mass) of the adhesive composition, for example. That is, the adhesive composition of the present embodiment preferably has a solid content (total amount of compounding components excluding the solvent component) concentration in the range of 10 to 80% by mass. When the content of the solvent component is within the above-mentioned preferable range, the viscosity can be easily adjusted.

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

According to the adhesive composition of the present embodiment, when the semiconductor substrate or the like and the support are temporarily bonded, an adhesive composition layer is formed between the semiconductor substrate or the like and the support and cured. Let me. As a result, an adhesive layer for temporarily adhering the semiconductor substrate or the like and the support is formed. Since the adhesive layer is cured by the crosslinked structure, it has high heat resistance and the elastic modulus does not decrease even at a high temperature (for example, 200 ° C. or higher). Therefore, even when high-temperature processing is performed when processing a semiconductor substrate or an electronic device, problems such as misalignment and sinking are unlikely to occur.
On the other hand, when the adhesive layer is irradiated with light such as laser light, the component (A) in the adhesive layer absorbs the light and the adhesive layer is denatured. As a result, the adhesive force of the adhesive layer is reduced, and the semiconductor substrate and the like can be separated from the support. Therefore, it is not necessary to provide a separation layer.
Further, since the adhesive layer contains a urethane resin, the adhesive layer can be decomposed by decomposing the urethane bond with an acid or an alkali. Therefore, even when the residue of the adhesive layer adheres to the semiconductor substrate or the like separated from the support, the residue of the adhesive layer can be easily removed by washing with an acid or an alkali.

(Laminate)
The laminate according to the second aspect of the present invention is a laminate in which a support that transmits light, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, and the adhesive layer is the first aspect. It is a cured product of such an adhesive composition.

FIG. 1 shows an embodiment of the laminated body according to the second aspect.
The laminate 100 shown in FIG. 1 includes a support 1 that transmits light, an adhesive layer 3, and a semiconductor substrate 4. In the laminated body 100, the support 1, the adhesive layer 3, and the semiconductor substrate 4 are laminated in this order.

FIG. 2 shows another embodiment of the laminate according to the second aspect.
The laminate 200 shown in FIG. 2 has the same configuration as the laminate 100 except that the electronic device 456 composed of the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 is laminated on the adhesive layer 3. ..

FIG. 3 shows yet another embodiment of the laminate according to the second aspect.
The laminated body 300 shown in FIG. 3 has the same configuration as the laminated body 100 except that the electronic device is composed of the wiring layer 6.

FIG. 4 shows yet another embodiment of the laminate according to the second aspect.
The laminate 400 shown in FIG. 4 has the same configuration as the laminate 100 except that the electronic device 645 composed of the wiring layer 6, the semiconductor substrate 4, and the sealing material layer 5 is laminated on the adhesive layer 3. ..

<Support>
The support is a member that supports a semiconductor substrate or an electronic device. The support has the property of transmitting light. The support is attached to the semiconductor substrate or electronic device via an adhesive layer. Therefore, it is preferable that the support has the strength necessary to prevent the semiconductor substrate from being damaged or deformed when the device is thinned, the semiconductor substrate is transported, or the semiconductor substrate is mounted on the semiconductor substrate.
As the material of the support, for example, glass, silicon, acrylic resin and the like are used. Examples of the shape of the support include, but are not limited to, a rectangle, a circle, and the like. As the support, in order to further increase the density and improve the production efficiency, a large circular support or a large panel having a quadrangular shape in a plan view can be used.

<Adhesive layer>
The adhesive layer is provided to temporarily bond the semiconductor substrate or the electronic device to the support. The adhesive layer is a cured product of the adhesive composition according to the first embodiment. Curing of the adhesive composition according to the first embodiment can be performed by heating the adhesive composition. The thickness of the adhesive layer is preferably in the range of, for example, 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.

