TW201801906A - Laminate manufacturing method and application thereof to produce a laminate having high heat resistance and capable of adequately removing an adhesive layer by grinding - Google Patents

Abstract

The subjective of this invention is to produce a laminate having high heat resistance and capable of adequately removing an adhesive layer by grinding. The solution of the laminate manufacturing method comprises the following steps: an adhesive layer forming step for forming an adhesive layer (3) on a substrate (1); a lamination step for laminating the substrate (1) and a support plate (2); and a curing step of curing the adhesive layer (3) for heating a polymerizable resin ingredient to polymerize. The cured adhesive layer (3) has a Young's modulus of 2 GPa or more at 25 DEG C and a dynamic viscosity of 1000 Pa·s or more at 250 DEG C.

Description

Laminated manufacturing method and use thereof

The present invention relates to a method for manufacturing a laminate and its use.

As a semiconductor package (semiconductor device) including a semiconductor element (electronic component), a WLP (Wafer Level Package) is known. Semiconductor packages such as WLP and PLP (Panel Level Package) are known as fan-in WLP (Fan-in Wafer Level Package), etc., in which the terminals at the bare die end are relocated in the chip area. Fan-in technology and fan-out technology such as fan-out type WLP (Fan-out Wafer Level Package) in which terminals are relocated outside the chip area. In particular, the fan-out technology is a fan-out panel level package (PLP) in which semiconductor elements are arranged on a panel and packaged. In order to achieve the integration, thinness, and miniaturization of semiconductor devices, such as These fan-out technologies have attracted much attention.

For example, Patent Document 1 describes a method of transmitting light. The support and the semiconductor wafer are bonded together via a light-to-heat conversion layer and an adhesive layer provided on the support side. After the semiconductor wafer is processed, radiation is radiated from the support side to decompose the light-to-heat conversion layer, and the semiconductor wafer is decomposed. Method for separating self-supporting body.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-64040 (published on February 26, 2004)

The technique described in Patent Document 1 is to form a laminate including an adhesive layer formed using a mechanically peelable adhesive, and to process a substrate. Therefore, when the substrate is processed under high temperature conditions, there is a problem that the adhesion between the adhesive layer and the substrate cannot be maintained. In addition, Patent Document 1 does not disclose any method for manufacturing a laminated body having a bonding layer that can be removed well by grinding.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a method for producing a laminate having high heat resistance and capable of removing an adhesive layer by grinding, and a related technology.

In order to solve the above-mentioned problems, the method for manufacturing a laminate of the present invention is a method for manufacturing a laminate in which a substrate and a support that supports the substrate are laminated via an adhesive layer, and is characterized by including the following steps: the substrate and the support A bonding layer forming step of forming the bonding layer containing a polymerizable resin component and a polymerization initiator on at least one of the substrates, a laminating step of laminating the substrate and the support through the bonding layer, and heating Or the hardening step of polymerizing the polymerizable resin component by exposure to harden the adhesive layer, and the Young's modulus of the cured adhesive layer at 25 ° C is 2 GPa or more, and the dynamic viscosity at 250 ° C is 1000 Pa. s or more.

The laminated body of the present invention is a laminated body in which a substrate and a support for supporting the substrate are laminated via an adhesive layer, wherein the adhesive polymerizable resin component of the adhesive layer is polymerized by using heat or light. The hardened product polymerized by the polymerization initiator, the Young's modulus of the above adhesive layer at 25 ° C is 2 GPa or more, and the dynamic viscosity at 250 ° C is 1000 Pa. s or more.

In addition, the adhesive composition of the present invention is an adhesive composition for forming an adhesive layer in a laminate in which a substrate and a support for supporting the substrate are laminated via an adhesive layer, and is characterized by containing a polymerizable property. A resin component and a polymerization initiator that starts polymerization by heat or light. The cured product of the polymerizable resin component polymerized by the polymerization initiator has a Young's modulus at 25 ° C of 2 GPa or more, at 250 GPa. The dynamic viscosity at ℃ is 1000Pa. s or more.

According to the present invention, it is possible to exert the effect of providing a method of manufacturing a laminated body having high heat resistance and a good removal of the adhesive layer by grinding, and related technologies.

1‧‧‧ substrate

2‧‧‧ support plate

3‧‧‧ Adjacent layer

4‧‧‧ separation layer

5‧‧‧ redistribution layer

6‧‧‧sealing material

7‧‧‧Sealed substrate

20‧‧‧Grinding machine

30, 31, 32‧‧‧ laminated

FIG. 1 is a diagram illustrating the outline of a method for manufacturing a laminated body and a method for processing a substrate according to an embodiment (first embodiment) of the present invention.

FIG. 2 is a diagram illustrating the outline of a method for manufacturing a laminated body and a substrate processing method according to another embodiment (second embodiment) of the present invention.

FIG. 3 is a schematic diagram illustrating a method for manufacturing a laminate and a method for processing a substrate according to a modification of the present invention.

The manufacturing method of the laminated body of the present invention is to make the Young's modulus of the adhesive layer after hardening at 25 ° C is 2 GPa or more, and the dynamic viscosity at 250 ° C is 1000 Pa. The method of laminated body above s.

Thereby, it is possible to form a laminate having high heat resistance and capable of removing the adhesive layer by grinding, and to perform various processes on the substrate. Therefore, for example, based on a so-called fan-in technology, a sealing substrate including an element, a sealing element, and a Si interposer (silicon wafer) on which the element is mounted can be preferably manufactured. In addition, based on the so-called fan-out technology, a sealing substrate including an element, a sealing material for a sealing element, and a redistribution layer can be manufactured satisfactorily.

<Manufacturing method of laminated body (first embodiment)>

The manufacturing method of the laminated body of one Embodiment (1st Embodiment) of this invention is demonstrated in detail using (a)-(c) of FIG. The manufacturing method of the laminated body of this embodiment includes a separation layer formation step, a subsequent layer formation step, a hardening step, and a lamination step. In addition, if the separation layer formation step (FIG. 1 (a)) and the subsequent layer formation step (FIG. 1 (b)) precede the lamination step and the hardening step (FIG. 1 (c)), either It can be done simultaneously or simultaneously. In this embodiment, the curing step is performed after the lamination step.

[Separation layer forming step]

As shown in FIG. 1 (a), in the separation layer forming step, a separation layer 4 which is deteriorated by irradiation of light is formed on a flat portion of a support plate 2 through which light can pass.

[Support plate 2]

The support plate (support body) 2 is a support body that supports the substrate 1. Therefore, as the support plate 2, as long as the substrate 1 is thinned, transported, and mounted, it has the strength necessary to prevent the substrate 1 from being damaged or deformed. In addition, the support plate 2 may be used so long as it allows the light of the separation layer 4 to deteriorate. From these viewpoints, a support made of glass, silicon, or acrylic resin can be used as the support plate 2.

[Separation layer 4]

The separation layer 4 is a layer that is deteriorated by irradiation with light. By irradiating the separation layer 4 with light through the support plate 2 to modify the separation layer 4, the support plate 2 can be separated from the substrate 1.

In the present specification, the term "deterioration" means a state in which the separation layer can be broken by a slight external force, or a phenomenon in which the adhesion force of the layer in contact with the separation layer is reduced. As a result of the deterioration of the separation layer due to the absorption of light, the separation layer loses its strength or adhesion before receiving light irradiation. Eventually, the separation layer becomes brittle by absorbing light. The so-called metamorphism of the separation layer may be the decomposition of the separation layer due to the absorbed light energy, the change in the three-dimensional configuration, or the dissociation of functional groups. The metamorphism of the separation layer is caused by the absorption of light.

Therefore, for example, only the support plate is pulled up and the separation layer is deteriorated as if destroyed, and the support plate and the substrate can be easily separated. More specifically, for example, one of the substrate and the support plate in the laminate is fixed to a mounting table by a support separation device or the like, and the other is held by an adsorption pad (adsorption section) having an adsorption means and the like, and Pull up to separate the support plate from the substrate, or the chamfered part of the end face of the peripheral portion of the support plate is held by a separation plate with a clamp (claw) or the like to apply force, and the substrate and the support plate can be separated. . In addition, for example, a support separation device provided with a peeling means for supplying a peeling liquid for peeling the adhesive may peel the support plate from the substrate of the laminate. By this peeling means, a peeling liquid is supplied to at least a part of the peripheral end portion of the adhesive layer of the laminate to swell the adhesive layer of the laminate. After the adhesive layer is swollen, the substrate can be concentrated on the separation layer by force. Apply force to the support plate. Therefore, the substrate can be better separated from the support plate.

The force to be applied to the laminated body may be adjusted as appropriate according to the size of the laminated body, and is not limited. For example, if the laminated body has an area of about 40,000 to 70,000 mm ² , a force of about 0.1 to 5 kgf may be used. Ground to separate the substrate from the support plate.

Further, another layer may be further formed between the separation layer 4 and the support plate 2. In this case, the other layers may be made of a light-transmissive material. This makes it possible to appropriately add a layer having better properties and the like without hindering the light from entering the separation layer 4. The usable light wavelength varies depending on the kind of material constituting the separation layer 4. Therefore, it is not necessary for the materials constituting the other layers to transmit all light, but it is possible to appropriately select from materials that can transmit light of a wavelength capable of deteriorating the material constituting the separation layer 4.

The separation layer 4 is preferably formed only of a material having a structure that absorbs light, but the separation layer 4 may be formed by adding a material that does not have a structure that absorbs light to the extent that the essential characteristics of the present invention are not impaired. In addition, the surface of the separation layer 4 facing the side of the adhesive layer 3 is preferably flat (no unevenness is formed), so that the formation of the separation layer 4 can be easily performed, and uniform adhesion can also be performed at the time of attachment.

The method for forming the separation layer 4 on the support plate 2 may be appropriately selected in accordance with the material of the separation layer to be used. For example, the composition for forming the separation layer may be applied by a conventional method such as a spin coating method. The form may be a form formed by a chemical vapor growth (CVD) method or the like.

The thickness of the separation layer 4 is preferably in a range of, for example, 0.05 μm or more and 50 μm or less, and more preferably in a range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer 4 is limited to a range of 0.05 μm or more and 50 μm or less, Then, by short-time light irradiation and low-energy light irradiation, the separation layer 4 can have a desired deterioration. The thickness of the separation layer 4 is preferably limited to a range of 1 μm or less from the viewpoint of productivity.

The materials used to form the separation layer 4 are described in detail below.

(Fluorocarbon)

The separation layer 4 may be formed of fluorocarbon. Since the separation layer 4 is made of fluorocarbon, it can be deteriorated by absorbing light, and as a result, the strength or adhesiveness before receiving light irradiation is lost. Therefore, a slight external force (for example, pulling up the support plate 2 or the like) can break the separation layer 4, and the support plate 2 can be easily separated from the substrate 1. The fluorocarbon constituting the separation layer 4 can be preferably formed into a film by a plasma CVD (chemical vapor deposition) method.

Fluorocarbon, depending on its type, can absorb light with a wavelength in its inherent range. By irradiating the separation layer 4 with light having a wavelength in a range absorbed by the fluorocarbon used in the separation layer 4, the fluorocarbon can be appropriately modified. The light absorption rate of the separation layer 4 is preferably 80% or more.

As the light irradiated to the separation layer 4, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or an optical fiber laser is appropriately used depending on the wavelength that can be absorbed by the fluorocarbon. Liquid lasers such as pigment lasers, gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, etc. Laser light is sufficient. The wavelength at which the fluorocarbon can be deteriorated is not limited to these, and a wavelength in a range of 600 nm or less can be used, for example.

(The repeating unit contains a polymer having a light absorbing structure)

The separation layer 4 may contain a polymer having a light-absorbing structure in its repeating unit. The polymer is deteriorated upon exposure to light. The deterioration of the polymer is caused by the above structure absorbing the irradiated light. As a result of the deterioration of the polymer, the separation layer 4 loses its strength or adhesiveness before receiving light irradiation. Therefore, a slight external force (for example, pulling up the support plate 2 or the like) can break the separation layer 4, and the support plate 2 can be easily separated from the substrate 1.

The aforementioned structure having light absorption is a chemical structure that absorbs light and deteriorates a polymer containing the structure as a repeating unit. This structure is, for example, a conjugated π-electron-containing atomic group formed of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocyclic ring. More specifically, the structure may be a cardo structure, or a benzophenone structure, a diphenylsulfide structure, a diphenylfluorene structure (bisphenylfluorene structure), Diphenyl structure or diphenylamine structure.

When the structure is present in the polymer side chain, the structure can be represented by the following formula.

(Wherein R is independently alkyl, aryl, halo, hydroxy, keto, fluorenyl, fluorenyl, or N (R ⁴ ) (R ⁵ ) (here, R ⁴ and R ⁵ are each independently A hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is -CO-, -SO _2- , -SO-, or -NH-, and n is an integer of 0 or 1 to 5).

In addition, the polymer contains, for example, a repeating unit represented by any one of (a) to (d) in the following formula, or a structure represented by (e) or containing (f) in its main chain.

(In the formula, l is an integer of 1 or more, m is an integer of 0 or 1 to 2, and X in (a) to (e) is any one of the formulas shown in "Chemical 1" above, in ( f) is any one of the formulas shown in "Chemical Formula 1" above, or does not exist, and Y ₁ and Y ₂ are each independently -CO- or -SO _2- , and 1 is preferably an integer of 10 or less).

Examples of the benzene ring, condensed ring, and heterocyclic ring shown in the above “Chem. 1” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthyl, substituted naphthyl, Anthracenyl, substituted anthracenyl, anthraquinone, substituted anthraquinone, acridine, substituted acridine, azobenzene, substituted azobenzene, fluorescent, substituted fluoramine, fluorimon, substituted fluorimon, carbazole , Substituted carbazole, N-alkylcarbazole, benzofuran, substituted benzofuran, phenanthrene, substituted phenanthrene, fluorene, and substituted fluorene. When the exemplified substituent further has a substituent, the substituent is selected from, for example, an alkyl group, an aryl group, a halogen atom, an alkoxy group, a nitro group, an aldehyde, a cyano group, a sulfonylamine, a dialkylamino group, and a sulfonium Amines, amines, carboxylic acids, carboxylic acid esters, sulfonic acids, sulfonic acid esters, alkylamines and arylamines.

Among the substituents represented by the above-mentioned "Chem. 1", examples of the case where the fifth substituent having two phenyl groups and Z is -SO ₂ -are bis (2,4-dihydroxyphenyl) fluorene, Bis (3,4-dihydroxyphenyl) fluorene, bis (3,5-dihydroxyphenyl) fluorene, bis (3,6-dihydroxyphenyl) fluorene, bis (4-hydroxyphenyl) fluorene, bis (3-hydroxyphenyl) fluorene, bis (2-hydroxyphenyl) fluorene, and bis (3,5-dimethyl-4-hydroxyphenyl) fluorene.

Among the substituents represented by the above-mentioned "Chem. 1", examples of the case where the fifth substituent having two phenyl groups and Z is -SO- are bis (2,3-dihydroxyphenyl) sulfenyl, Bis (5-chloro-2,3-dihydroxyphenyl) fluorene, bis (2,4-dihydroxyphenyl) fluorene, bis (2,4-dihydroxy-6-methylphenyl) fluorene , Bis (5-chloro-2,4-dihydroxyphenyl) fluorene, bis (2,5-dihydroxyphenyl) fluorene, bis (3,4-dihydroxyphenyl) fluorene, bis (3 , 5-dihydroxyphenyl) fluorene, bis (2,3,4-trihydroxyphenyl) fluorene, bis (2,3,4-trihydroxy-6-methylphenyl) -fluorene, bis (5-chloro-2,3,4-trihydroxyphenyl) fluorene, bis (2,4,6-trihydroxyphenyl) fluorene, and bis (5-chloro-2,4,6-trihydroxy) Phenyl) sulfene and the like.

Among the substituents represented by the above-mentioned "Chem. 1", as an example when the fifth substituent having two phenyl groups and Z is -C (= O)-, 2,4-dihydroxybenzophenone is listed. , 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy- 4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4 -Amino-2'-hydroxybenzophenone, 4-dimethylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamine -4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone, and 4-dimethylamino-3', 4 '-Dihydroxybenzophenone and the like.

When the structure exists in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer 4 is within a range of 0.001% to 10%. When the polymer is prepared so that the ratio is limited to the range, the separation layer 4 can sufficiently absorb light and can be surely and rapidly deteriorated. That is, the support plate 2 can be easily removed from the substrate 1, and the light irradiation time necessary for the removal can be shortened.

The above-mentioned structure can absorb light having a wavelength in a desired range depending on the selection of its kind. For example, the wavelength of light that can be absorbed by the structure is more preferably within a range of 100 nm to 2000 nm. In this range, the wavelength of the light that can be absorbed by the structure is on the shorter wavelength side, for example, in the range of 100 nm or more and 500 nm or less. For example, the structure described above can preferably deteriorate a polymer containing the structure by absorbing ultraviolet light having a wavelength in a range of approximately 300 nm to 370 nm.

The light that can be absorbed by the above structure is, for example, from a high-pressure mercury lamp (wavelength: 254 nm or more and 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F ₂ excimer laser ( Wavelength: 157nm, XeCl laser (wavelength: 308nm), XeF laser (wavelength: 351nm) or solid UV laser (wavelength: 355nm), or g-line (wavelength: 436nm), h-line (wavelength : 405 nm) or i-line (wavelength: 365 nm).

The separation layer 4 contains a polymer including the structure as a repeating unit, but the separation layer 4 may further contain a component other than the polymer. This component is exemplified by a filler, a plasticizer, and a component capable of improving the peelability of the support plate 2. These components are appropriately selected from the conventionally known substances or materials that do not hinder the light absorption by the above-mentioned structure and the deterioration of the polymer or can promote the absorption and deterioration.

(Inorganic)

The separation layer 4 may be made of an inorganic substance. The separation layer 4 is made of an inorganic substance, and can be deteriorated by absorbing light. As a result, the strength or adhesiveness before receiving light irradiation is lost. Therefore, the separation layer 4 can be broken by applying a slight external force (for example, pulling up the support plate 2 and the like), and the support plate 2 and the substrate 1 can be easily separated.

The inorganic substance may have a structure that is deteriorated by absorbing light. For example, one or more inorganic substances selected from the group consisting of a metal, a metal compound, and carbon may be used as appropriate. The metal compound means a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. Examples of the inorganic substance are not limited thereto, and examples thereof include a group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more selected inorganic substances. In addition, the so-called carbon is also a concept that can include carbon isotopes, and examples thereof include diamond, fullerene, diamond-like carbon, and carbon nanotubes.

The inorganic substance absorbs light having a wavelength in an inherent range depending on the type. By irradiating the separation layer 4 with wavelength light in a range absorbed by the inorganic substance used in the separation layer 4, the inorganic substance can be appropriately modified.

As the light irradiating the separation layer 4 made of an inorganic substance, as long as it corresponds to a wavelength that the inorganic substance can absorb, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and an optical fiber are appropriately used. Solid lasers such as lasers, liquid lasers such as pigment lasers, gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, and other laser light , Or non-laser light.

The separation layer 4 made of an inorganic substance can be formed on the support plate 2 by conventional techniques such as sputtering, chemical vapor deposition (CVD), electroplating, plasma CVD, and spin coating. The thickness of the separation layer 4 made of an inorganic substance is not particularly limited as long as it is a film thickness that can sufficiently absorb the light used, but it is more preferably a film thickness in the range of 0.05 μm or more and 10 μm or less, for example. In addition, an adhesive may be applied to both sides or one side of an inorganic film (for example, a metal film) made of an inorganic substance constituting the separation layer 4 in advance, and the adhesive may be attached to the support plate 2.

When a metal film is used as the separation layer 4, The film quality of 4, the type of laser light source, and laser output conditions can cause laser reflection or charge the film. Therefore, it is preferable to implement such countermeasures by arranging an antireflection film or an antistatic film on or under the separation layer 4 or on one side thereof.

(Compound with infrared absorbing structure)

The separation layer 4 may be formed of a compound having a structure having infrared absorption. This compound deteriorates by absorbing infrared rays. As a result of the deterioration of the compound, the separation layer 4 loses its strength or adhesiveness before receiving infrared radiation. Therefore, the separation layer 4 can be broken by applying a slight external force (for example, pulling up the support plate 2 or the like), and the support plate 2 can be easily separated from the substrate 1.

The structure having an infrared absorbing structure or a compound containing a structure having an infrared absorbing property may be, for example, an alkane, an olefin (vinyl, trans, cis, vinylene, tri-substituted, tetra-substituted, conjugated, cumulene) , Cyclic), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohols and phenols (free OH, intramolecular hydrogen bonding, intermolecular hydrogen bonding, Saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, ethylene oxide cyclic ether, peroxide ether, ketone Type, dialkylcarbonyl, aromatic carbonyl, enol of 1,3-dione, o-hydroxyaryl ketone, dialkylaldehyde, aromatic aldehyde, carbonic acid (dimer, carbonic acid anion), formate , Acetate, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic hydrochloride, aromatic hydrochloride, acid anhydride (conjugated, non-conjugated (Yoke, cyclic, acyclic), primary amine, secondary amine, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary (Aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carboxyimine, aliphatic isonitrile, aromatic isonitrile, isocyanate, Thiocyanate, aliphatic isothiocyanate, aromatic isothiocyanate, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosoamine, nitrate, nitrous acid Esters, nitroso bonds (aliphatic, aromatic, monomers, dimers), thiols and thiophenes, and sulfur compounds such as thioglycolic acid, thiocarbonyl, fluorene, sulfonium, sulfonium chloride, primary sulfonamide , Secondary sulfonamide, sulfate, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O, or halogen), PA ² bond (A ² is H, C, or O), or Ti- O key.

Examples of the structure including the above carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF _2- , -CF ₃ , -CH = CF ₂ , -CF = CF ₂ , fluorinated aromatic compound. And chlorinated aryl.

The above Si-A ¹ bond-containing structures are listed as SiH, SiH ₂ , SiH ₃ , Si-CH ₃ , Si-CH _2- , Si-C ₆ H ₅ , SiO-aliphatic, Si-OCH ₃ , Si-OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ , and SiF ₃ . The structure containing the Si-A ¹ bond is preferably a siloxane skeleton and a silsesquioxane skeleton.

The structures containing the PA ² bond are listed as PH, PH ₂ , P-CH ₃ , P-CH _2- , PC ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic), (A ⁴ O ) ₃ -PO (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH and O = P-OH.

The above structure can be absorbed according to the choice of its type. Infrared with a desired wavelength. Specifically, the infrared light that can be absorbed by the structure has a wavelength of, for example, 1 μm or more and 20 μm or less, and can be better absorbed in a range of 2 μm or more and 15 μm or less. When the structure is a Si—O bond, a Si—C bond, or a Ti—O bond, the structure may be in a range of 9 μm or more and 11 μm or less. In addition, those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each structure. For example, the absorption band in each structure can refer to the non-patent literature: SILVERSTEIN. BASSLER. MORRILL, "The Identification Method by the Spectra of Organic Compounds (Fifth Edition)-MS, IR, NMR, and UV-" (published in 1992) pages 146 to 151.

The compound having an infrared-absorbing structure for forming the separation layer 4 is not particularly limited as long as it is a compound having the structure as described above, which is soluble in the solvent used for coating and which can be cured to form a solid layer. However, in terms of effectively deteriorating the compounds in the separation layer 4 and making it easy to separate the support plate 2 from the substrate 1, it is preferable to increase the absorption of infrared rays in the separation layer 4, that is, when the separation layer 4 is irradiated with infrared rays The infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 4 is preferably less than 90%, and the infrared transmittance is more preferably less than 80%.

If an example is given, as the compound having a siloxane skeleton, for example, a resin of a copolymer represented by a repeating unit represented by the following chemical formula (RL1) and a repeating unit represented by the following chemical formula (RL2), or a resin represented by the following chemical formula (RL1) 1) Resin of a copolymer represented by a repeating unit and a repeating unit derived from an acrylic compound.

(In the chemical formula (RL2), R ⁶ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms).

Among them, the compound having a siloxane skeleton is more preferably a tertiary butyl styrene (TBST) -dimethyl copolymer of a repeating unit represented by the aforementioned chemical formula (RL1) and a repeating unit represented by the following chemical formula (RL3) The siloxane copolymer is more preferably a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (RL2) and a repeating unit represented by the following chemical formula (RL3) at 1: 1.

In addition, as the compound having a silsesquioxane skeleton, for example, a repeating unit represented by the following chemical formula (RL4) and the following chemical formula can be used. (RL5) Resin of a copolymer of a repeating unit.

(In Chemical Formula (RL4), R ⁷ is hydrogen or an alkyl group having 1 or more and 10 carbon atoms, and in Chemical Formula (RL5), R ⁸ is an alkyl group having 1 or more and 10 carbon atoms or phenyl group)).

In addition to the compound having a silsesquioxane skeleton, Japanese Patent Application Laid-Open No. 2007-258663 (published on October 4, 2007) and Japanese Patent Application Laid-Open No. 2010-120901 (2010) Published on March 3), Japanese Patent Laid-Open Publication No. 2009-263316 (published on November 12, 2009) and Japanese Patent Laid-Open Publication No. 2009-263596 (published on November 12, 2009) Resin.

Among them, the compound having a silsesquioxane skeleton is more preferably a copolymer represented by a repeating unit represented by the following chemical formula (RL6) and a repeating unit represented by the following chemical formula (RL7), and more preferably contains the following chemical formula by 7: 3 (RL6) Repeat unit and the following chemical formula Copolymer of repeating units represented by (RL7).

The polymer having a silsesquioxane skeleton has a random structure, a step structure, and a cage structure, and can be any structure.

Examples of the compounds containing a Ti-O bond include (i) tetra-isopropyl titanium oxide, tetra-n-butyl titanium oxide, titanium (2-ethylhexyloxy) titanium, and isopropyl titanium oxide octanediol. Titanium alkoxide, (ii) di-isopropoxy. Chelated titanium, such as bis (ethylfluorenylacetone) titanium and propanedioxytitanium bis (ethylethylfluorenyl acetate), (iii) iC ₃ H ₇ O-[-Ti (OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ and nC ₄ H ₉ O-[-Ti (OnC ₄ H ₉ ) ₂ -O-] _n -nC ₄ H ₉ and other titanium polymers, (iv) tri- Titanium n-butoxy monostearate, titanium stearate, titanium diisopropoxy diisostearate, and (2-n-butoxycarbonylbenzyloxy) tributoxide, etc. Titanium, (v) di-n-butoxy. Water-soluble titanium compounds such as bis (triethanolamine) titanium.

Among them, the compound containing a Ti-O bond is preferably di-n-butoxy. Bis (triethanolamine) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ ).

The separation layer 4 contains a compound having a structure having infrared absorption, but the separation layer 4 may further contain components other than the above-mentioned compounds. Examples of the components include fillers, plasticizers, and components capable of improving the peelability of the support. These components may be appropriately selected from conventionally known substances or materials that do not hinder infrared absorption by the above-mentioned structure and deterioration of the compound, or promote the absorption and deterioration.

(Infrared absorbing substance)

The separation layer 4 may contain an infrared absorbing substance. The separation layer 4 is constituted by containing an infrared absorbing substance, and can be deteriorated by absorbing light. As a result, the strength or adhesiveness before receiving light irradiation is lost. Therefore, the separation layer 4 can be broken by applying a slight external force (for example, pulling up the support body), and the support plate 2 and the substrate 1 can be easily separated.

The infrared absorbing substance may have a structure that deteriorates by absorbing infrared rays, and for example, carbon black, iron particles, or aluminum particles can be preferably used. The infrared absorbing substance absorbs light having an inherent range of wavelengths according to its type. By irradiating the separation layer 4 with light having a wavelength in a range absorbed by the infrared absorbing substance used in the separation layer 4, the infrared absorbing substance can be deteriorated.

(Reactive polysilsesquioxane)

The separation layer 4 can be formed by polymerizing a reactive polysilsesquioxane. Thereby, the separation layer 4 has high chemical resistance and high heat resistance.

In this specification, the so-called reactive polysilsesquioxane is a polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. The silanol group may condense a functional group capable of forming a silanol group and polymerize each other. In addition, as long as the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, a silsesquioxane skeleton having a random structure, a cage structure, a step structure, or the like can be used.

The reactive polysilsesquioxane preferably has a structure represented by the following formula (RL8).

In the formula (RL8), R "is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms, and more preferably selected from the group consisting of hydrogen and alkyl groups having 1 to 5 carbon atoms. If R "is hydrogen or an alkyl group having 1 to 10 carbon atoms, the reactive polysilsesquioxane represented by formula (RL8) can be condensed well by heating in the separation layer forming step.

In formula (RL8), p is preferably an integer of 1 or more and 100 or less, more preferably an integer of 1 or more and 50 or less. The reactive polysilsesquioxane has a repeating unit represented by the formula (RL8), and can form a higher Si-O bond content and infrared rays (0.78 μm or more and 1000 μm or less), which are better than those formed using other materials. Far-infrared rays (3 μm or more and 1000 μm or less), and further preferably a separation layer 4 having a high absorbance at a wavelength of 9 μm or more and 11 μm or less.

In the formula (RL8), R "is independently an organic group that is the same or different from each other. Here, R is, for example, an aryl group, an alkyl group, and an alkenyl group, and these organic groups may have a substituent.

When R 'is an aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like can be exemplified, and a phenyl group is more preferable. The aryl group can also be bonded to the polysilsesquioxane skeleton through an alkylene group having 1 to 5 carbon atoms.

When R 'is an alkyl group, examples of the alkyl group include a linear, branched or cyclic alkyl group. When R is an alkyl group, the number of carbon atoms is preferably 1 to 15, more preferably 1 to 6. When R is a cyclic alkyl group, it may be an alkyl group having a monocyclic or bicyclic structure.

When R 'is an alkenyl group, as in the case of an alkyl group, linear, branched or cyclic alkenyl groups can be exemplified. The alkenyl group preferably has 2 to 15 carbon atoms, more preferably 2 to 6. When R is a cyclic alkenyl group, the alkenyl group may have a monocyclic or bicyclic structure. Examples of the alkenyl group include a vinyl group and an allyl group.

Examples of the substituent which R 'may have include a hydroxyl group and an alkoxy group. When the substituent is an alkoxy group, a linear or branched chain may be exemplified. The number of carbon atoms in the cyclic or cyclic alkoxy group is preferably 1 to 15, more preferably 1 to 10.

Further, in one aspect, the content of the siloxanes in the reactive polysilsesquioxane is preferably 70 mol% or more and 99 mol% or less, more preferably 80 mol% or more and 99 mol% or less. . If the content of the siloxane in the reactive polysilsesquioxane skeleton is 70 mol% or more and 99 mol% or less, it can be formed by irradiating infrared rays (preferably far infrared rays, and more preferably a wavelength of 9 μm). Above, 11 μm or less), and the separation layer 4 is better deteriorated.

Moreover, in one viewpoint, the weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 or more and 50,000 or less, more preferably 1,000 or more and 10,000 or less. If the weight-average molecular weight (Mw) of the reactive polysilsesquioxane is 500 or more and 50,000 or less, it can be well dissolved in a solvent and can be applied to a support plate.

Examples of commercially available products that can be used as the reactive polysilsesquioxane include, for example, SR-13, SR-21, SR-23, and SR-33 manufactured by Konishi Chemical Industry Co., Ltd.

[Next layer forming step]

As shown in FIG. 1 (b), in the step of forming an adhesive layer, an adhesive layer 3 is formed on a flat portion of the substrate 1 by applying an adhesive composition.

[Substrate 1]

The substrate 1 is supported by the supporting plate 2 and can be used for processes such as thinning and mounting. And the substrate 1 can be used for components such as integrated circuits (bare die) And metal bumps and other structures are installed and sealed with a sealing material. That is, in the manufacturing method of the laminated body of this embodiment, the substrate 1 can typically be a Si interposer (silicon wafer). In addition, as the substrate 1, a substrate made of any material such as a silicon wafer, a ceramic substrate, a thin film substrate, and a flexible substrate used to form a bare crystal can also be exemplified.

[Next to layer 3]

The adhesive layer 3 is a layer for attaching the substrate 1 and the support plate 2, and is formed by coating an adhesive composition containing a polymerizable resin component, a polymerization initiator, and a solvent on a flat surface of the substrate 1. The polymerization initiator contained in the adhesive composition may be a thermal polymerization initiator or a photopolymerization initiator, but is more preferably a thermal polymerization initiator.

As a method for coating the adhesive composition, conventional coating methods such as spin coating, dipping, roll knife, spray coating, and slit coating can be used.

The thickness of the next layer 3 may be appropriately set according to the types of the substrate 1 and the support plate 2 and the processing performed on the substrate 1, but it is preferably within a range of 10 to 150 μm, more preferably within a range of 15 to 100 μm.

In addition, the adhesion layer forming step is performed after the substrate 1 is coated with the adhesive composition, and then the diluent solvent is preferably removed from the adhesive composition in advance. Thereby, in the subsequent hardening step, when the laminate is heated, it is possible to prevent the adhesion between the adhesive layer 3 and the substrate 1 from being lowered due to volatilization of the diluent solvent contained in the adhesive layer. As a method for removing the diluent solvent from the adhesive composition, for example, the temperature can be raised in steps to heat the adhesive layer 3 to remove the diluent solvent. method.

The temperature conditions when the substrate 1 is heated in order to remove the diluent solvent are performed in an attachable area where the substrate 1 and the support plate 2 can be attached via the adhesive layer 3. Here, the term “attachable region” means a temperature region in which a dynamic viscosity is obtained at which an adhesive layer can attach a substrate to a support. For example, in the manufacturing method of the laminated body of this embodiment, the polymerizable resin component contained in the adhesive layer can be polymerized and thickened, and the dynamic viscosity of the adhesive layer shows 1 Pa. A temperature region having a value of s or less is set as an attachable region.

In addition, as a method of removing the diluting solvent from the adhesive layer 3, a method of removing the diluting solvent by placing the substrate 1 in a reduced pressure environment may be exemplified. This makes it possible to remove the diluting solvent from the adhesive layer 3 irrespective of the type of the polymerization initiator. Moreover, by diluting the solvent from the adhesive layer 3 by heating the adhesive layer 3 under a reduced pressure environment.

[Lamination step]

As shown in FIG. 1 (c), the lamination step included in the method for manufacturing the laminated body of this embodiment is to sequentially laminate the substrate 1, the adhesive layer 3, the separation layer 4, and the support plate 2. The laminating step is to attach the adhesive layer 3 formed on the substrate 1 to the support plate 2 in the attachable area. The adhesive composition used in the method for producing a laminated body according to this embodiment is a polymerizable resin component that is polymerized and cured by a polymerization initiator. Therefore, in the attachable area, the dynamic viscosity of the adhesive layer 3 can be 1 Pa. Below s, the adhesive layer 3 formed on the substrate 1 can adhere to the support plate 2 with good wettability, and is also one of the advantages of the method for manufacturing the laminated body of the present invention.