As described above, the adhesive layer is a cured product of the adhesive composition, and the material (cured product) constituting the adhesive layer preferably satisfies the following characteristics.
That is, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 200 ° C. is preferably 1.0 × 10 ⁴ Pa or more, and 5.0 × 10 ⁴ Pa or more. more preferably in, further preferably 1.0 × ¹⁰ 5 Pa or more. Further, the complex elastic modulus at 200 ° C. is more preferably 1.0 × 10 ⁶ Pa or more, further preferably 5.0 × 10 ⁶ Pa or more, and 1.0 × 10 ⁷ Pa or more. Is particularly preferred. The upper limit of the complex elastic modulus at 200 ° C. is, for example, 1.0 × 10 ¹⁰ Pa or less.
Further, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 250 ° C. is preferably 5.0 × 10 ⁶ Pa or more, preferably 1.0 × 10 ⁷ Pa or more. Is more preferable. The upper limit of the complex elastic modulus at 250 ° C. is, for example, 1.0 × 10 ¹⁰ Pa or less.

The complex elastic modulus of the cured product can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition is applied onto a PET film with a mold release agent, and heated in an oven under a nitrogen atmosphere at 180 ° C. for 1 hour to form a test piece having a thickness of 50 μm, and then PET. The test piece (size 5 mm × 40 mm, thickness 50 μm) peeled off from the film can be measured using the above-mentioned measuring device. As the measurement conditions, a condition may be adopted in which the temperature is raised from a starting temperature of 50 ° C. to 300 ° C. at a heating rate of 5 ° C./min under a tensile condition having a frequency of 1 Hz.

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

≪Semiconductor substrate≫
The semiconductor substrate is not particularly limited, and examples thereof are the same as those exemplified in the above "(adhesive composition)". The semiconductor substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure.

≪Electronic device≫
The electronic device is not particularly limited, and examples thereof are the same as those exemplified in the above "(adhesive composition)". The electronic device is preferably a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and can further include a semiconductor substrate.
In the laminate 200 shown in FIG. 2, the electronic device 456 is composed of a semiconductor substrate 4, a sealing material layer 5, and a wiring layer 6. In the laminated body 300 shown in FIG. 3, the electronic device 6 is composed of the wiring layer 6. In the laminate 400 shown in FIG. 4, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5.

[Encapsulant layer]
The encapsulant layer is provided for encapsulating the semiconductor substrate, and is formed by using the encapsulant. As the sealing material, a member capable of insulating or sealing a member made of metal or a semiconductor is used.
As the sealing material, for example, a resin composition can be used. The encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and / or insulate a metal or semiconductor, and examples thereof include epoxy resins and silicone resins.
The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles and the like.

≪Wiring layer≫
The wiring layer is also called an RDL (Redistribution Layer), and is a thin film wiring body constituting a wiring connected to a substrate, and may have a single layer or a plurality of layers structure. The wiring layer is composed of conductors (for example, metals such as aluminum, copper, titanium, nickel, gold and silver, and silver-tin) between dielectrics (silicon oxide (SiO _x ), photosensitive resins such as photosensitive epoxy). The wiring may be formed of an alloy such as an alloy), but the wiring is not limited to this.

In the laminated body of FIGS. 1 to 4, the support 1 and the adhesive layer 3 are adjacent to each other, but the present invention is not limited to this, and another layer is further formed between the support 1 and the adhesive layer 3. It may have been done. In this case, the other layer may be composed of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties and the like to the laminated bodies 100 to 400 without hindering the incident of light on the adhesive layer 3. The wavelength of light that can be used differs depending on the type of material constituting the adhesive layer 3. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from the materials transmitting light having a wavelength capable of altering the material constituting the adhesive layer 3.

(Manufacturing method of laminated body (1))
The method for producing a laminate according to a third aspect of the present invention is a method for producing a laminate in which a support that transmits light, an adhesive layer, and a semiconductor substrate are laminated in this order, and the support or the semiconductor substrate is provided with a laminate. A step of applying the adhesive composition according to the first aspect to form an adhesive composition layer (hereinafter, also referred to as an "adhesive composition layer forming step") and a step of forming the semiconductor substrate on the support. The adhesive composition layer is cured by a step of placing the adhesive composition layer via the adhesive composition layer (hereinafter, also referred to as a “semiconductor substrate mounting step”) and a polymerization reaction of the urethane resin to cure the adhesive layer. (Hereinafter, also referred to as an “adhesive layer forming step”).

5 to 6 are schematic process diagrams illustrating one embodiment of the method for manufacturing a laminated body according to the present embodiment.
5 (a) to 5 (b) are views for explaining the manufacturing process of the laminate 100'in which the support 1, the adhesive composition layer 3', and the semiconductor substrate 4 are laminated in this order. FIG. 5A is a diagram illustrating an adhesive composition layer forming step. FIG. 5B is a diagram illustrating a semiconductor substrate mounting process.
FIG. 6 is a diagram illustrating an adhesive layer forming step. The adhesive composition layer 3'in the laminated body 100'is thermoset to form the adhesive layer 3 to obtain the laminated body 100.

[Adhesive composition layer forming step]
The method for producing a laminate according to the present embodiment includes an adhesive composition layer forming step. The adhesive composition layer forming step is a step of applying the adhesive composition to the support or the semiconductor substrate to form the adhesive composition layer.
In FIG. 5A, the adhesive composition layer 3'is formed on the support 1 by using the adhesive composition.

The method for forming the adhesive composition layer 3'on the support 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blades, spray coating, and slit coating.
The adhesive composition layer may be formed on the semiconductor substrate 4 in the same manner.

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

[Semiconductor substrate mounting process]
The method for manufacturing a laminate according to the present embodiment includes a semiconductor substrate mounting step. The semiconductor substrate mounting step is a step of mounting the semiconductor substrate on the support via the adhesive composition layer. As a result, the laminated body 100'can be obtained.
In FIG. 5C, the semiconductor substrate 4 is placed on the support 1 via the adhesive composition layer 3'formed on the support 1.

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

[Adhesive layer forming process]
The method for producing a laminate according to the present embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of curing the inside of the adhesive composition layer to form an adhesive layer. Thereby, the laminated 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 depending on the type of the curing component.

When the curing component is the component (a) above, the curing reaction can be allowed to proceed by heating. The heating temperature can be equal to or higher than the temperature at which the cross-linking reaction of the component (I) and the component (O) is started. For example, when the component (I) contains a blocked polyisocyanate, the heating temperature can be a temperature equal to or higher than the dissociation temperature of the thermally dissociable blocking agent that blocks the isocyanate group in the blocked polyisocyanate. The heating temperature may vary depending on the type of the heat dissociative blocking agent, and examples thereof include 80 ° C. and higher, 100 ° C. and higher, 130 ° C. and higher, and 150 ° C. and higher. The upper limit of the heating temperature is not particularly limited, but from the viewpoint of energy consumption, for example, 350 ° C. or lower, 300 ° C. or lower, 250 ° C. or lower, or the like can be mentioned. Examples of the heating temperature range include 80 to 350 ° C., 100 to 300 ° C., 130 to 300 ° C., 150 to 300 ° C., and the like.
The heating time is not particularly limited as long as it is a time sufficient for thermosetting the components (I) and (O). The heating time can be, for example, 15 minutes or more, 30 minutes or more, 45 minutes or more, and the like. The upper limit of the heating time is not particularly limited, but may be, for example, 120 minutes or less, 100 minutes or less, 80 minutes or less, 60 minutes or less, etc. from the viewpoint of work efficiency and the like. Examples of the heating time range include 15 to 120 minutes, 30 to 120 minutes, 45 to 120 minutes, and the like.

When the curing component is the component (b) and the component (P1) contains a methacryloyl group or an acryloyl group, the curing reaction can be allowed to proceed by heating. Examples of the heating temperature include 80 to 350 ° C., 100 to 300 ° C., 130 to 300 ° C., 150 to 300 ° C., and the like. The heating time is not particularly limited as long as it is a time sufficient for the component (P1) to polymerize and cure. The heating time is, for example, preferably 30 to 180 minutes, more preferably 45 to 120 minutes, and even more preferably 60 to 120 minutes. The curing reaction can be carried out, for example, in a nitrogen atmosphere.