In the laminating step, under a reduced pressure environment, the surface on the substrate 1 where the adhesion layer 3 is formed and the surface on which the separation layer 4 is formed on the support plate 2 are adhered and laminated to be laminated. In the laminating step, the pressure applied when the substrate 1 and the support plate 2 are bonded together may be set appropriately according to the sizes of the substrate 1 and the support plate 2. In addition, when the hardened adhesive layer 3 is formed by a thermal polymerization initiator, for example, the plate member is heated by one of the heating means including a heater and the substrate 1 and the support plate 2 are pressed while the plate member is laminated. After that, a hardening step by heating is quickly performed.

[Hardening step]

The hardening step is a step of polymerizing and curing the polymerizable resin component contained in the adhesive layer 3 by heating or exposing the adhesive layer 3 of the laminate 30 obtained after the laminating step (FIG. 1 (c)).

When the polymerizable resin component is hardened by heating in the hardening step, the temperature and time as hardening conditions may be specified based on the attachable area. That is, in the temperature range above the attachable area, it is preferably heated for 5 to 120 minutes, and more preferably for 10 to 60 minutes. With this, the dynamic viscosity of the adhesive layer 3 containing the polymerizable resin component and the thermal polymerization initiator at 250 ° C or higher can be improved to 1000 Pa. s or more.

In addition, when the polymerizable resin component is hardened by exposure in the hardening step, regardless of temperature conditions, for example, the adhesive layer 3 is exposed through a light-transmissive support plate 2 by an LED lamp or a mercury lamp, and the temperature is 250 ° C or higher. Then the dynamic viscosity of layer 3 was increased to 1000Pa. s or more is sufficient.

<Laminated body 30>

As shown in FIG. 1 (c), the laminated body 30 is formed by laminating the substrate 1 and the support plate 2 via the adhesive layer 3 and the separation layer 4. Adhesive layer 3 of laminate 30 has a dynamic viscosity of 1000 Pa above 250 ° C. High heat resistance above s. Therefore, by performing a thinning step such as thinning the substrate 1, the laminated body 30 can mount components on, for example, a through electrode exposed on a flat portion of the substrate 1 (mounting step), and use an epoxy-based resin or A sealing material such as a silicone resin seals the element (sealing step). Thereby, a sealing substrate can be formed from the substrate 1 well. That is, the method for manufacturing a laminated body according to this embodiment can better manufacture a semiconductor device (electronic part) based on a fan-in WLP (Fan-in Wafer Level Package) technology. Therefore, the laminated body manufactured by the manufacturing method of the laminated body of this invention is also the scope of the present invention.

<Substrate Processing Method (First Embodiment)>

Next, a substrate processing method according to an embodiment (first embodiment) will be described. The substrate processing method of this embodiment includes the steps of manufacturing a laminated body (see (a) to (c) in FIG. 1) of manufacturing the laminated body 30 by the method of manufacturing a laminated body according to an embodiment of the present invention, and after the manufacturing step of the laminated body, The separation layer 4 is deteriorated by irradiating the separation layer 4 with light through the support plate 2, and a separation step of separating the support plate 2 from the substrate 1 ((d) and (e) in FIG. 1). An adhesive layer removing step of removing the residue of the adhesive layer 3 on the substrate 1 side ((f) and (g) in FIG. 1). In addition, the manufacturing steps of the laminate shown in (a) to (c) of FIG. Since the manufacturing method of the laminated body 30 of embodiment is the same, description is abbreviate | omitted.

[Separation step]

As shown in FIG. 1 (d), after the separation step and the laminated body manufacturing step, the separation layer 4 is irradiated with light L through the support plate 2. Thereby, the separation layer 4 of the laminated body 30 is deteriorated, and the support plate 2 can be completely and well separated from the laminated body 30.

In the separation step, the type and wavelength of the light L irradiated to the separation layer 4 may be appropriately selected according to the permeability of the support plate 2 and the material of the separation layer 4. For example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber laser, solid laser, pigment laser, liquid laser, CO ₂ laser, excimer laser, Ar laser, He-Ne laser, etc. Laser, semiconductor laser, free electron laser, etc., or non-laser light. Thereby, the separation layer 4 is modified, and the support plate 2 and the substrate 1 can be easily separated.

In addition, as an example of laser light irradiation conditions when laser light is irradiated, the following conditions can be exemplified, but are not limited thereto: The average output value of the laser light 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 laser light repetition frequency is preferably from 20 kHz to 60 kHz, more preferably from 30 kHz to 50 kHz; The scanning speed of laser light is preferably from 100 mm / s to 10000 mm / s.

Subsequently, as shown in FIG. 1 (e), in the separation step, separation is performed by applying a force in a direction to move the support plate 2 and the substrate 1 away from each other. For example, in a state where one of the support plate 2 and the substrate 1 of the laminate 30 is fixed on a table, the other is adsorbed and held by a separation plate provided with an adsorption pad such as a belly pad. The substrate 1 and the support plate 2 can be separated by pulling up, or by holding a chamfered portion of the end surface of the peripheral portion of the support plate 2 with a separating plate (not shown) provided with a jig (holding member) and pulling up.

[Next layer removal step]

As shown in FIG. 1 (f), in the subsequent layer removing step, the residue of the adhesive layer 3 on the substrate 1 side after the separated support plate 2 is removed by grinding. Here, the Young's modulus at 25 ° C. of the adhesive layer 3 remaining on the substrate 1 side is 2.0 GPa or more. Therefore, it is possible to prevent the grinding meal adhering to the layer 3 from blocking the holes of the grinding device. Therefore, a conventional grinding device used for thinning a silicon wafer (rear-side polishing) in the field of manufacturing a semiconductor device can better grind and remove the residue of the subsequent layer 3.

More specifically, in the adhesive layer removing step, the residue on the adhesive layer 3 on the substrate 1 side is removed by grinding with a grinder 20 including a BG (back surface polishing) wheel or the like. For example, while the substrate 1 is fixed and rotated by a rotating jig, the grinder 20 is brought into contact with the residue of the adhesive layer 3 and rotated, and the residue of the adhesive layer 3 may be ground. Here, the conditions such as the number of rotations of the rotating shaft in the polishing machine 20 can be set according to the conditions generally used in a polishing device for grinding silicon wafers, and as an example, reference can be made to the embodiment of this specification. In addition, the grinder 20 is preferably supplied with grinding water from a rotating shaft portion (not shown) or an external nozzle (not shown) in an amount of 2 to 4 L / min to grind the adhesive layer 3. With these conditions, the maximum current value of the grinder 20 can be set within the range of 5 to 20A according to the grinding and bonding layer 3. Therefore, the residue of the bonding layer 3 can be ground under the same conditions as those for grinding a semiconductor wafer substrate.

<Adhesive composition>

As described above, the method for manufacturing a laminated body according to an embodiment of the present invention can use a dynamic viscosity of 1000 Pa which can be formed above 250 ° C. The adhesive composition of the adhesive layer 3 with a Young's modulus at 25 ° C. of more than s and a curing temperature of 2 GPa or more at 25 ° C. can be preferably implemented from the laminating step to the adhesive layer removing step. In addition, the adhesive layer formed by the adhesive composition of an embodiment can display 1 Pa. The temperature range of the dynamic viscosity below s is set as the attachable area.

The temperature range of the adhesive layer 3 formed by the adhesive composition and the dynamic viscosity at 250 ° C can be measured using a conventional dynamic viscosity measurement device at a frequency of 1Hz and a speed of 5 ° C / min at 40 ° C ~ 300. The temperature was raised in a temperature range of ℃, and the dynamic viscosity (η *) was measured and specified.

Since the adhesive composition of one embodiment forms a cured product by polymerizing a polymerizable resin component, the dynamic viscosity of the adhesive layer in the low-temperature region at the initial stage of dynamic viscosity measurement tends to be low, and during the period up to the high-temperature region It suddenly increases viscosity and shows a tendency of dynamic viscosity to become higher. Therefore, 1Pa can be displayed. The low-temperature region of dynamic viscosity below s is set as the attachable region of layer 3. In addition, in the dynamic viscosity measurement, as the temperature was further increased, the layer 3 hardened and showed 1000 Pa at 250 ° C. Dynamic viscosity above s. In contrast, the use of an adhesive layer of a thermoplastic resin shows 1000 Pa in a low-temperature region at the initial stage of dynamic viscosity measurement. The dynamic viscosity above s shows 1000Pa as the temperature rises further. Trend of dynamic viscosity below s. Therefore, it is necessary to use a thermoplastic resin adhesive layer. To get 1000Pa. The high-temperature region with dynamic viscosity below s is set as the attachable region. That is, the adhesive composition according to one embodiment can adhere the substrate 1 and the support plate 2 at a lower temperature than the adhesive layer formed using a thermoplastic resin, and has good wettability, and further heat can form heat resistance under high temperature conditions. Adhesive layer with high sex.

The Young's modulus of the adhesive layer formed from the adhesive composition can be measured using a conventional elastic modulus measuring device (such as a FISCHERSCOPE Hm2000 measuring device (manufactured by FISCHER INSTRUMENTS)) with a maximum test load: 5 mN, and a load application period: 20 seconds Latent time: 5 seconds at 25 ° C.

The adhesive composition is based on the above-mentioned dynamic viscosity measurement method and Young's modulus evaluation method, and the composition of each polymerizable resin component described in detail below is prepared. The dynamic viscosity of the adhesive layer 3 at 250 ° C. can be set to 1000 Pa. ． s or more and the Young's modulus of the adhesive layer 3 at 25 ° C. is set to 2 GPa or more. In the next layer, in order to make the dynamic viscosity at 250 ° C and the Young's modulus at 25 ° C equal to or more than a specific value, reference is made to, for example, the functional group equivalent of each polymerizable resin component and the number of functional groups per single molecule to adjust the formulation of each resin. Just fine. For example, when a polymerizable resin component having a higher functional group equivalent is used, the adhesive layer tends to have a higher dynamic viscosity at 250 ° C, and a Young's modulus also tends to become higher at 25 ° C. More specifically, for example, when an epoxy resin is used as the polymerizable resin component, if a resin component composition having an epoxy equivalent of 100 g / eq or more is prepared, the dynamic viscosity at 250 ° C. can be 1000 Pa. Adhesive layer having a Young's modulus of 2 GPa or more at s or higher at 25 ° C. When using epoxy, it is better to use functional groups per molecule The number is one or more. Further, for example, when an acrylic polymerizable resin component is used, it is preferable to prepare a resin component composition in which the equivalent of the ethylenically unsaturated bond group is 100 g / eq or more. When an acrylic polymerizable resin component is used, it is more preferable to use one having a functional group number of 1 or more per single molecule.

And different types of polymerizable resin components of polymerizable resin components can also be used together, as long as the dynamic viscosity of layer 3 before curing is 1000Pa. s is sufficient, but it is better to be 1.0Pa. The polymerizable resin component is prepared in the following manner.

Hereinafter, the polymerizable resin component, the polymerization initiator, and other components that can be used in the adhesive composition of one embodiment will be described in more detail.

(Polymerizable resin component)

As the polymerizable resin component, an addition polymerizable resin component having at least one functional group selected from the group consisting of an ethylenically unsaturated bond and an epoxy group can be selected. This compound group is widely known in the industrial field. In an adhesive composition of one embodiment, if it can be formed at 250 ° C, the dynamic viscosity is 1000 Pa. Adhesive layers having a Young's modulus of 2 GPa or more at 25 ° C or higher can be used without particular limitation.

Although it does not specifically limit as a polymerizable resin component, It is preferable that it is formed by containing the polymerizable resin component which has an epoxy group, the polymerizable resin component which has an ethylenically unsaturated double bond, and the crosslinkable group containing siloxane. The polymerizable resin component of at least one of the groups preferably contains a polymerizable resin component having an epoxy group.

The polymerizable resin component having an epoxy group is not particularly limited as long as it is a compound capable of cleaving an epoxy group and polymerizing each other by using a polymerization initiator. In addition, the polymerizable resin component having an epoxy group is irrespective of its molecular weight, as long as an epoxy group is introduced into at least one of a side chain or a terminal. Therefore, the polymerizable resin component having an epoxy group may be, for example, a compound having an epoxy group and an ethylenically unsaturated double bond and a compound having an epoxy group and an ethylenically unsaturated double bond, which are copolymerized with each other. Epoxy-based resin.

The polymerizable resin component having an ethylenically unsaturated double bond may be a low-molecular compound or a polymer such as a homopolymer or a copolymer resin, as long as it has an ethylenically unsaturated double bond.

The low molecular compound having an ethylenically unsaturated double bond preferably has a molecular weight of 2,000 or less, more preferably 1500 or less, and most preferably a molecular weight of 900 or less. The so-called low-molecular compound in the present invention is obtained by using a polymerization initiator to break the unsaturated bond and grow the chain bond. It is not a so-called polymer or oligomer, but has a molecular weight of 2000 or less (more preferably 1500 or less, Even more preferably 900 or less) compounds of a certain molecular weight (compounds having substantially no molecular weight distribution). The molecular weight of the low-molecular compound is usually 100 or more.

Examples of low-molecular compounds having ethylenically unsaturated double bonds include unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid) or esters thereof. And amines are preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amines of unsaturated carboxylic acids and aliphatic polyamine compounds.

In addition, the low-molecular compound having an ethylenically unsaturated double bond may be an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group added to a monofunctional or polyfunctional isocyanate or epoxy. Addition reactants derived from esters or amidines. In addition, as the low-molecular compound having an ethylenically unsaturated double bond, an unsaturated carboxylic acid ester or amidoamine having a detachable substituent such as a halogen group or tosylsulfonyl group, and a monofunctional or polyfunctional Substitute reactants for alcohols, amines, and thiols.

In addition, for a copolymer resin having an ethylenically unsaturated double bond, for example, an unsaturated carboxylic acid ester having a functional group such as a hydroxyl group, an amino group, or a mercapto group, or a copolymer of amidines, and the functional group having Isocyanate-based or epoxy-based ethylenically unsaturated double-bond compounds react to introduce ethylenically unsaturated double-bond resins. The copolymer resin having an ethylenically unsaturated double bond may be, for example, a copolymer of an unsaturated carboxylic acid ester or amidine having a functional group such as a hydroxyl group, an amine group, or a mercapto group with a carboxylic acid and an ethylenic compound. A resin obtained by condensing a compound with a saturated double bond.

In addition, the polymerizable resin component may have, for example, a siloxane skeleton and at least one of an epoxy group and an ethylenically unsaturated double bond in at least one of a terminal and a side chain of the siloxane skeleton. Siloxane containing a crosslinkable group.

Such polymerizable resin components may be used in combination of two or more.

(1. Polymerizable resin component having epoxy group)

The polymerizable resin component having an epoxy group may have a resin component having a sufficient epoxy group in one molecule for curing by heating or exposure. Among them, it is preferably selected from the group consisting of a novolac epoxy resin (Anv), a bisphenol epoxy resin (Abp), an alicyclic epoxy resin, and an acrylic resin (Aac) having an epoxy group. At least one resin. Among these epoxy resins, novolac-type epoxy resins are more preferably used from the viewpoint that a high dynamic viscosity at 250 ° C or higher and a high Young's modulus at 25 ° C of the adhesive layer 3 after hardening can be better obtained. . Moreover, these polymerizable resin components which have an epoxy group can be used individually by 1 type or in combination of 2 or more types. Specific examples of these better epoxy resins are shown below.

(1) Novolac epoxy resin (Anv)

As the novolak-type epoxy resin (Anv), a resin represented by the following general formula (anv0) can be used.

(In the formula, R ^a11 and R ^a12 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, na ¹¹ is an integer of 1 to 5 and R ^EP is an epoxy group-containing group).

In the formula (anv0), the alkyl group having 1 to 5 carbon atoms of R ^a11 and R ^{a12 is} , for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, third butyl, pentyl, isopentyl, neopentyl, etc. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among them, R ^a11 and R ^{a12 are} preferably a hydrogen atom or a methyl group.

In the formula (anv0), R ^EP is an epoxy-containing group. The epoxy-containing group as the R ^EP is not particularly limited, and examples include a group formed only from an epoxy group; a group formed only from an alicyclic epoxy group; an epoxy group or an alicyclic epoxy Base and base of divalent linking base. The alicyclic epoxy group is an alicyclic group having an oxeane structure having a 3-membered cyclic ether, and specifically is a group having an alicyclic group and an oxeane structure. The alicyclic group as a basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. The hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. When a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, the epoxy group or the alicyclic group is preferably bonded via a divalent linking group bonded to an oxygen atom (-O-) in the formula. Epoxy. Here, the divalent linking group is not particularly limited, and preferred examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

For divalent hydrocarbon groups which may have a substituent:

The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Make The aliphatic hydrocarbon group which is a divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, a ring-containing aliphatic hydrocarbon group in the structure, and the like.

The carbon number of the linear aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include methylene [-CH _2- ], ethylene [-(CH ₂ ) _2- ], and trimethylene [- (CH ₂ ) _3- ], tetramethylene [-(CH ₂ ) _4- ], pentamethylene [-(CH ₂ ) _5- ], and the like.

The carbon number of the branched chain aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 2 or 3. The branched chain aliphatic hydrocarbon group is preferably a branched chain alkylene group, and specific examples are -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- , etc. alkyl methylene groups;- CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ CH ₂ -and other alkylene groups; -CH (CH ₃ ) CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH ₂ -and other alkyltrimethylene groups; -CH (CH ₃ ) Alkyl alkylene and the like of CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -and the like. The alkyl group in the alkylene alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the ring-containing aliphatic hydrocarbon group in the above structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms are removed from the aliphatic hydrocarbon group), and the alicyclic hydrocarbon group is bonded to the end of the linear or branched aliphatic hydrocarbon group. Base, alicyclic hydrocarbon group is interposed between the linear or branched aliphatic hydrocarbon group Base etc. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The carbon number of the alicyclic hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

The polycyclic alicyclic hydrocarbon group is preferably one in which two hydrogen atoms are removed from the polycycloalkane. The polycycloalkane is preferably one having 7 to 12 carbon atoms, and specific examples include adamantane, norbornane, Isobornane, tricyclodecane, tetracyclododecane, etc.