By this step, the component (I) and the component (O) or the component (P1) in the adhesive composition layer 3'are crosslinked and cured, and the adhesive layer 3 which is a cured body of the adhesive composition layer 3' Is formed. As a result, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, the laminated body 100 can be obtained.

[Arbitrary process]
The method for producing a laminate according to the present embodiment may include other steps in addition to the above steps. Other steps include, for example, various mechanical or chemical treatments (thin film treatment such as gliding and chemical mechanical polishing (CMP), high temperature such as chemical vapor deposition (CVD) and physical vapor deposition (PVD)). Treatment under vacuum, treatment with organic solvents, chemicals such as acidic treatment liquids and basic treatment liquids, plating treatment, irradiation with active light, heating / cooling treatment, etc.) can be mentioned.

(Manufacturing method of laminated body (2))
In the method for manufacturing a laminate according to a fourth aspect of the present invention, after obtaining the laminate by the method for producing a laminate according to the third aspect, a member made of a metal or a semiconductor and the member are sealed. It is characterized by further having an electronic device forming step of forming an electronic device, which is a composite of a resin for stopping or insulating.

The laminate obtained by the method for producing a laminate of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order. The laminated body can be obtained by performing an electronic device forming step on the laminated body obtained by the method for producing a laminated body according to the third aspect.

[Electronic device formation process]
The method for producing a laminate according to the present embodiment includes an electronic device forming step. The electronic device forming step is a step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member.
The electronic device forming step can include any of a sealing 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 sealing step. In this case, the electronic device forming step may further include a grinding step and a wiring layer forming step.

-About the sealing process The sealing process is a step of sealing the substrate fixed on the support with a sealing material.
In FIG. 7A, a laminate 110 is obtained in which the entire semiconductor substrate 4 temporarily adhered to the support 1 via the adhesive layer 3 is sealed by the sealing material layer 5.

In the sealing step, for example, a sealing material heated to 130 to 170 ° C. is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity state, and is compression-molded. As a result, a laminated body 110 in which the sealing material layer 5 is provided on the adhesive layer 3 is produced.
At that 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 encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

-About the grinding step The grinding step is a step of grinding the sealing material portion (sealing material layer 5) in the sealing body after the sealing step so that a part of the semiconductor substrate is exposed.
As shown in FIG. 7B, for example, the encapsulant portion is ground by grinding the encapsulant layer 5 to a thickness substantially equal to that of the semiconductor substrate 4.

-About the wiring layer forming step 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, the wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5. As a result, the laminated body 120 can be obtained. In the laminated body 120, the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 constitute an electronic device 456.

Examples of the method for forming the wiring layer 6 include the following methods.
First, a dielectric layer such as silicon oxide (SiO _x ) or a photosensitive resin 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 vapor deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roller blade, spray coating, slit coating or the like. ..

Subsequently, wiring is formed on the dielectric layer with a conductor such as metal. As a method for forming the wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resistography) or an etching process can be used. Examples of such a lithography process include a lithography process using a positive resist material and a lithography process using a negative resist material.

In the method for manufacturing a laminate according to the present embodiment, bumps can be further formed or elements can be mounted on the wiring layer 6. The element can be mounted on the wiring layer 6 by using, for example, a chip mounter or the like.

(Manufacturing method of laminated body (3))
The method for producing a laminated body according to a fifth aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer, and an electronic device are laminated in this order, and the first aspect is described on the support. A step of applying such an adhesive composition to form a layer of the adhesive composition (adhesive composition layer forming step), a member composed of a metal or a semiconductor, and a resin for sealing or insulating the member. An electronic device forming step (electronic device forming step) of forming an electronic device, which is a composite of the above, on the adhesive composition layer, and a step of curing the adhesive composition layer to form an adhesive layer. It is characterized by having (adhesive layer forming step).

The laminate obtained by the method for producing a laminate of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, as in the production method according to the fourth aspect.