The aromatic hydrocarbon group in the divalent 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 monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene or heteroaryl); and an aromatic compound containing two or more aromatic rings. (Such as biphenyl, fluorenyl, etc.) to remove two hydrogen atoms; remove one hydrogen atom (aryl or heteroaryl) from the aromatic hydrocarbon ring or aromatic heterocyclic ring 1 alkylene substituted group of hydrogen atom (e.g. from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl The aryl group in the arylalkyl group and the like further removes a hydrogen atom) and the like. The number of carbon atoms of the alkylene group bonded to the aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent 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.

The alicyclic hydrocarbon group in the ring-containing aliphatic hydrocarbon group in the structure as the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, and third butyl. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a third group. Butoxy is preferably methoxy or ethoxy. Examples of the halogen atom of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and more preferably a fluorine atom. Examples of the halogenated alkyl group as the substituent include a group in which part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. An alicyclic hydrocarbon group may be substituted with a part of carbon atoms constituting a ring structure by a hetero atom-containing substituent. As the hetero atom-containing substituent, -O-, -C (= O) -O-, -S-, -S (= O) _2- , -S (= O) ₂ -O- are preferred.

The aromatic cyclic hydrocarbon group as a divalent hydrocarbon group is an aromatic hydrocarbon group having Some hydrogen atoms may be substituted by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, and third butyl. Examples of the alkoxy group, a halogen atom, and a halogenated alkyl group as the substituent include substituents that substitute a hydrogen atom that the alicyclic hydrocarbon group has.

For heterovalent divalent linking groups:

The heteroatom in the heterovalent divalent linking group is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. Among the divalent linking groups containing hetero atoms, preferred examples of the linking group are -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O- ; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H can also be substituted by alkyl, fluorenyl, etc. substituted); - S -, - S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 -C (= O) -O-, -C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] m ”-Y ²² -or -Y ²¹ -OC (= O) -Y ²² -a group represented by [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m 'is an integer of 0 to 3] and the like. When the heterovalent divalent linking group is -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-, its H is also It may be substituted by a substituent such as an alkyl group, a fluorenyl group, and the like. The carbon number of the substituent (alkyl, fluorenyl) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. -Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ²¹ -C (= O) -O-, -C (= O) -OY ²¹ -,-(Y ²¹ -C (= O) Y ²¹ and Y ^{22 in} -O] m "-Y ²² -or -Y ²¹ -OC (= O) -Y ²² -are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group are The "divalent hydrocarbon group which may have a substituent" which is exemplified in the description of the divalent linking group is the same. As Y ²¹ , a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, and a linear alkylene group having 1 to 5 carbon atoms is more preferred. Methylene or ethylene is particularly preferred. base. Y ^{22 is} preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylidene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In the base represented by the formula-[Y ²¹ -C (= O) -O] m "-Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1 , Especially good for 1. That is, the base represented by the formula-[Y ²¹ -C (= O) -O] m "-Y ²² -is particularly preferably the base represented by the formula -Y ²¹ -C (= O) -OY ^22- . Among them, a base represented by the formula-(CH ₂ ) a'-C (= O) -O- (CH ₂ ) b'- is preferred. In the formula, a 'is an integer from 1 to 10, preferably 1 An integer of ~ 8, more preferably an integer of 1 to 5, and more preferably 1 or 2, b is preferably 1. b 'is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5. , More preferably 1 or 2, and most preferably 1. Among them, the epoxy-containing group in R ^EP is preferably a glycidyl group.

As the novolac-type epoxy resin (Anv), a resin containing a constituent unit represented by the following general formula (anv1) can be preferably used.

(In the formula, R ^EP is an epoxy-containing group, and R ^a22 and R ^a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.)

In the formula (anv1), the alkyl groups having 1 to 5 carbons in R ^a22 and R ^{a23 are} the same as the alkyl groups having 1 to 5 carbons in R ^a11 and R ^{a12 in} the above formula (anv0). The halogen atom of R ^a22 and R ^a23 is preferably a chlorine atom or a bromine atom. In the formula (anv1), same as in the formula R ^EP (anv0) R ^EP, and preferably a glycidyl group.

Specific examples of the constituent units represented by the above formula (anv1) are shown below.

The novolak epoxy resin (Anv) may be a resin composed of only the above-mentioned constituent unit (anv1), and a resin having the constituent unit (anv1) and other constituent units is also preferred. Examples of other constituent units include constituent units represented by the following general formulae (anv2) to (anv3), for example.

(In the formula, R ^a24 is a hydrocarbon group which may have a substituent, R ^a25 to R ^a26 and R ^a28 to R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R ^a27 is an epoxy group-containing group. Or a hydrocarbon group which may have a substituent).

In the formula (anv2), R ^a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group and a cyclic hydrocarbon group. The carbon number of the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples are methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is more preferred.

The branched alkyl group preferably has a carbon number of 3 to 10, more preferably 3 to 5. Specific examples are isopropyl, isobutyl, third butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, and the like, and more preferably Isopropyl.

When R ^a24 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be polycyclic or monocyclic. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a group that removes one hydrogen atom from the polycycloalkane. The polycycloalkane is preferably one having 7 to 12 carbon atoms. Specific examples include adamantane, norbornane, Isobornane, tricyclodecane, tetracyclododecane, etc.

When the cyclic hydrocarbon group of R ^a24 is an aromatic hydrocarbon group, 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 monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group of R ^a24 include a group (aryl group or heteroaryl group) having one hydrogen atom removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring; and an aromatic group containing two or more aromatic rings. Compounds (e.g. biphenyl, fluorene, etc.) remove one hydrogen atom; one alkylene substituted group (e.g. benzyl, phenethyl) from a hydrogen atom in the above aromatic hydrocarbon ring or aromatic heterocyclic ring , Arylalkyl such as 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl) and the like. The number of carbons of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the formulas (anv2) and (anv3), R ^a25 to R ^a26 and R ^a28 to R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and an alkyl group having 1 to 5 carbon atoms or a halogen atom. They are the same as the above-mentioned R ^a22 and R ^a23 , respectively.

In the formula (anv3), R ^a27 is a group containing epoxy groups or substituted hydrocarbon group, the same as the group R containing epoxy groups ^a27 of the above formula (anv0) R ^EP, R ^a27 may have a substituent of The hydrocarbyl group is the same as for R ^a24 .

Specific examples of the constituent units represented by the formulae (anv2) to (anv3) are shown below.

In addition, as another constituent unit that can replace the constituent unit represented by the general formula (anv1), in addition to the constituent units represented by the above (anv2) to (anv3), polycycloalkane constituent units can be exemplified. In this way, as the constituent unit of polycycloalkane, a carbon number of 7 to 12 is preferred. Specific examples include an adamantane constituent unit, a norbornane constituent unit, an isobornane constituent unit, a tricyclodecane constituent unit, Cyclododecane constituting unit and the like.

The proportion of each constituent unit in the resin (Anv) when the novolac epoxy resin (Anv) contains other constituent units in addition to the constituent unit (anv1) is not particularly limited, but it is relative to all constituent units of the constituent resin (Anv) In total, the constituent units with epoxy groups The total is preferably 10 to 90 mole%, more preferably 20 to 80 mole%, and still more preferably 30 to 70 mole%.

Examples of commercially available novolac epoxy resins (Anv) are, for example, JER-152, JER-154, JER-157S70, JER-157S65 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N- 740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000, EPICLON HP7200 (above for DIC (stock) system), EOCN-1020 (above for Nippon Kayaku (stock) system), etc.

(2) Bisphenol epoxy resin (Abp)

As the bisphenol type epoxy resin (Abp), an epoxy resin having a structure represented by the following general formula (abp1) can be used.

(In the formula, R ^EP is an epoxy-containing group, R ^a31 and R ^a32 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and na ³¹ is an integer of 1 to 50).

In the formula (abp1), the alkyl group having 1 to 5 carbon atoms of R ^a31 and R ^{a32 is} the same as the alkyl group having 1 to 5 carbon atoms of R ^a11 and R ^{a12 in} the above formula (anv0). Among them, R ^a31 and R ^{a32 are} preferably a hydrogen atom or a methyl group. And R ^EP (anv0) in the above formula R ^EP of the same, and preferably a glycidyl group.

Examples of the bisphenol epoxy resin (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, and JER-1009. , JER-1010 (above are manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON1050, EPICLON1051, EPICLON1055 (above are manufactured by DIC), etc .; Examples of bisphenol F-type epoxy resin are JER-806, JER -807, JER-4004, JER-4005, JER-4007, JER-4010 (the above are manufactured by Mitsubishi Chemical Corporation), LCE-21, RE-602S (the above are manufactured by Nippon Kayaku Corporation).

(3) Alicyclic epoxy resin (A1)

As the epoxy-aliphatic polymerizable resin component, an alicyclic epoxy resin (A1) (hereinafter sometimes referred to as "(A1) component") can be used. The alicyclic epoxy resin (A1) is represented by the following formula (A1).

(Wherein R ¹ and R ² are each independently an organic group which may have an alicyclic epoxy group, and at least one of R ¹ and R ² is an group having an alicyclic epoxy group, and Y ¹ and Y ² are each Independently, it is a single bond or a divalent linking group).

In the formula (A1), R ¹ and R ² are each independently an organic group which may have an alicyclic epoxy group, and at least one of R ¹ and R ² is an alicyclic epoxy group. In this embodiment, the "organic group which may have an alicyclic epoxy group" includes not only a combination of an alicyclic epoxy group and an organic group, but also a group (organic group) composed of only alicyclic epoxy groups ).

Examples of the organic group include a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and an arane which may have a substituent. Or a heteroaralkyl group which may have a substituent.

The organic groups of R ¹ and R ² may have an alicyclic epoxy group, and at least one of R ¹ and R ² may have an alicyclic epoxy group. The organic groups of R ¹ and R ² which may have an alicyclic epoxy group may be different or the same. As R ¹ and R ² , both of them are preferably organic groups having an alicyclic epoxy group, more preferably both are groups formed from an alicyclic epoxy group, and particularly preferably, both are 1, 2-epoxycyclohexyl.

In formula (A1), Y ¹ and Y ² are each independently a single bond or a divalent linking group. The divalent linking group is not particularly limited, but examples thereof include a linear, branched, or ring-containing aliphatic hydrocarbon group or aromatic hydrocarbon group in the structure. The aliphatic hydrocarbon group or the aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. In the aliphatic hydrocarbon group or the aromatic hydrocarbon group, a part of the carbon atom and the hydrogen atom constituting the structure may be substituted with a hetero atom-containing substituent. Examples of the hetero atom-containing substituent include -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-; -C (= O) -NH -, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H can also be substituted by substituents such as alkyl and fluorenyl); -S-, -S _{(= O) 2 -, -} S (= O) 2 -O-, the formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] m ”-Y ²² -or -Y ²¹ -OC (= O) -Y ²² -The basis [in the formula, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, preferably a linear or branched alkylene. O in the formula is an oxygen atom, and m ”is an integer of 0 to 3] and the like .

Y ²¹ and Y ²² may be different or the same. When Y ²¹ and Y ²² are divalent linking groups, the divalent linking group is preferably a linear, branched chain, or a ring-containing aliphatic hydrocarbon group having a substituent, and more preferably a substituent having a substituent. The linear or branched aliphatic hydrocarbon group is more preferably a linear or branched alkylene group which may have a substituent. The carbon number of the aliphatic hydrocarbon group and the alkylene group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 3. Y ²¹ and Y ^{22 are} preferably a single bond, methylene, ethylene or propyl, more preferably a single bond or methylene, particularly preferably Y ¹ is a single bond, and Y ² is a methylene group.

Preferable examples of the component (A1) include compounds represented by the following formulae (A1-1) to (A1-2).

(In the formula, R ¹ and R ² are the same as above, Y ⁰² is a single bond or a divalent linking group, n ¹ and n ⁴ are each independently an integer of 0 to 3, n ² is an integer of 0 to 10, and n ³ is 0 or 1).

In the formulae (A1-1) to (A1-2), R ¹ and R ² are the same as above, preferably both are organic groups having an alicyclic epoxy group, and more preferably both are alicyclic epoxy groups . In the formulae (A1-1) to (A1-2), Y ⁰² is a single bond or a divalent linking group, and examples of the divalent linking group are the same as the above-mentioned Y ¹ and Y ² . Among them, a single bond or a linear, branched chain or a ring-containing aliphatic hydrocarbon group in the structure which may have a substituent is preferred. In the formulae (A1-1) to (A1-2), n ¹ and n ⁴ are each independently an integer of 0 to 3, preferably 0 or 1. In the formulae (A1-1) to (A1-2), n ² is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0. In the formulae (A1-1) to (A1-2), n ³ is 0 or 1, and preferably 0.

Specific examples of the (A1) component are as follows. In the following formula, n ²¹ is an integer of 1-10.

Examples of commercially available alicyclic epoxy compounds include CELLOXIDE 2021, 2021P, 2081, 2083, and 2085 (manufactured by DAICEL Chemical Industry Co., Ltd.).

(4) Multifunctional alicyclic epoxy resin (A2)

As the polymerizable resin component having an epoxy group, a polyfunctional alicyclic epoxy resin (A2) (hereinafter sometimes referred to as "(A2) component") can be used. Polyfunctional alicyclic epoxy resin (A2) is a compound which does not correspond to the said (A1) component. The component (A2) may be a low-molecular compound or a high-molecular compound, but a high-molecular compound is preferred. (A2) The component is a polyfunctional epoxy compound having more than two functions, and preferably a trifunctional or more compound. The component (A2) is preferably a compound represented by the following formula (A2-1) because it is excellent in chemical resistance and light resistance.

(In the formula, R ¹¹ is a residue from which active hydrogen groups in organic compounds having q active hydrogen groups are removed. N ¹¹ , n ¹² , ... n ^q each independently represent an integer from 0 to 100, and the sum is 1 to 100.q integer of 1 to 100. .A having a substituent group R ¹² of cyclohexyl skeleton or a substituent group R ¹² of a norbornene skeleton, and represented by the following formula (a1) or (A2)) .

(In the formula, R ^{12 is} independently a group represented by the following formulae (a11) to (a13), and a compound represented by the formula (A2-1) contains one or more groups represented by (a11). Formulas (a1), ( a2) represents a base, which is bound to the R ¹¹ in the compound represented by the formula (A2-1) in the bond of the fold line, and is bound to the formula (A2-1) in the * -labeled bond. (A hydrogen atom (H)) in the represented compound.

(R ¹³ represents an alkyl group, an alkyl carbonyl group, or an aryl carbonyl group. The groups represented by the formulae (a11) to (a13) are the bonds represented by the wave-shaped lines, and are bonded to the groups represented by the formulae (a1) and (a2)).

In the above formula (A2-1), R ¹¹ is a residue from which an active hydrogen group is removed from an organic compound having an active hydrogen group. Examples of the "organic compound having an active hydrogen group" as a precursor thereof are alcohols and phenols. Types, carboxylic acids, amines, thiols, etc.

The alcohol may be a monohydric alcohol or a polyhydric alcohol. Specifically, examples include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol; aromatic alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, and triethylene glycol Alcohol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl hydroxypyruvate Glycol esters, cyclohexanedimethanol, glycerol, diglycerol, polyglycerol, Polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol. Examples of the above phenols are phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxydiol Benzophenone, bisphenol S, phenol resin, cresol novolac resin, etc. Examples of the aforementioned carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, poly Acrylic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Examples of the compound include lactic acid, citric acid, and oxyhexanoic acid, and compounds having both a hydroxyl group and a carboxyl group. Examples of the amines are monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylene glycol triamine, triethylene glycol tetraamine, ethanolamine and the like. Examples of the thiols include thiols such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan; ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionic acid Ester, pentaerythritol tetramercaptopropionate, and the like;

Examples of the organic compound having an active hydrogen group include polyvinyl alcohol, polyvinyl acetate partial hydrolysate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, and hydroxyethyl fiber. Element, acrylic polyol resin, styrene acryl alcohol copolymer resin, styrene maleic acid copolymer resin, alkyd resin, polyester polyol, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol Alcohol, polytetramethylene glycol, etc.

The organic compound having an active hydrogen group may have an unsaturated double bond in its skeleton. Specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexene methanol, and tetrahydrophthalic acid. The above organic compounds having an active hydrogen group may be used alone or in combination of two or more kinds.

In the above formula (A2-1), n ¹¹ , n ¹² ,... N ^q each independently represent an integer of 0 to 100, and the sum is 1 to 100. In addition, q represents an integer from 1 to 100. Among them, n ¹¹ , n ¹² , ... n ^q are each preferably an integer of 2 to 10, more preferably an integer of 3 to 6. The sum of n ¹¹ , n ¹² , ... n ^q is preferably 4 to 30, more preferably 4 to 20. When the sum is 4 or more, the crosslinking density after hardening can be increased and the hardness can be increased. Moreover, when the said sum is 30 or less, the solubility to a solvent can be improved and handling property can be improved.

In the formula (A2-1), A represents a substituent group and having a cyclohexyl group or the backbone group R ¹² R ¹² group-containing substituent group of the norbornene skeleton in the above formula (a1) or (a2). A is preferably represented by the formula (a1). The q As may be the same or different.

The epoxy compound represented by the formula (A2-1) must contain one or more groups represented by the formula (a11), and the more the better. On the other hand, the fewer the bases represented by the formula (a13), the better.