In the production method of the present embodiment, the adhesive composition layer forming step can be performed in the same manner as in the production method of the laminate according to the third aspect.

In the manufacturing method of the present embodiment, an electronic device forming step is performed after the adhesive composition layer forming step. Such an electronic device forming step can include a wiring layer forming step. The electronic device forming step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, and the like. Further, the electronic device forming step may be a step in which the semiconductor substrate is placed on the support via the adhesive composition layer of the encapsulant sealed with the encapsulant.

The adhesive layer forming step can be performed in the same manner as in the method for producing a laminate according to the third aspect.

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

According to the method for manufacturing a laminate according to the third to fifth aspects, the support and the semiconductor substrate or the electronic device are temporarily bonded to each other via an adhesive layer having high heat resistance. A laminated body in which the adhesive layer and the semiconductor substrate or the electronic device are laminated in this order can be stably manufactured. Such a laminate is a laminate produced in a process based on a fan-out type technology in which terminals provided on a semiconductor substrate are mounted on a wiring layer extending outside the chip area.

(Manufacturing method of electronic parts)
In the method for manufacturing an electronic component according to a sixth aspect of the present invention, after obtaining a laminated body by the method for manufacturing a laminated body according to any one of the third to fifth aspects, the bonding is performed via the support. A step of separating the electronic device and the support by irradiating the layer with light to alter the adhesive layer (hereinafter, also referred to as a “separation step”) and a urethane bond in the adhesive layer are formed. It is characterized by having a step of removing the adhesive layer (hereinafter, also referred to as "adhesive layer removing step") by decomposing with an acid or an alkali.

FIG. 8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). 8 (a) is a diagram showing the laminated body 120, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining an adhesive removing step.

[Separation process]
The separation step is a step of separating the electronic device 456 and the support 1 by irradiating the adhesive layer 3 with light (arrows) via the support 1 to change the quality of the adhesive layer 3.
As shown in FIG. 8A, in the separation step, the adhesive layer 3 is altered by irradiating the adhesive layer 3 with light (arrows) via the support 1 that transmits light.

The wavelength of light used in the separation step may be selected according to the wavelength of 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.
Type of irradiated light may be appropriately selected depending on the permeability of the support 1, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, a dye laser, Liquid laser, CO ₂ laser, excimer laser, Ar laser, gas laser such as He-Ne laser, laser light such as semiconductor laser and free electron laser, and non-laser light can be used. As a result, the adhesive layer 3 can be altered so that the support 1 and the electronic device 456 can be easily separated.

When irradiating the laser beam, the following conditions can be mentioned as an example of the laser beam irradiation condition.
The average output value of the laser beam is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10000 mm / s or less.

After irradiating the adhesive layer 3 with light (arrows) to alter the adhesive layer 3, the support 1 is separated from the electronic device 456 as shown in FIG. 8 (b).
For example, the support 1 and the electronic device 456 are separated by applying a force in a direction in which the support 1 and the electronic device 456 are separated from each other. Specifically, one of the support 1 or the electronic device 456 side (wiring layer 6) is fixed to the stage, and the other is lifted while being sucked and held by a separation plate provided with a suction pad such as a bellows pad. The support 1 and the electronic device 456 can be separated.
The force applied to the laminated body 200 may be appropriately adjusted depending on the size of the laminated body 200 and the like, and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, 0.1 to 5 kgf (0). By applying a force of about .98 to 49N), the support 1 and the electronic device 456 can be suitably separated.

[Adhesive layer removal process]
The method for manufacturing an electronic component according to the present embodiment includes an adhesive layer removing step. The adhesive layer removing step is a step of decomposing the urethane bond in the adhesive layer with an acid or an alkali to remove the adhesive layer.
In FIG. 8B, the adhesive layer 3 is attached to the electronic device 456 after the separation step. In this step, the adhesive layer 3 is removed by decomposing the adhesive layer 3 with an acid or an alkali to obtain an electronic component 50.