The epoxy compound represented by the above formula (A2-1) can be 4-vinylcyclohexene, as described in Japanese Patent Publication No. 7-119270, by using an organic compound having an active hydrogen group as a starter. Polyether resin obtained by ring-opening polymerization of a mixture of -1-oxide or 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide and a compound having 1 epoxy group, that is, A polyether resin having a vinyl side chain and a cyclohexane skeleton or a vinyl side chain and a norbornene skeleton is produced by epoxidation with peracetic acid or hydrogen peroxide. A commercially available product is, for example, EHPE3150 (average of n ¹¹ to n ^q is 15) manufactured by DAICEL Chemical Industry Co., Ltd.

In addition, by using the alicyclic epoxy resin (A1) and the polyfunctional alicyclic epoxy resin (A2) together, the compounding ratio of the (A1) component and the (A2) component when preparing the adhesive composition is (A1) ) / (A2) = 70/30 ~ 51/49 (mass ratio), more preferably 70/30 ~ 60/40 (mass ratio). By setting the blending ratio as described above, the melt viscosity of the obtained adhesive composition can be in a preferable range described later. Thereby, the adhesive composition can be applied in a uniform film thickness. Moreover, an adhesive layer having high chemical resistance can be formed. Commercial products of epoxy resins in which an alicyclic epoxy resin (A1) and a polyfunctional alicyclic epoxy resin (A2) are used in combination. For example, EHPE3150CE manufactured by DAICEL Chemical Industry Company is preferred.

(5) Acrylic resin (Aac) with epoxy group

As the polymerizable resin component having an epoxy group, an acrylic resin (Aac) having an epoxy group obtained by copolymerizing at least an unsaturated carboxylic acid and a compound having an epoxy group and an ethylenically unsaturated double bond can be used.

Examples of unsaturated carboxylic acids are monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and the like Acid anhydride; etc. Among these, (meth) acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and availability. Unsaturated carboxylic acids They can be used alone or in combination of two or more.

In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid.

In the present specification, the "compound having an ethylenically unsaturated double bond" is also referred to as an "unsaturated compound".

The proportion of the constituent units derived from the unsaturated carboxylic acid (the constituent unit having a carboxyl group) in the acrylic resin having an epoxy group is preferably 5 to 29% by mass, more preferably 10 to 25% by mass.

Examples of the so-called unsaturated carboxylic acids are monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and these dicarboxylic acids Acid anhydride; etc. Among these, (meth) acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and availability. These unsaturated carboxylic acids can be used alone or in combination of two or more.

The compound having an epoxy group and an ethylenically unsaturated double bond may be one having no alicyclic epoxy group, or one having an alicyclic epoxy group, but more preferably one having an alicyclic epoxy group .

Examples of the compound having an epoxy group and an ethylenically unsaturated double bond other than an alicyclic epoxy group include glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and (meth) (Meth) acrylic epoxy such as 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, etc. Alkyl esters; α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7- Α-alkylacrylic epoxy alkyl esters such as epoxy heptyl; shrinkage of o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. Glyceryl ethers; etc. Among these, from the viewpoints of copolymerization reactivity, resin strength after curing, and the like, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and (meth) acrylic acid 6 are preferred. , 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether.

The alicyclic group of the compound having an alicyclic epoxy group and an ethylenically unsaturated double bond may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl, cyclohexyl, and the like. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Specifically, examples of the compound having an alicyclic epoxy group and an ethylenically unsaturated double bond include compounds represented by the following formulae (a4-1) to (a4-16). Among these, in order to make the hardenability of the adhesive composition moderate, the compounds represented by the following formulae (a4-1) to (a4-6) are preferred, and the following formulae (a4-1) to are more preferred (a4-4).

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a5 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^{a4 is} preferably a linear or branched alkylene group, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, and hexamethylene base. R ^{a5 is} preferably, for example, methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, hexamethylene, phenylene, cyclohexyl, or -CH. _2- Ph-CH _2- (Ph stands for phenylene).

These compounds having an epoxy group and an ethylenically unsaturated bond can be used alone or in combination of two or more.

The constituting unit derived from the unsaturated compound having an epoxy group in the acrylic resin having an epoxy group (the constituent unit having an epoxy group The ratio of bit is preferably 5 to 90% by mass, more preferably 15 to 85% by mass, and particularly preferably 50 to 85% by mass. By setting it as the said range, the acrylic resin which has an epoxy group can be hardened suitably.

The acrylic resin having an epoxy group is preferably one in which a compound having an alicyclic group and an ethylenically unsaturated double bond is further copolymerized.

The alicyclic group of the compound having an alicyclic group and an ethylenically unsaturated double bond may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl, cyclohexyl, and the like. Examples of the polycyclic alicyclic group include adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Specifically, examples of the compound having an alicyclic group and an ethylenically unsaturated double bond include compounds represented by the following formulae (a5-1) to (a5-8). Among these, in order to make the hardenability of the adhesive composition moderate, compounds represented by the following formulae (a5-3) to (a5-8) are preferable, and the following formulae (a5-3), (a5-4).

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a8 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{a7 is} preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, Hexamethylene. R ^{a8 is} preferably, for example, a methyl group or an ethyl group.

The proportion of the constituent units derived from the compound having an alicyclic group and an ethylenically unsaturated double bond in the acrylic resin having an epoxy group is preferably 1 to 40% by mass, more preferably 5 to 30% by mass.

The acrylic resin having an epoxy group may be one in which other compounds than those described above are further copolymerized. Examples of such other compounds include (meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds can be used alone or in combination of two or more.

Examples of (meth) acrylates are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and tert-octyl (meth) acrylate Linear or branched alkyl (meth) acrylates such as esters; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl ester, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, and the like.

Examples of (meth) acrylamide are (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (Meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl ( (Meth) acrylamide and the like.

Examples of allyl compounds are allyl acetate, hexanoic acid Allyl, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc. Class; allyloxyethanol; etc.

Examples of vinyl ethers are hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorine Ethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, diethyl ether Alkyl vinyl ethers such as methylamino ethyl vinyl ether, diethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, etc. ;Wait.

Examples of vinyl esters are vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and dichloroacetic acid. Vinyl Ester, Vinyl Methoxy Acetate, Vinyl Butoxy Ethyl Acetate, Vinyl Phenyl Acetate, Vinyl Acetate, Vinyl Lactate, Vinyl β-Phenyl Butyrate, Vinyl Benzoate, Salicylic Acid Vinyl ester, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.

Examples of styrenes are styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylbenzene Ethylene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethyl Alkyl styrene, ethoxymethylstyrene, ethoxymethylstyrene, etc .; methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxy Alkoxystyrene such as styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene , Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc .;

The weight average molecular weight of the acrylic resin having an epoxy group is preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000.

(2. Polymerizable resin component having ethylenically unsaturated double bonds)

If the polymerizable resin component having an ethylenically unsaturated double bond has a sufficient ethylenically unsaturated double bond in one molecule to be hardened by heating or exposure, it may be a low-molecular compound, a homopolymer, or Polymers such as copolymer resins. Specific examples of the polymerizable resin component having a more preferable ethylenically unsaturated double bond among these are shown below.

(1) Low molecular compounds with ethylenically unsaturated double bonds

The low-molecular compound having an ethylenically unsaturated double bond is typically exemplified by a condensate of (meth) acrylic acid and a polyhydric alcohol or polycarboxylic acid, or an unsaturated carboxylic acid having a functional group such as a hydroxyl group, an amino group, or a mercapto group. Polyfunctional monomers of addition polymers in which esters or amidines and polyhydric alcohols or polycarboxylic acids are polymerized via isocyanate groups or epoxy groups, and monofunctional monomers having ethylenically unsaturated double bonds.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, three Methylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate Ester, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (form Propyl) propenyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) propenyloxy polyethoxyphenyl) propane, 2-hydroxy-3- (methyl) Acrylic acid oxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether bis (methyl) ) Acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate ( (I.e. toluene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, styrene bis (meth) acrylamide, Group) polyfunctional monomers such as acrylamide methylene ether, polycondensates of polyhydric alcohols and N-methylol (meth) acrylamide, or triacrylmethyl formal. These polyfunctional monomers can be used individually or in combination of 2 or more types.

Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylic acid Amine-2-methylpropanesulfonic acid, tertiary butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl ester, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (formyl) Base) 2-phenoxy-2-hydroxypropyl acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, (methyl ) Tetrahydrofurfuryl acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate , 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, semi (meth) acrylate of phthalic acid derivatives, etc. . These monofunctional monomers can be used alone or in combination of two or more.

(2) Copolymer resins with ethylenically unsaturated groups

As the polymerizable resin having an ethylenically unsaturated double bond, a copolymer resin having an ethylenically unsaturated double bond can also be used. As such, copolymer resins having an ethylenically unsaturated double bond can be exemplified by, for example, (meth) acrylic acid (Meth) acrylic resins, etc., in which a side chain of an acrylic skeleton composed of (meth) acrylate and an ethylenic double bond is introduced.

Examples of the polymerizable resin component having an ethylenically unsaturated group include, for example, at least a carboxyl group of a resin obtained by copolymerizing an unsaturated carboxylic acid and an epoxy-containing unsaturated compound, and a ring of an epoxy-containing unsaturated compound. A resin obtained by reacting an oxy group, or at least an epoxy group of a resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated compound containing an epoxy group, and a resin obtained by reacting a carboxyl group of an unsaturated carboxylic acid. That is, as a resin for copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, one form of the above-mentioned acrylic resin (Aac) having an epoxy group can be exemplified.

In addition, as a method for introducing an ethylenically unsaturated double bond into an acrylic resin skeleton, as described above, the method is not limited to the carboxylic acid possessed by the acrylic resin skeleton and the form of introducing an ethylenically unsaturated double bond through an epoxy group. For example, an acrylic resin having a carboxylic acid group, a hydroxyl group, an amine group, a fluorenamine group, and a thiol group in a side chain, and an ethylenically unsaturated double bond and a carboxylic acid group, a hydroxyl group, an amine group, and a fluorenamine group A monomer such as a mercaptan group and a mercapto group are formed by reacting a polyfunctional isocyanate or a polyfunctional epoxy resin to introduce an ethylenically unsaturated double bond.

Further, the (meth) acrylic resin to which an ethylenic double bond is introduced may be a homopolymer or copolymer of a (meth) acrylic acid ester having an ethylenically unsaturated double bond and an epoxy group.

In addition, the proportion of the constituent unit (the constituent unit having an epoxy group) derived from the epoxy-containing unsaturated compound occupied by the polymerizable resin component having an ethylenically unsaturated group is preferably 5 to 90% by mass, more Good for 15 ~ 75 mass%. By setting it as the said range, the adhesive layer 3 can be hardened suitably.

The weight average molecular weight of the polymerizable resin component having an ethylenically unsaturated group is preferably 2,000 to 50,000, more preferably 5,000 to 30,000. By setting it as the said range, the favorable coating workability | operativity of an adhesive composition can be obtained.

(3. Crosslinkable group containing siloxane)

The polymerizable resin component may be a crosslinkable group-containing siloxane (Asi).

In the present specification, the crosslinkable group-containing siloxane (Asi) is a compound having a crosslinkable group such as an epoxy group and a vinyl group on the side chain of the siloxane skeleton as shown in the following formula (Asi0). .

-(SiO _3/2 (R ¹ )) _m- (SiO _3/2 (R ² )) _n -‧‧ (Asi0) (Here, R ¹ is a crosslinkable group, and R ² is selected from aryl or Aromatic groups, m and n represent the mole percentages of the structural units with the above-mentioned indices relative to all the structural units in the above polysiloxane, n + m = 100%, and n> 0).

The epoxy siloxane can be polymerized by cross-linking and polymerizing the above epoxy groups with a photocationic polymerization initiator or a thermal cationic polymerization initiator.

From the viewpoint of producing a laminate having excellent physical properties such as heat resistance of the adhesive layer 3, the crosslinkable group-containing siloxane is preferably a crosslinkable group-containing siloxane represented by the following general formula (Asi1).

(In the formula, R ^c1 is a group containing an epoxy group, an oxetanyl group, a vinyl group, and a (meth) acrylfluorenyl group, and R ^c2 is an alkyl group or an aryl group, and the indices m and n are relative to the polysilicon Molar percentage of all structural units in the oxane with the above indexed structural units, m is 50 ~ 90 mol%, n is 10 ~ 50 mol%, but the total of m and n is 100 mol%) .

Specific examples of the crosslinking agent-containing siloxane include polymer E, polymer F represented by the following formula, and trade names X-22-2046 and KF-102 manufactured by Shin-Etsu Polysilicon Co., Ltd.

Polymer E: epoxy-modified siloxane represented by the following formula (Asi2) (mass average molecular weight: 1000 to 20,000)

(In formula (Asi2), the indices m1 and n1 represent the mole percentage of the structural unit with the above index relative to all the structural units in the polymer E, m1 = 50 ~ 90 mole%, n1 = 10 ~ 50 mole Ear%, but the total of m1 and n1 is 100 mole%).

Polymer F: epoxy-modified siloxane represented by the following formula (Asi3) (Mass average molecular weight: 1000 ~ 20000)

(In formula (Asi3), the indices m2, n2, and n3 represent the mole percentages of the structural units with the above indices relative to all the structural units in the polymer F, m2 = 50 ~ 90 mole%, n2 = 1 ~ 10 mole%, n3 = 5 ~ 50 mole%, but the total of m2, n2 and n3 is 100 mole%).

[Polymerization initiator]

The polymerization initiator may be any one that can harden the polymerizable resin component. Examples of the polymerization initiator are a thermal polymerization initiator and a photopolymerization initiator. Regardless of the composition of the manufactured laminate, a thermal polymerization initiator is preferred from the viewpoint that the adhesive layer 3 can be hardened well. .

Examples of the thermal polymerization initiator include a thermal cationic polymerization initiator and a thermal radical polymerization initiator. In addition, examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator. The thermal cationic polymerization initiator, thermal radical polymerization initiator, photocationic polymerization initiator, and photoradical polymerization initiator are described in detail below.

(1) Thermal cationic polymerization initiator

The adhesive composition contains a thermal cationic polymerization initiator as a polymerization initiation Agent. In addition, among the thermal cationic polymerization initiators, a polymerization initiator that generates an acid by heat is sometimes referred to as a thermal acid generator. When the adhesive composition is subjected to heat curing treatment, the polymerization of polymerizable groups can be promoted by the action of cations generated by heat. The compounds which can be used as a thermal cationic polymerization initiator are described in detail below.

(cation)

Examples of the thermal cationic polymerization initiator include compounds having a cationic moiety represented by the following general formula (h01) or (h02).

(In the above formula (h01), R ^h01 to R ^h04 are each independently an organic group selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group. The aryl group may also have a substituent, R at least one of ^h01 to R ^h04 is an aryl group).

(In the above formula (h02), R ^h05 to R ^h07 are each independently an organic group selected from the group consisting of an alkyl group and an aryl group having 1 to 20 carbon atoms. The above aryl group may also have a substituent, R ^h05 to At least one of R ^h07 is aryl).

When R ^h01 to R ^h07 are aryl groups, the aryl group is preferably a phenyl group represented by the following general formula (hr-1).

(In the above formula hr-1, R ^hc01 may be hydrogen, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be bonded to (hr-1) via an ether bond or an ester bond. Phenyl. In addition, hr-1 in R ^h01 to R ^h07 may be a different substituent independently).

As a preferable aspect of a cation part represented by General formula (h01), the following cation part is mentioned.

Moreover, as a cation part represented by general formula (h02), it is preferable Examples of the form include the following cationic moiety. In this way, the aromatic onium salt having a cationic moiety is excellent in stability at room temperature and generates an acid by heat, so it can be suitably used as a thermal acid generator.

In addition, as a preferable form of the cation part represented by General formula (h02), the following cation part can be illustrated.

(Anion part)

Examples of the anion portion as a thermal cationic polymerization initiator include, for example, a hexafluoride phosphate anion, a trifluoromethanesulfonic acid anion, a perfluorobutanesulfonic acid anion, a tetrakis (pentafluorophenyl) borate anion, and the like.

Examples of thermal cationic polymerization initiators available as commercial products are, for example, SANAID SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI -110, SI-110L, SI-145, I- 150, SI-160, SI-180, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 (Sanxin Chemical Industry Co., Ltd.) and so on. In addition, examples are CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (made by Japan Soda Co., Ltd.), CP-66, CP-77 (ADEKA (Stock system), FC-520 (3M company) K-PURE, TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2678, TAG-2681, TAG-2679, TAG-2689, TAG-2690, TAG-2700, TAG-2710, TAG-2100 (made by KING Industry), CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC- 1821, CXC-1802-60 (made by Nanben Chemical Co., Ltd.), etc. Among the above, trifluoromethanesulfonate or hexafluorophosphate is preferred, and trifluoromethanesulfonate is more preferred.

The temperature for generating an acid in the thermal cationic polymerization initiator is preferably a temperature region above the attachable region of the adhesive layer 3, specifically preferably 110 ° C or higher, more preferably 130 ° C or higher.

The formulation of the thermal cationic polymerization initiator is preferably 0.01% by weight or more and 20% by weight or less, more preferably 0.1% by weight or more and 10% by weight or less, and more preferably the total solid content of the adhesive composition. 0.5% by weight or more and 5% by weight or less. If the blending amount of the thermal acid generator is 0.1% by weight or more, the polymerizable resin component can be polymerized well, and a dynamic viscosity at 250 ° C or higher and a Young's modulus at 25 ° C can be formed. Landing layer.

(2) Thermal radical polymerization initiator

Examples of the thermal radical polymerization initiator include a peroxide and an azo-based polymerization initiator. These thermal radical polymerization initiators polymerize a polymerizable monomer by a radical generated by heating.

Examples of the peroxide include ketone peroxide, peroxyacetal, hydrogen peroxide, dialkyl peroxide, peroxyester, peroxycarbonate, and peroxyacetal. Specific examples are acetamidine peroxide, cumene peroxide, third butyl peroxide, third butylpentyl peroxide, propylammonium peroxide, benzoylperoxide (BPO), 2-peroxide Chlorobenzidine, 3-chlorobenzyl peroxide, 4-chlorobenzyl peroxide, 2,4-dichlorobenzyl peroxide, 4-bromobenzyl peroxide, lauryl peroxide, Potassium sulfate, diisopropyl peroxycarbonate, tetrahydronaphthalene peroxide, 1-phenyl-2-methylpropane-1-hydrogen peroxide, third butyl pertriphenylacetate, third butyl peroxy Hydrogen oxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxy 4-methoxyacetate and per-N- ( 3-tolyl) carbamic acid tert-butyl ester, dicumyl peroxide, tert-butylperoxy-2-ethylhexyl monocarbonate, bis (4-tert-butylcyclohexyl) peroxide Oxydicarbonate, 2,5-dimethyl-2,5-di (third butylperoxy) hexane, 1,1-bis (third butylperoxy) cyclohexane, and the like.

Examples of commercially available peroxides are, for example, the trade name "PERCUMYL (registered trademark)", the trade name "PERBUTYL (registered trademark)", and the trade name "PEROCTA" (Registered trademark) ", trade name" PEROYL (registered trademark) ", and trade name" PERHEXA (registered trademark) ".

Examples of the azo-based polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl ) Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azo Azobisisobutane, 2,2'-azobisisobutylammonium amine, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropanoic acid methyl ester, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyric acid dimethyl ester, 1,1'-azobis (1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalononitrile, 4,4'- Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis-2-methylvaleronitrile, 4, 4'-Azobis-4-cyanovaleric acid dimethyl ester, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanonitrile, 2,2 '-Azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptane , 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-nitrophenylazobenzylcyanoacetate, phenylazobis Phenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A -4,4'-azobis-4-cyanovalerate) and poly (tetraethylene glycol-2,2'-azobisisobutyrate).

The blending amount of the thermal radical polymerization initiator is preferably 0.1 part by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the polymerizable monomer. With this, you can better By polymerizing a polymerizable resin component having an ethylenically unsaturated double bond, it is possible to form an adhesive layer having a dynamic viscosity above 250 ° C and a high Young's modulus at 25 ° C. The thermal radical polymerization initiator is preferably formulated in the adhesive composition by a conventional method immediately before the adhesive composition is used. The thermal radical polymerization initiator may be added to the adhesive composition after dilution with a solvent as described below.

The 1-minute half-decay temperature of the thermal radical polymerization initiator is preferably 90 ° C or higher and 200 ° C or lower, more preferably 120 ° C or higher and 180 ° C or lower.

The one-and-a-half hour decay temperature of the thermal radical polymerization initiator is preferably 50 ° C or higher and 140 ° C or lower, more preferably 80 ° C or higher and 140 ° C or lower.

By making the 1-minute half-decay temperature of the thermal radical polymerization initiator preferably 90 ° C or higher and 200 ° C or lower, and the 1-hour half-decay temperature preferably 50 ° C or higher and 140 ° C or lower, self-adjusting thermal radicals can be achieved. The time from the polymerization initiator to the time when the polymerizable resin component having an ethylenically unsaturated double bond is polymerized and the gelation time is extended. Thereby, the workable time when the adhesive composition is applied to the support plate 2 can be lengthened. Moreover, the one-minute half-decay temperature of the thermal radical polymerization initiator is preferably 90 ° C. or higher and 200 ° C. or lower, and the one-hour half-decay temperature is preferably 50 ° C. or higher and 140 ° C. or lower on the support plate 2. When applying the adhesive composition, it is possible to set a higher temperature condition when the diluent solvent is removed by heating. From the viewpoint of extending the workable time, it is preferably higher than the one-and-a-half-minute decay temperature and the one-and-a-half hour decay temperature of the thermal radical polymerization initiator. From the viewpoint of rapid gelation, it is preferably lower than the 1 minute and a half decay temperature and 1 hour of the thermal radical polymerization initiator. Half decay temperature.

In addition, the theoretical active oxygen amount of the thermal radical polymerization initiator is preferably 3.0% or more and 13.0% or less, and it is appropriate to adjust the blending amount of the thermal radical polymerization initiator according to the theoretical active oxygen amount.

(3) Photocationic polymerization initiator

The photocationic polymerization initiator of the present invention is preferably one or more types of cationic polymerization selected from the group consisting of a compound represented by the following general formula (b0-1) and a compound represented by the following general formula (b0-2). Starter (B0) (hereinafter referred to as "(B0) component").

(In the formula, R ^b01 to R ^b04 are each independently a fluorine atom or an aryl group which may have a substituent. R ^b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent. The plural R ^b05 may be the same or different. They are different, q is an integer of 1 or more, and Q ^{q + is} independently a q-valent organic cation).

[(B0) ingredients]

(B0) the component is one or more selected from the group consisting of a compound represented by the general formula (b0-1) and a compound represented by the general formula (b0-2) The cationic polymerization initiator. These two compounds generate stronger acids by exposure. Therefore, the adhesive composition having the (B0) component can harden the polymerizable resin component having an epoxy group by exposure.

In the formula (b0-1), R ^b01 to R ^b04 are each independently a fluorine atom or an aryl group which may have a substituent. The aryl group which may have a substituent in R ^b01 to R ^b04 is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples include naphthyl, phenyl, and anthracenyl. From the viewpoint of availability, phenyl is preferred. An aryl group may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, or a hydrocarbon group (preferably a linear or branched alkyl group, preferably 1 to 5 carbon atoms), and more preferably a halogen atom or carbon. The halogenated alkyl group having 1 to 5 is particularly preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. It is preferable that the aryl group has a fluorine atom and the polarity of the anion portion is increased. Among them, as R ^b01 to R ^b04 in formula (b0-1), a fluorinated phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

As a preferable specific example of the anion part of the compound represented by the formula (b0-1), tetra (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ); tetra [(trifluoromethyl) Phenyl) phenyl] borate ([B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ); difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ); three Fluoro (pentafluorophenyl) borate ([(C ₆ F ₅ ) BF ₃ ] ^- ); Tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ) and the like. Among them, particularly preferred is tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ).

In Formula (b0-2), R ^b05 is a fluorine atom or a fluorinated alkyl group may have a substituent group, the plurality of R ^b05 may be the same or different from each other.

The carbon number of the fluorinated alkyl group which may have a substituent in R ^b05 is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 5. Specifically, for example, in the above description of R ^a22 and R ^a23 , in the alkyl group having 1 to 5 carbon atoms, a part or all of hydrogen atoms are substituted with fluorine atoms. Among them, R ^{b05 is} preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom or a trifluoromethyl group. Or pentafluoroethyl.

The anion part of the compound represented by formula (b0-2) is preferably one represented by the following general formula (b0-2a).

(In the formula, R ^bf05 is a fluorinated alkyl group which may have a substituent, and n ^b1 is an integer of 1 to 5).

In the formula (b0-2a), the fluorinated alkyl group which may have a substituent as R ^{bf05 is} the same as the fluorinated alkyl group which may have a substituent as exemplified in the above R ^b05 . In formula (b0-2a), n ^{b1 is} preferably 1 to 4, more preferably 2 to 4, and most preferably 3.

In the formulae (b0-1) to (b0-2), q is an integer of 1 or more, and Q ^{q +} is a q-valent organic cation. Preferable examples include a sulfonium cation and a sulfonium cation. Particularly preferred is the following general formula (ca- 1) Organic cations represented by (ca-5).

(Wherein, R ²⁰¹ ~ R ²⁰⁷ and R ²¹¹ ~ R ²¹² each independently represents a substituent group of the aryl group having, heteroaryl, alkyl or alkenyl ^{group, R 201 ~ R 203, R} 206 ~ R 207, R 211 ~ R ²¹² can be bonded to each other to form a ring with the sulfur atom in the formula, R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²¹⁰ represents an aryl group which may have a substituent, which may have An alkyl group of a substituent, an alkenyl group which may have a substituent, or a cyclic group containing -SO ₂ -which may have a substituent, L ²⁰¹ is -C (= O)-or C (= O) -O-, Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenyl group, x is 1 or 2, and W ²⁰¹ represents a (x + 1) -valent linking group).

Examples of the aryl group of R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. Examples of the heteroaryl group of R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include those in which a part of carbon atoms constituting the above aryl group is substituted with a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group in which one hydrogen atom is removed from 9H-oxanthracene; and examples of the substituted heteroaryl group include a group in which one hydrogen atom is removed from 9H-oxanthracene-9-one. Examples of the alkyl group of R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include a linear or cyclic alkyl group, and a carbon number of 1 to 30 is preferred. The alkenyl group of R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is preferably 2 to 10 carbon atoms. Examples of the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amine group, an oxo group (= O), an aryl group, The groups represented by the following formulae (ca-r-1) to (ca-r-10), respectively.

(In the formula, ^{R'201 is} each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or an alkenyl group which may have a substituent.)

^R'201 is a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or an alkenyl group which may have a substituent.

Cyclic radicals which may have substituents:

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

R ^'201 in the aromatic hydrocarbon group having an aromatic hydrocarbon rings. The carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, particularly preferably from 6 to 15, and most preferably from 6 to 10. However, the carbon number does not include the carbon number in the substituent. R ^'201 in the aromatic ring of the aromatic hydrocarbon group having specifically exemplified benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, substituted or forming part of an aromatic ring carbon atoms of such heteroatom-aromatic heterocyclic A ring or a ring in which a part of hydrogen atoms constituting such an aromatic ring or an aromatic heterocyclic ring is substituted with an oxo group or the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. As R ^'201 in particular of aromatic hydrocarbon, for example for the removal from said group one aromatic ring hydrogen atoms (an aryl group; for example phenyl, naphthyl, anthryl, etc.), from said hydrogen atoms of the aromatic ring 1 alkyl substituted (e.g. benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. arylalkyl Etc.), removing a hydrogen atom from a ring (e.g., anthraquinone, etc.) substituted for a part of the hydrogen atoms constituting the aromatic ring by an oxo group, etc. Thia anthracene-9-one, etc.) removes one hydrogen atom, etc. The carbon number of the above-mentioned alkylene (an alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

R ^'201 in the example a cyclic aliphatic hydrocarbon group of an aliphatic hydrocarbon-containing rings for the structure. Examples of the ring-containing aliphatic hydrocarbon group in the structure include an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from the aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group bonded to a linear or branched aliphatic hydrocarbon group. The terminal group and the alicyclic hydrocarbon group are intervened by a linear or branched aliphatic hydrocarbon group. The carbon number of the alicyclic hydrocarbon group is preferably 3-20, more preferably 3-12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane, or the like. The polycyclic aliphatic hydrocarbon group is preferably a group in which one or more hydrogen atoms are removed from the polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; having a steroid; Polycyclic alkanes having a condensed ring system such as a cyclic radical of a skeleton.

Wherein, as R 'of the cyclic aliphatic hydrocarbon group of ²⁰¹ is preferably from a monocyclic or polycyclic alkyl alkoxy removing one or more hydrogen atoms of the groups, more preferably from polycyclic alkyl group removal of a hydrogen atom, and particularly preferably Adamantyl and norbornyl, preferably adamantyl.

The linear or branched aliphatic hydrocarbon group which can be bonded to the alicyclic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3. . The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specific examples thereof include methylene [-CH _2- ], ethylene [-(CH ₂ ) _2- ], and trimethylene [- (CH ₂ ) _3- ], tetramethylene [-(CH ₂ ) _4- ], pentamethylene [-(CH ₂ ) _5- ], and the like. The branched aliphatic hydrocarbon group is preferably a branched chain alkylene, and specific examples are -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -CH (CH ₃ ) ₂ -,- C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- , etc. alkyl methylene; -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 -etc. alkylene ethyl groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. alkyltrimethylene groups; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- , etc. alkyl alkylenes such as tetramethylene and the like. The alkyl group in the alkylene alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Chain alkyl groups which may have substituents:

^R'201 may have a linear alkyl group which may have a substituent and either a linear or branched chain. As the linear alkyl group, the carbon number is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specific examples are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, undecyl, eicosyl, twenty-one Alkyl, behenyl, etc.

As the branched chain alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specific examples are 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methyl Ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like.

Alkenyl group which may have a substituent:

As R ^'201 of chain alkenyl group may be any linear or branched chain of one, preferably from 2 to 10 carbon atoms, more preferably 2 to 5, and more preferably from 2 to 4, particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, an allyl group, an allyl group, and a butenyl group. Examples of the branched alkenyl group include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, 2-methpropenyl, and the like. As the chain-shaped alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

As the cyclic group R ^'201, the chain of the alkyl or alkenyl group of substituent groups, for example, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, nitro group, amino group, oxo group, the above-described R ^'201 of a cyclic group.

Among these, ^{R'201 is} preferably a cyclic group which may have a substituent, and a linear alkyl group which may have a substituent.

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , R ²¹¹ to R ²¹² are bonded to each other to form a ring together with a sulfur atom in the ring, a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, or a carbonyl group, Functional groups such as -SO-, -SO _2- , -SO _3- , -COO-, -CONH-, or -N (R _N )-(the R _N is an alkyl group having 1 to 5 carbon atoms) are bonded. The formed ring is preferably a ring having 3 to 10 members, and particularly preferably a ring having 5 to 7 members, in which one ring contains a sulfur atom in the formula. Specific examples of the formed ring include, for example, thienyl, thiazolyl, benzothiophene ring, thioanthracene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioanthracene ring, thioanthrone ring, thia Anthracene ring, phenoxathiin, tetrahydrothienium ring, tetrahydrothiopyranium ring and the like.

R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When they are alkyl groups, they may be bonded to each other to form a ring.

R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cyclic group containing -SO ₂ -which may have a substituent. Examples of the aryl group of R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group and a naphthyl group. The alkyl group in R ²¹⁰ is a chain or cyclic alkyl group, and it is preferably one having 1 to 30 carbon atoms. The alkenyl group of R ²¹⁰ preferably has 2 to 10 carbon atoms.

Y ²¹⁰ each independently represents an arylene group, an alkylene group or an alkylene group.

Y ²¹⁰ Examples of an arylene group is exemplified an aryl group from the R 'group is removed ^201. aromatic hydrocarbon one hydrogen atoms. Examples of the alkylene group and the alkenyl group of Y ²¹⁰ include a group in which one hydrogen atom is removed from the group exemplified as the linear alkyl group and the alkenyl group of R ′ ²⁰¹ .

In the formula (ca-4), x is 1 or 2. W ²⁰¹ is a (x + 1) valence, that is, a divalent or trivalent linking group. The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and is preferably the same group as the divalent hydrocarbon group which may have a substituent exemplified by R ^EP in the formula (anv0). The divalent linking group in W ²⁰¹ may be any of linear, branched, and cyclic, and is preferably cyclic. Among them, a group formed by combining two carbonyl groups at both ends of an arylene group, or a group formed by only an arylene group is preferred. Examples of the arylene group include a phenylene group and a naphthyl group. Particularly preferred is a phenylene group. W ²⁰¹ in the example 3 divalent linking group connected to a group-based removal of a hydrogen atom from the above-described W ²⁰¹ of divalent, linking group to the divalent linking group and further the above-described divalent linking group of the like. The trivalent linking group in W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

Specific examples of preferred cations represented by the formula (ca-1) are cations represented by the following formulae (ca-1-1) to (ca-1-24).

(In the formula, R " ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as those exemplified as the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have).

The cation represented by the formula (ca-1) is also preferably a cation represented by the following general formulae (ca-1-25) to (ca-1-36).

(In the formula, R ' ²¹¹ is an alkyl group, and R ^hal is a hydrogen atom or a halogen atom).

Specific examples of the preferable cation represented by the formula (ca-2) include a diphenylsulfonium cation, a bis (4-thirdbutylphenyl) sulfonium cation, and the like.

Specific examples of preferred cations represented by the formula (ca-4) are cations represented by the following general formulae (ca-4-1) to (ca-4-2), respectively.

The cation represented by the formula (ca-5) is preferably a cation represented by the following general formulae (ca-5-1) to (ca-5-2), respectively.

(Wherein R ' ²¹¹ is an alkyl group).

Among the above, the cation part [(Q ^{q +} ) 1 / q] is preferably a cation represented by the general formula (ca-1), more preferably represented by the formulas (ca-1-1) to (ca-1-36), respectively. cation.

In addition, among the photocationic polymerization initiators, a polymerization initiator that generates an acid by light is also referred to as a photoacid generator.

(B0) A component may be used individually by 1 type of the said photo-acid generator, and may use 2 or more types together. The content ratio of the component (B0) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 100 parts by mass of the polymerizable resin component containing an epoxy group. It is 0.2 to 5 parts by mass, and particularly preferably 0.5 to 2 parts by mass. The content of the (B0) component in the photocationic polymerization initiator in the adhesive composition is not particularly limited, and can be appropriately determined depending on the structure of the (B0) component or the acid derived from the anion part. Specifically, the content ratio of the (B0) component in the photocationic polymerization initiator is preferably 20 to 99.999% by mass, more preferably 30 to 99.99% by mass, still more preferably 40 to 99.9% by mass, and particularly preferably 60 to 99.9 mass%, preferably 90 to 99.6 mass%. When the content ratio of the (B0) component is in the above range, the strength of the plurality of acids generated from the polymerization initiator by exposure can be made moderate as a whole, and the polymerizable resin component can be hardened well.

The content of the photocationic polymerization initiator in the adhesive composition is preferably 0.01 to 60 parts by mass, more preferably 0.05 to 30 parts by mass, and more relative to 100 parts by mass of the polymerizable resin component having an epoxy group. It is preferably from 0.05 to 20 parts by mass, and particularly preferably from 0.1 to 10 parts by mass. If the content of the photocationic polymerization initiator is 0.01 to 60 parts by mass, the adhesive layer can be hardened well, and an adhesive layer having a high dynamic viscosity at 250 ° C and a Young's modulus at 25 ° C can be formed. .