In this step, the urethane bond in the adhesive layer 3 is decomposed with an acid or an alkali. The adhesive layer 3 contains a urethane resin formed by the copolymerization of the component (I) and the component (O), or a crosslinked urethane resin formed by the polymerization of the component (P1). By treating these urethane resins with an acid or an alkali, the urethane bond is broken and decomposed. As a result, the adhesive layer 3 can be decomposed and the residue of the adhesive layer 3 adhering to the electronic device 456 can be removed.

The acid or alkali used in this step is not particularly limited as long as it can decompose the urethane bond. Examples of the acid capable of decomposing the urethane bond include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of alkalis capable of decomposing urethane bonds include, but are not limited to, inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine.

The acid or alkali can be dissolved in a solvent and used as a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, and examples thereof include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, and propylene glycol.
The adhesive removing treatment liquid may contain a known additive such as a surfactant in addition to the above components.
The content of the acid or alkali in the treatment liquid is not particularly limited, and examples thereof include 1 to 50% by mass. The content of the polar solvent in the treatment liquid is 50 to 99% by mass.
As the treatment liquid for removing the adhesive layer, a commercially available alkaline treatment liquid or acid treatment liquid may be used. Examples of commercially available treatment solutions include ST-120 and ST-121 (both manufactured by Tokyo Ohka Kogyo Co., Ltd.).
By bringing the above-mentioned treatment liquid containing an acid or an alkali into contact with the adhesive layer 3, the urethane bond in the adhesive layer 3 is decomposed, and the adhesive layer 3 can be removed.

In the method for manufacturing an electronic component of the present embodiment, after the above-mentioned adhesive layer removing step, the electronic component 50 may be further subjected to a treatment such as solder ball formation, dicing, or oxide film formation.

According to the method for producing an electronic component according to the present embodiment, (a) a light absorber, a polyisocyanate, and a polyol, or (b) a light absorber, a urethane resin containing a polymerizable carbon-carbon double bond, and polymerization. By curing the adhesive composition using the adhesive composition containing the initiator, the semiconductor substrate or the like and the support are temporarily bonded. Therefore, it is possible to form an adhesive layer having high heat resistance that can withstand high temperature treatment in an electronic device forming process or the like.
Further, since the adhesive composition contains a light absorber, the adhesive layer is denatured and the adhesive strength is lowered by irradiating with light. Therefore, even if there is no separation layer, the temporarily bonded semiconductor substrate or the like and the support can be easily separated.
Further, the residue of the adhesive layer attached to the semiconductor substrate or the like separated from the support can be easily removed by decomposing the urethane bond in the adhesive layer with an acid or an alkali.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

<Synthesis example of urethane resin ((P1) component)>
Propylene glycol monomethyl ether acetate (PGMEA), 36 parts of castor oil modified diol, 17 parts of polycarbonate diol (Mw1,000), 18 parts of pentaerythritol diacrylate, neo in a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer. One part of pentyl glycol and a prohibiting agent were added, and the mixture was uniformly mixed under a nitrogen stream. Next, 7 parts of diphenylmethane diisocyanate (MDI) and 21 parts of hydrogenated xylylene diisocyanate (H6XDI) were charged into a dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was performed for 4 to 5 hours. Then, 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 urethane resin (P1) -1 (molecular weight of urethane resin per equivalent of polymerizable carbon-carbon double bond) is 600 g / eq. Met.

The polycarbonate diol (Mw1,000) used in the synthesis of the urethane resin (P1) -1 is a polycarbonate diol represented by the following formula (PC-1-1) (R =-(CH ₂ ) _6-. ,-(CH ₂ ) _5- ).