(4) Photo radical polymerization initiator

The adhesive agent composition may be configured by polymerizing a polymerizable resin component with a photoradical polymerization initiator.

Specific examples of the photo-radical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2- Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane- 1-ketone, ethyl ketone 1- [9-ethyl-6- (2-methylbenzylidene) -9-H-carbazol-3-yl] -1- (o-acetamidooxime), 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 4-benzylidene-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Methyl aminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoate, 4-dimethylamino 2-Isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylacetal, 1-phenyl-1,2-propanediol-2- (o-ethyl (Oxycarbonyl) oxime, methyl o-benzylidenebenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro- 4-propoxythioxanthone, thioanthracene, 2-chlorothioanthracene, 2,4-diethylthioanthracene, 2-methylthio Anthracene, 2-isopropylthioanthracene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Benzamyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-dibenzene Diimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e. rice Ketone), 4,4'-bisdiethylaminobenzophenone (also known as ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxydi Benzophenone, Biphenylhydrazone, Benzoin, Benzoin methyl ether, Benzoin ether, Benzoin isopropyl ether, Benzoin n-butyl ether, Benzoin isobutyl ether, Benzoin tert-butyl Ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminophenylacetone, dichloroacetophenone, trichloroacetophenone, p- Tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4 -Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzene Formates, 9-phenylacridine, 1,7-bis- (9-acridyl) heptane, 1,5-bis- (9-acridyl) heptane, 1,3-bis- ( 9-acridyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( Furan-2-yl) ethylene ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (tri Chloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) vinyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloro (Methyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl- 6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s- Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6 -(2- Bromo-4-methoxy) styrylphenyl-s-triazine and the like. As the photoradical polymerization initiator, commercially available products such as "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", and "IRGACURE 907" (trade names: all manufactured by BASF) ), And "NCI-831" (brand name: ADEKA).

The blending amount of the photo radical polymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the polymerizable monomer.

(3. Other ingredients)

The adhesive agent composition may contain a surfactant and a diluent in addition to the polymerizable component and the polymerization initiator.

(1) Surfactant

The adhesive composition may also contain a surfactant. Examples of the surfactant include a polysiloxane-based surfactant and a fluorine-based surfactant. As the polysiloxane surfactant, specifically, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK can be used. -322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354 , BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (BYK Chemie)). As the fluorine-based surfactant, specifically, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, and F-445 can be used. , F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F -484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130 , TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (manufactured by DIC Corporation); PF-636, PF-6320, PF-656, PF-6520 (OMNOVA of POLYFOX series) Company system) and so on.

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 2 parts by mass, and still more preferably 0.03 to 1 part by mass based on 100 parts by mass of the polymerizable resin component in total. By setting it as the said range, when the adhesive composition is apply | coated to the support plate 2, the adhesive layer 3 with high flatness can be formed.

(2) Diluted solvent

The adhesive composition preferably contains a diluent solvent. The diluent is not limited as long as it is a solvent that can dissolve the polymerizable resin component and the polymerization initiator, and the following solvents can be preferably used.

Examples of the diluting solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane, and carbon. 4 to 15 branched chain hydrocarbons, such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, etc. Hydrocarbons, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpenediol, 1,8-terpenediol, norbornane, norbornane, pinane, side Pane, pinane, longifolene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, alpha-terpineol, beta-terpineol Alcohol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, terpineol acetate, 1,4-eucalyptol, 1,8-eucalyptol, dragon Cerebral, carvone, ionone, thujone, camphor, d-limonene, l-limonene, dipentene and other terpenoid solvents; lactones such as γ-butyrolactone; acetone and methyl ethyl ketone , Ketones such as cyclohexanone (CH), methyl-n-pentyl ketone, methyl isoamyl ketone, 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; Compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the aforementioned polyols, or a single compound Methyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc. Derivatives of polyhydric alcohols such as ether-containing compounds having ether bonds (of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred); such as the ring of dioxane Ethers, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methoxypyruvate Esters of methyl ester, ethyl ethoxypyruvate, anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butyl phenyl ether, etc. Aromatic organic solvents.

Moreover, the adhesive agent composition may contain a sensitizer suitably according to the composition of a polymerizable resin component and a polymerization initiator.

<The manufacturing method of the laminated body of another embodiment (second embodiment)>

The manufacturing method of the laminated body of this invention is not limited to the manufacturing method of the laminated body of the said embodiment (1st embodiment). As shown in (a) to (J) of FIG. 2, for example, a method for manufacturing a laminated body according to one embodiment (second embodiment) includes the following steps: forming a borrow on a light-transmissive support plate 2 (support body) A step of forming a separation layer of the separation layer 4 that is degraded by irradiation with light; a step of forming an adhesion layer of the adhesion layer 3 by applying an adhesive composition of an embodiment to the separation layer 4; A hardening step of hardening the layer 3; and a laminating step of laminating the substrate through the bonding layer 3, the laminating step includes a rewiring layer forming step of forming a rewiring layer on the bonding layer 3; and mounting a component on the rewiring layer Installation steps; and a sealing step of sealing components mounted on the redistribution layer by a sealing material. Here, the dynamic viscosity at 250 ° C of the adhesive layer 3 after the hardening step is 1000 Pa. s or more, and the Young's modulus at 25 ° C is 2 GPa or more. Therefore, in the same manner as the method for manufacturing the laminated body of the first embodiment, the laminated body 31 can be formed better by using the adhesive composition of one embodiment.

That is, the manufacturing method of the laminated body of this embodiment replaces the substrate 1 and manufactures the laminated body of the sealing substrate 7 laminated with the element 11, the sealing material 6 of the sealing element 11, and the rewiring layer 5 of the mounting element 11. method. More specifically, the semiconductor is integrated, thinned, and miniaturized by arranging terminals outside the wafer area of a component sealed by a sealing material, which is a method of manufacturing a laminate based on a fan-out technology. The fan-out technology is an example of a fan-out type in which semiconductor elements are arranged on a wafer and packaged. WLP (Fan-out Wafer Level Package) and fan-out WLP (Fan-out Wafer Level Package) in which semiconductor elements are arranged on the panel and packaged.

In addition, for convenience of explanation, the components having the same functions as those described in the first embodiment are denoted by the same reference numerals, and descriptions thereof are omitted.

[Separation layer forming step ~ hardening step]

In the separation layer forming step ((a) in FIG. 2), the same steps as those in the first embodiment are used to form the separation layer, and therefore description thereof is omitted. The step of forming an adhesive layer (FIG. 2 (b)) is the same as the first embodiment except that the adhesive layer 3 is formed on the separation layer 4 formed on the support plate 2, so the description is omitted.

[Hardening step]

In the manufacturing method of the laminated body of this embodiment, a hardening process is performed before a lamination process. In the hardening step, it is preferable to pre-heat the adhesive layer 3 formed in the adhesive forming step or to place the adhesive layer 3 under a reduced pressure environment or both, and remove the diluent solvent contained in the adhesive layer 3.

In the hardening step, when the diluent solvent contained in the adhesive layer 3 is removed by heating, it is preferable to remove the diluent solvent by heating the adhesive layer 3 in the attachable area. Subsequently, before the redistribution layer 5 is formed on the bonding layer 3, the bonding layer 3 is heated at a higher temperature than the attachable area under an inert gas environment such as nitrogen or an inert gas environment such as nitrogen. 10 ~ 60 minutes Just harden.

In the hardening step, when the adhesive layer 3 is hardened by exposure, the adhesive layer 3 may be exposed and hardened in an inert environment such as nitrogen or a reduced pressure environment.

[Lamination step]

As shown in (c) to (f) of FIG. 2, in the laminating step, a sealing substrate 7 is formed on the hardened adhesive layer 3. The lamination step in this embodiment includes a re-layer formation step, a mounting step, a sealing step, and a thinning step, and the sealing substrate 7 is formed on the adhesive layer 3 by performing in this order.

[Rewiring layer formation step]

As shown in FIG. 2 (c), in the redistribution layer forming step, a redistribution layer 5 is formed on the bonding layer 3.

In one embodiment, the sequence for forming the rewiring layer 5, and then based on the first layer 3, a dielectric layer is formed a silicon oxide (SiO _x), the photosensitive resin. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin by a method such as spin coating, dipping, roll knife, spray coating, and slit coating.

Next, a wiring is formed on the dielectric layer by a conductive material such as a metal. As a method of forming the wiring, a conventional semiconductor manufacturing method such as photolithography (resistive lithography) or the like can be used.

In this way, when performing photolithographic processing, etching processing, etc., the adhesive layer 3 is exposed to an acid such as hydrogen fluoride, an alkali such as TMAH, and a resist solvent. In particular, in the fan-out technology, cyclopentanone, cyclohexanone, and the like are used as the resist solvent in addition to PGMEA. However, by forming the adhesive layer 3 using the adhesive composition of one embodiment, the adhesive layer 3 is provided with high chemical resistance. Therefore, it is possible to prevent the separation layer from being dissolved or peeled off due to not only exposure to acids and alkalis, but also exposure to a resist solvent. Therefore, the redistribution layer 5 can be formed on the support plate 2 well.

(Rewiring layer 5)

The redistribution layer 5 is also referred to as an RDL (Redistribution Layer, redistribution layer), and is a thin film wiring body constituting wirings connected to the element 11, and may have a single-layer or multi-layer structure. In one embodiment, the redistribution layer 5 may be a dielectric (such as a photosensitive resin such as silicon oxide (SiO _x ), a photosensitive epoxy resin, or the like), and a conductive body (such as aluminum, copper, titanium, Metals such as nickel, gold, and silver, and alloys such as silver-tin alloys) form wiring, but are not limited thereto.

[installation steps]

As shown in (d) of FIG. 2, in the mounting step, the component 11 is mounted on the redistribution layer 5. For example, the component 11 can be mounted using, for example, a wafer mounter. More specifically, for example, a form in which the element 11 is mounted on the redistribution layer 5 through a solder bump can be exemplified.

(Element 11)

The element 11 is a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the element 11 is a semiconductor element, an electronic portion obtained by cutting the sealing substrate 7 becomes a semiconductor device. In the element 11, a wiring layer (not shown) may be formed on a surface facing the side above the redistribution layer 5.

[Sealing step]

As shown in (e) of FIG. 2, in the sealing step, the element 11 is sealed with a sealing material 6. It is not particularly limited, but for reference, the sealing material 6 is, for example, heated to 100 ° C. or higher, and is maintained in a high viscosity state by injection molding using a molding die. Here, since the adhesive layer 3 has high heat resistance, deformation of the adhesive layer 3 due to the pressure applied during the injection molding of the sealing material 6 can be better prevented. Therefore, deformation of the redistribution layer formed on the bonding layer 3 can be prevented, and the element can be sealed with high accuracy. In addition, in the mounting step, if the component 11 is mounted on the redistribution layer 5 via a solder bump, the solder bump can also be sealed by underfilling before the sealing element 11.

(Sealing material 6)

As the sealing material 6, for example, an epoxy resin or a silicone resin can be used. The sealing material 6 is preferably not provided for each of the elements 11, but is one in which the plurality of elements 11 mounted on the redistribution layer 5 are all integrally sealed.

(Sealed substrate 7)

The sealing substrate 7 includes an element 11, a sealing material 6 for the sealing element 11, and The redistribution layer 5 of the component 11 is mounted. The sealing substrate 7 preferably includes a plurality of elements 11. By cutting such a sealing substrate 7, a plurality of electronic components can be obtained.

[Thinning step]

As shown in FIG. 2 (f), in the thinning step, the sealing material 6 is thinned. Thereby, the sealing substrate 7 provided with the redistribution layer 5 can be formed on the adhesive layer 3 well.

<Substrate Processing Method of Another Embodiment (Second Embodiment)>

Next, a substrate processing method according to another embodiment (second embodiment) will be described. The substrate processing method of this embodiment includes the steps of manufacturing the laminated body 30 (see (a) to (f) in FIG. 2) by using the manufacturing method of the laminated body of the second embodiment; after the manufacturing step of the laminated body, The separation layer 4 is deteriorated by irradiating the separation layer 4 with light through the support plate 2 and the separation step of separating the support plate 2 from the substrate 1 ((g) and (h) in FIG. 2); after the separation step, it is removed by grinding and then The adhesive layer removing step of the residue of the adhesive layer 3 on the wiring layer 5 side ((i) and (j) in FIG. 2). In addition, since the manufacturing steps of the laminated body shown in (a) to (f) of FIG. 2 are the same as the manufacturing method of the laminated body of the second embodiment, the description thereof is omitted.

The separation step and the subsequent layer removal step are the same as those of the first embodiment except that the sealing substrate 7 is used instead of the substrate 1, and the description thereof is omitted.

[Other steps]

In addition, the substrate processing method of this embodiment may also form a BGA (Ball Grid Array) on the redistribution layer 5 of the sealing substrate 7 obtained in (j) of FIG. 2 and perform processing such as cutting. Accordingly, since a semiconductor device can be manufactured without using a silicon interposer, further reduction in thickness of the semiconductor device can be achieved.

<Manufacturing method of laminated body of a modification>

The manufacturing method of the laminated body of this invention is not limited to the said embodiment. For example, in a manufacturing method of a laminated body according to a modified example, an element 11 is first mounted on the adhesive layer 3, and the element 11 is sealed with a sealing material 6 to form a rewiring layer 5.

[Separation layer forming step ~ Next layer forming step]

Since the separation layer forming step (FIG. 3 (a)) and the subsequent layer forming step (FIG. 3 (b)) are the same as those in the second embodiment, description thereof will be omitted.

[Lamination step]

As shown in (c) to (f) of FIG. 3, the lamination step is performed on the adhesion layer 3 to form a sealing substrate 7. The lamination step in this embodiment is performed sequentially in the mounting step, the sealing step, the thinning step, and the re-forming step, and the hardening step is performed after the mounting step and before the sealing step.

[installation steps]

As shown in FIG. 3 (c), in the mounting step, the component 11 is mounted on the bonding layer 3. The arrangement of the element 11 on the bonding layer 3 can be performed while heating the bonding layer 3, for example, using a wafer mounter or the like.

[Hardening step]

The manufacturing method of the laminated body of this modification is hardening the adhesive layer 3 after an installation process. Thereby, in the subsequent sealing step, the positional deviation of the component 11 mounted on the bonding layer 3 can be better prevented. The hardening conditions of the bonding layer 3 in the hardening step are the same as those in the manufacturing method of the laminated body of the first embodiment and the second embodiment, and therefore description thereof is omitted.

[Sealing step]

As shown in FIG. 3 (d), in the sealing step, the element 11 is sealed by the sealing material 6. The sealing material 6 is injection-molded using a molding die, for example. It is needless to say that, similarly to the second embodiment, deformation of the adhesive layer 3 can be prevented when the element 11 is sealed in the sealing step.

[Thinning step]

As shown in FIG. 3 (e), in the thinning step, the sealing material 6 is thinned. The sealing material 6 may be thinned so that, for example, the terminal portion of the element 11 is exposed from the sealing material 6.

[Rewiring layer formation step]

As shown in (f) of FIG. 3, in the wiring forming step, A redistribution layer 5 is formed on the element 11 sealed by the sealing material 6.

Since the formation sequence of the redistribution layer 5 in one embodiment can be performed in the same manner as in the second embodiment, the description thereof is omitted.

Through the above steps, a laminate 32 can be obtained.

<Variation of substrate processing method>

A substrate processing method according to a modification includes a laminate manufacturing step ((a) to (f) in FIG. 3), a separation step ((g) and (h) in FIG. 3), and a subsequent layer removing step ((3) i) and (j)) are the same as those of the substrate processing method of the second embodiment, so descriptions thereof are omitted.

<Manufacturing method and substrate processing method of laminated body of another embodiment>

The manufacturing method and substrate processing method of the laminated body of this invention are not limited to the said embodiment (1st embodiment, 2nd embodiment, and a modification). For example, in the method for manufacturing a laminated body according to another embodiment, the sealing substrate formed by the method for manufacturing a laminated body according to the first embodiment, the second embodiment, and the second embodiment described above is laminated on another support through another bonding layer. In the method for manufacturing a laminate of a board (support), the other adhesive layer is formed of the adhesive composition according to an embodiment of the present invention.

According to the above structure, for example, because the dynamic viscosity at 250 ° C is 1000Pa. For a bonding layer with high heat resistance above s, the sealing substrate is bonded to the support plate, and an insulating layer or solder ball can be formed on the sealing substrate with a silicon interposer or on the sealing substrate with a redistribution layer instead of the silicon interposer. Wait. In addition, the sealing substrate can also be laminated with a seal mounted with other components. body. In this case, it is possible to better prevent voids from being generated between the sealing substrate and the adhesive layer due to outgassed from a sealing material containing an epoxy resin or a silicone resin.

Furthermore, the manufacturing method of the laminated body and the method of processing the substrate of the other embodiments have a configuration that does not include a step of forming a separation layer. Instead of forming a separation layer, the structure of the substrate and the support may be separated by mechanical means such as a blade. . In this mounting form, the adhesive layer remaining on the substrate separated from the support can also be removed well by grinding.

The present invention is not limited to the above-mentioned embodiments, and various changes can be made within the scope shown in the scope of the patent application. Embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention. Inside.

[Example] <Evaluation of Adhesive Layer and Laminate>

The dynamic viscosity of the adhesive layer formed using the following polymerizable resin component and polymerization initiator was measured, and the attachable area of each adhesive layer was specified. In addition, the adhesiveness of the substrate and the support using each of the adhesive composition was evaluated, and the heat resistance of the produced laminate and the removability of the adhesive layer after separation of the support were evaluated.