<Preparation of adhesive composition>
(Examples 1 to 6, Comparative Example 1)
The components shown in Table 1 were mixed to prepare the adhesive compositions of each example. More specifically, it was prepared as follows. First, the components (P1), (A), (Ad), and (S) were mixed in the blending amounts shown in Table 1. Next, the component (B) was added in the proportions shown in Table 1 and mixed so that the entire composition became uniform.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass). The value of wt% in () is the ratio (mass%) of the pigment solid content to the total mass (100% by mass) of the adhesive composition.
(P1) -1: Urethane resin (P1) -1 synthesized in the above synthesis example.
(A) -1: Peroxide (Park Mill (registered trademark) D, NOF CORPORATION).
(Ad) -1: Polyester-modified polydimethylsiloxane (BYK-310 (trade name), Big Chemie).
(S) -1: PGMEA.
(B) -1: Carbon black (acrylic resin dispersed volume average particle diameter 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 applied onto the bare glass support by the spin coater method. It was cured by heating at 180 ° C. for 1 hour in an oven under a nitrogen atmosphere to form adhesive layers having the film thicknesses shown in Table 2. The transmittance of light having a wavelength of 532 nm was evaluated by irradiating the adhesive layer with light having a wavelength of 380 to 780 nm using a spectroscopic analysis measuring device UV-3600 (manufactured by Shimadzu Corporation). The results are shown in Table 2.

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

≪Evaluation of detergency≫
The adhesive composition of Example 6 was applied onto a glass support (size diameter 30 cm, thickness 700 μm) by the spin coater method. An adhesive layer (thickness 18 μm) was formed by heating and curing at 180 ° C. for 1 hour in an oven under a nitrogen atmosphere. The support on which the adhesive layer has been formed is subjected to a treatment solution (tetramethylammonium hydroxide (TMAH) is a mixed solvent of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and propylene glycol (PG) at 50 ° C. It was treated with NMP: DMS: PG = 10: 78: 12 (mass ratio)) diluted at a concentration of 2% by mass), and the time for complete dissolution was measured. The dissolution rate of the adhesive layer was calculated from the dissolution time with respect to the film thickness. If the dissolution rate is 50 nm / sec or more, the detergency is judged to be good.
The dissolution rate of the adhesive layer was 70 nm / sec. Therefore, it was confirmed that the detergency of the adhesive layer formed by using the adhesive composition of Example 6 was good.

1 Support 3 Adhesive layer 3'Adhesive composition layer 4 Semiconductor substrate 5 Encapsulant layer 6 Wiring layer 20 Laminated body 50 Electronic components 100 Laminated body 100' Laminated body 110 Laminated body 120 Laminated body 200 Laminated body 300 Laminated body 400 Laminate 456 Electronic Device 645 Electronic Device

Claims (7)

An adhesive composition used for forming an adhesive layer that temporarily adheres a semiconductor substrate or an electronic device to a support that transmits light .
(B) a light absorbing agent, polymerizable carbon - urethane resin containing a carbon double bond, and containing a thermally polymerization initiator, the adhesive composition. Before SL urethane resin, a reaction product of a polyol and a polyisocyanate,
At least one of the polyol and the polyisocyanate comprises the polymerizable carbon-carbon double bond.
The adhesive composition according to claim 1. The electronic device is characterized in that a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member is laminated on the support via the adhesive layer. The adhesive composition according to claim 1 or 2. A laminate in which a support that transmits light, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order.
The adhesive layer is a cured product of the adhesive composition according to any one of claims 1 to 3.
Laminated body. A method for manufacturing a laminated body in which a support that transmits light, an adhesive layer, and a semiconductor substrate are laminated in this order.
A step of applying the adhesive composition according to any one of claims 1 to 3 to the support or a semiconductor substrate to form an adhesive composition layer.
A step of placing the semiconductor substrate on the support via the adhesive composition layer, and
A step of heating and curing the adhesive composition layer to form the adhesive layer, and
A method for producing a laminated body. After obtaining a laminate by the method for producing a laminate according to claim 5, an electronic device is formed which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Further has the process of
A method for manufacturing a laminated body in which a support that transmits light, an adhesive layer, and an electronic device are laminated in this order. After obtaining the laminate by the method for producing the laminate according to claim 6,
A step of separating the electronic device from the support by irradiating the adhesive layer with light through the support to alter the adhesive layer.
A step of removing the adhesive layer adhering to the electronic device by decomposing the urethane bond in the adhesive layer with an acid or an alkali.
A method for manufacturing electronic components.

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