[Evaluation of dynamic viscosity]

Dynamic adhesion of the adhesive layers of Examples 1 to 4 and Comparative Examples 1 and 2 Degree evaluation. The dynamic viscosity evaluation was performed by dynamic viscosity measurement using a dynamic viscosity measuring device Reogel-E4000 (manufactured by UBM Co., Ltd.). The dynamic viscosity (η *) was evaluated under a condition of a frequency of 1 Hz, and the temperature was raised at a rate of 5 ° C / min in a temperature range of 100 ° C to 260 ° C.

(Adhesive layer of Examples 1 to 4)

A polymerization initiator is prepared in a polymerizable resin component, a base resin composition of an adhesive composition is prepared, and dynamic viscosity measurement is performed using a liquid shearing cell. The polymerizable resins and polymerization initiators used in the base resin compositions of Examples 1 to 4 are shown below. In addition, Table 1 below shows the evaluation results of the composition and dynamic viscosity of the adhesive layers of Examples 1 to 4.

<< Polymer resin composition >>

． JER157S70 (Novolac epoxy resin, manufactured by Mitsubishi Chemical Corporation)

<< Polymerization initiator >>

． CXC-1821 (Thermal cationic polymerization initiator, manufactured by Kusumoto Kasei Co., Ltd.)

． TAG-2678 (thermal cationic polymerization initiator, manufactured by King Industries)

． TAG-2689 (thermal cationic polymerization initiator, manufactured by King Industries)

(Comparative Examples 1 and 2)

The resin component was dissolved at a concentration of 25% by weight in a solvent prepared with 15 parts by weight of butyl acetate with respect to 100 parts by weight of decalin. Next, IRGANOX 1010 (manufactured by BASF) was added to 100 parts by weight of the resin component, and 15 parts by weight of butyl acetate as an addition solvent was added to prepare the adhesive composition of Comparative Examples 1 and 2. The composition of the resin components used in Comparative Examples 1 and 2 is shown below.

<< resin composition >>

． Septon (trade name) V9827 (reactive cross-linked styrene-ethylene-butene-styrene block copolymer; SBPS, manufactured by Kuraray Co., Ltd.)

． Septon 2002 (trade name) (styrene-isobutylene-styrene block copolymer; SBPS, manufactured by Kuraray Co., Ltd.)

． Acrylic copolymer A1 (styrene / dicyclopentyl methacrylate / stearyl methacrylate = 20/60/20 (weight ratio) copolymer, molecular weight 10000)

． APL8008T (Cycloolefin copolymer, ethylene: tetracyclododecene = 80: 20 copolymer, manufactured by Mitsui Chemicals Corporation)

Next, the prepared adhesive composition of Comparative Examples 1 and 2 was coated on a PET film with a release agent, and baked at 100 ° C and 160 ° C for 60 minutes in an oven at atmospheric pressure to remove the adhesive layer. Contained solvents. Next, the adhesive layer peeled from the PET film was cut into samples having a thickness of 0.5 mm and 20 mm square, and the shear viscosity was measured through a gap to measure the dynamic viscosity. In Table 1 below, Evaluation results of the adhesive layer composition and dynamic viscosity of Comparative Examples 1 and 2.

As shown in Table 1, the adhesion viscosities of the adhesive layers of Examples 1 and 2 were 120 Pa below 120 ° C. s or less. In addition, the adhesive layers of Examples 3 and 4 had a dynamic viscosity of 1 Pa below 160 ° C. s or less. Therefore, it can be confirmed that the adhesive layers of Examples 1 to 4 can be used at a lower temperature than the adhesive layers of Comparative Examples 1 and 2 as the attachment temperature region, and can be used better.

And, as shown in Table 1, the adhesive layers of Examples 1 to 4 were at 250 ° C, and the dynamic viscosity of the adhesive layer was 1000 Pa. s or more. Therefore, it was confirmed that the adhesive layers of Examples 1 to 4 had higher heat resistance to a temperature of 250 ° C or higher than the adhesive layers of Comparative Examples 1 and 2.

[Evaluation of laminate]

As the evaluation of the laminate, the adhesive compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for adhesion, heat resistance, and peelability by grinding. The measurement of the Young's modulus was also performed with respect to the adhesive layer formed from each adhesive composition.

(Preparation of adhesive composition)

For the measurement of dynamic viscosity, the polymerizable resin component was diluted with PGMEA (propylene glycol monomethyl ether acetate) so as to have a concentration of 55% by weight with the base resin composition of the adhesive layer of the same Examples 1 to 4 , The adhesive composition of Examples 1 to 4 was prepared.

(Production of laminated body of Examples 1 to 4)

On a semiconductor wafer substrate (12-inch diameter Si, 0.7 μm thick) as a substrate, a mold substrate (epoxy-based sealing material, manufactured by Hitachi Chemical Co., Ltd.) was used to prepare a mold substrate having a mold material layer. The dewatering treatment of the molded substrate was performed under a pressure condition at 140 ° C for 10 minutes.

The adhesive composition of Example 1 was spin-coated on a molded substrate, and heated at 90 ° C. for 300 seconds to remove the PGMEA contained in the adhesive layer to form an adhesive layer (20 μm in thickness, followed by a step of forming a layer). . Next, on the separation layer side of the glass support (12 inches in diameter and 0.7 mm thickness) on which the separation layer was formed, the mold substrate was attached through the adhesive layer, and the mold was attached under the conditions of a load of 1t, 85 ° C, and 300 seconds. Substrate and glass support (Lamination step). Next, the adhesive layer was heated at 200 ° C. for 1 hour (hardening step) to prepare the laminate of Example 1.

The separation layer is formed on a glass support by a plasma CVD method using fluorocarbon. C ₄ F ₈ was used as a reaction gas, and a fluorocarbon film (1 μm thick) was formed on a glass support by plasma CVD under conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2500 W, and a film formation temperature of 240 ° C. Separation layer (separation layer formation step).

(Production of laminated body of Comparative Example 1)

The adhesive composition of Comparative Example 1 was spin-coated on a molded substrate prepared in the same order as the molded substrate used in Example 1, and baked at 90 ° C, 160 ° C, and 220 ° C for 180 seconds each, and An adhesive layer having a film thickness of 50 μm was formed. Next, the semiconductor wafer substrate, the adhesive layer, the separation layer, and the glass support are overlapped in this order, and the glass support and the semiconductor wafer substrate are attached under vacuum at 215 ° C., 300 seconds, and a load of 1 t. A laminate of Comparative Example 1 was prepared.

[Evaluation of heat resistance]

The laminated body using a molded substrate and the laminated body using a semiconductor wafer substrate in Example 1 and Comparative Example 1 were each heated at 250 ° C. for 2 hours under a nitrogen atmosphere to evaluate heat resistance. The evaluation of the heat resistance was performed visually, and it was judged as "○" when no pores occurred between the substrate and the adhesive layer, and "X" when pores occurred between the substrate and the adhesive layer.

As a result of the heat resistance evaluation, the following of Example 1 was provided. The laminated body of the layer has the result of having a high heat resistance at 250 ° C (molded substrate) (○). In contrast, the laminated body of the molded substrate of Comparative Example 1 was used to confirm the occurrence of voids (×) between the molded substrate and the subsequent layer. The high heat resistance of the adhesive layer of Example 1 in the laminate using a molded substrate can be discussed because, as shown in Table 1, the dynamic viscosity of the adhesive layer of Example 1 is higher than 1000 Pa. s, and can better prevent the occurrence of pores caused by the gas generated from the self-molded substrate.

After the heat resistance evaluation, the laminated body of Example 1 and the laminated body of Comparative Example 1 were irradiated with laser light to the separation layer through a glass support. The laser light irradiation conditions were a wavelength of 532 nm, a laser light diameter of 180 μm, a distance between the centers of the irradiated areas of the laser pulses of 180 μm, a scanning speed of 6500 mm / s, and irradiation at a repetition frequency of 40 kHz. Thereby, for each laminate, the substrate and the glass support were separated and evaluated for peelability by grinding as shown below.

[Evaluation of peelability of grinding]

The separated semiconductor wafer substrate and the molded substrate of the glass support were ground using a grinder with a wheel, and the peelability evaluation of the residue grinding of the adhesive layer of Example 1 was performed. For peelability evaluation, a grinder DAG810 (manufactured by Disco) equipped with a wheel GF13-SD180-R15009-100, GF13-SDC320-BE065-50, and GF13-SDC340-BE065-50 (both manufactured by Disco) was used. The peelability after grinding was evaluated for both the above-mentioned adhesive layer having a film thickness of 20 μm and the separately prepared adhesive layer having an evaluated film thickness of 55 μm. In addition, as a reference example, grinding with each wheel is used. Also, the semiconductor wafer substrate without the adhesive layer was evaluated for peelability.

In the peelability evaluation, the operating conditions of the grinder are as follows.

Air cutting: 50μm

Shaft speed: 3000r / min

Feeding speed of grinding machine: 1.0μm / s

Spark out: 3Rev

Gauge setting: 1 probe

Amount of escape: 3.0 μm

Detachment speed: 0.3μm / s

Grinding water (rotating shaft): 4.0L / min

Grinder grinding water (external nozzle): 0L / min

Fixture revolutions: 275r / min.

The evaluation of peelability is to evaluate the presence or absence of damage in each round and the presence or absence of blockage caused by the residue of the adhesive layer. Visually evaluate the presence or absence of damage to each wheel. If the damage of the wheel is the same as the damage suffered by the semiconductor wafer substrate (Si shown in Table 2), it is evaluated as "○", and suffered greater damage than the damage suffered by the semiconductor wafer substrate. The evaluation was “×”. In addition, the presence or absence of blockage of the wheel was evaluated visually. Those who did not block the wheel due to the residue of the subsequent layer were evaluated as "○", and those who were blocked were evaluated as "x". At the same time, the load applied during grinding should be evaluated and the maximum current value of the grinder should be measured. Table 2 shows the evaluation results of the peelability of the grinding.

As shown in Table 2, the damage of each round during the grinding of the bonding layer in Example 1 was not related to the thickness of the bonding layer, and was the same as that of the semiconductor wafer substrate (○). In addition, as shown in Table 2, the maximum current value of the adhesive layer of Example 1 in the polishing machine was the same as the maximum current value applied when the semiconductor wafer substrate was polished. Therefore, it was confirmed that the adhesive layer of Example 1 can be peeled off satisfactorily by grinding using a polishing apparatus for thinning the semiconductor wafer substrate.

[Evaluation of Young's Modulus]

The adhesive compositions of Examples 1 to 4 were spin-coated on individual semiconductor wafer substrates (12 inches, 0.7 mm thick), heated at 90 ° C for 5 minutes, and then heated at 200 ° C for 1 hour under N ₂ environment. It hardened and formed the adhesive layer (thickness 20 micrometers) of Examples 1-4. Next, the adhesive compositions of Comparative Examples 1 to 2 were spin-coated on individual semiconductor wafer substrates, and fired at 90 ° C, 160 ° C, and 220 ° C for 3 minutes each on a hot plate at atmospheric pressure to form an adhesive layer ( 20 μm thick).

Subsequently, using a FISCHER SCOPE Hm2000 measuring device (manufactured by FISCHER INSTRUMENTS), Examples 1 to 4 and Comparative Examples were measured under conditions of a maximum test load: 5 mN, a load application time: 20 seconds, a creep time: 5 seconds, and 25 ° C. Young's modulus of the adjoining layers of 1 and 2.

The measurement results of the Young's modulus of each adhesive layer are shown in Table 3 below. Meanwhile, Table 3 below shows the results of evaluating the heat resistance and peelability (p-menthane) of the adhesive composition of Examples 2 to 4 and Comparative Examples 1 and 2 according to the above-mentioned evaluation methods.

* Peel-off of the adhesive layer was performed using para-mentane as a peeling liquid.

The adhesive composition of Examples 1 to 4 can obtain 1 Pa at a lower temperature than the adhesive composition of Comparative Examples 1 and 2. Dynamic viscosity below s can confirm that the wettability of the substrate is improved. And in the evaluation of the heat resistance after hardening, the dynamic viscosity of the laminates of Examples 1 to 4 at 250 ° C or higher was 1000 Pa. s or more, and no pore generation (○) was observed in the laminated body using the molded substrate, it was confirmed that the laminated body was obtained as compared with Comparative Examples 1 and 2. Higher heat resistance. In addition, the Young's modulus of the adhesive layer of Examples 1 to 4 is 3.5 GPa or more, and the residue of the adhesive layer does not clog, and grinding can be performed in the same manner as the semiconductor wafer substrate (○). The thermoplastic resins of Comparative Examples 1 and 2 must have a temperature of 180 ° C. or higher in order to reach the dynamic viscosity of the attachable area. Also, although it is a thermoplastic resin, its dynamic viscoelasticity is lower in a high temperature region of 250 ° C. On the other hand, the adhesive compositions of Examples 1 to 4 used thermosetting resins. It was confirmed that the adhesive compositions at lower temperatures than the adhesive compositions of Comparative Examples 1-2, heat resistance after curing, and peeling Excellent grinding removability.

[Industrial availability]

The present invention can be suitably used for manufacturing a semiconductor device.

1‧‧‧ substrate

2‧‧‧ support plate

3‧‧‧ Adjacent layer

4‧‧‧ separation layer

20‧‧‧Grinding machine

30‧‧‧ laminated

Claims (20)

A laminated body manufacturing method is a laminated body manufacturing method in which a substrate and a supporting body supporting the substrate are laminated via an adhesive layer, and is characterized by including the following steps: at least one of the substrate and the supporting body A lamination step of forming the above-mentioned adhesion layer containing a polymerizable resin component and a polymerization initiator, a lamination step of laminating the substrate and the support via the adhesion layer, and polymerizing the above by heating or exposure The hardening step of polymerizing the resin component to harden the adhesive layer, the Young's modulus of the cured adhesive layer at 25 ° C is 2GPa or more, and the dynamic viscosity at 250 ° C is 1000Pa. s or more. For example, the method for manufacturing a laminated body according to claim 1, wherein the substrate is a sealed substrate including a component, a sealing material for sealing the component, and a rewiring layer or a silicon wafer on which the component is mounted. The method for producing a laminated body according to claim 1 or 2, wherein the polymerizable resin component is selected from the group consisting of a polymerizable resin component having an epoxy group, a polymerizable resin component having an ethylenically unsaturated double bond, and a crosslinkable group. At least one of the groups formed by siloxanes. The manufacturing method of the laminated body of Claim 1 or 2 whose said polymerizable resin component is a polymerizable resin component which has an epoxy group. The method for producing a laminated body according to claim 4, wherein the polymerizable resin component having an epoxy group is at least one selected from the group consisting of an epoxy resin and an acrylic resin having an epoxy group. For example, the method for producing a laminated body according to claim 1 or 2, wherein the polymerization initiator is a thermal polymerization initiator, and the hardening step is to harden the adhesive layer by heating. For example, the method for manufacturing a laminated body according to claim 1 or 2, wherein the dynamic viscosity of the adhesive layer before the hardening step is 1 Pa. s or less. For example, the method for manufacturing a laminated body according to claim 1 or 2, wherein the above-mentioned support system is made of a light-transmittable support body, and before the above-mentioned subsequent layer formation step, further comprising forming on the support body by irradiating light, A step of forming a separation layer of a deteriorated separation layer. A substrate processing method is a substrate processing method for processing a substrate, which is characterized by including the steps of: manufacturing a laminated body by a manufacturing method of a laminated body according to any one of claims 1 to 8, After the laminated body manufacturing step, the branch is separated from the laminated body. The support layer separation step and the subsequent layer removal step of removing the residue of the above-mentioned adhesion layer on the substrate side by grinding after the separation step. A substrate processing method, which is a substrate processing method for processing a substrate, is characterized by including the following steps: a laminated body manufacturing step of manufacturing a laminated body by the laminated body manufacturing method as claimed in claim 8, and the above laminated body manufacturing step Then, a step of separating the support from the laminate, and a step of separating the support from the laminate by irradiating the separation layer with light through the support through which the light is transmitted. A laminated body is a laminated body in which a substrate and a support supporting the substrate are laminated through an adhesive layer, wherein the adhesive polymerizable resin component is polymerized by a thermal polymerization initiator or a photopolymerization initiator. The resulting hardened product has a Young's modulus of 2 GPa or higher at 25 ° C and a dynamic viscosity of 1000 Pa at 250 ° C. s or more. For example, the laminated body according to claim 11, wherein the substrate is a sealed substrate including a component, a sealing material for sealing the component, and a rewiring layer or a silicon wafer on which the component is mounted. The laminate according to claim 11 or 12, wherein the polymerizable resin component is selected from the group consisting of a polymerizable resin component having an epoxy group, a polymerizable resin component having an ethylenically unsaturated double bond, and a silicon oxide containing a crosslinkable group. At least one of the groups formed by alkanes. The laminate according to claim 11 or 12, wherein the polymerizable resin component is a polymerizable resin component having an epoxy group. The laminated body according to claim 14, wherein the polymerizable resin component having an epoxy group is at least one selected from the group consisting of an epoxy resin and an acrylic resin having an epoxy group. The laminated body according to claim 11 or 12, wherein the polymerizable resin component is polymerized by the thermal polymerization initiator. For example, the laminated body of claim 11 or 12, wherein the supporting body made of a light-transmissive material is a supporting body formed between the supporting body and the adhesive layer, and a separation layer that is deteriorated by light irradiation is formed. An adhesive composition, which is used to form an adhesive composition of the adhesive layer in a laminate in which a substrate and a support for supporting the substrate are laminated via an adhesive layer, which comprises a polymerizable resin component and heat. Polymerization initiator or photopolymerization initiation Agent, the hardened product of the polymerizable resin component polymerized by the thermal polymerization initiator or the photopolymerization initiator has a Young's modulus at 25 ° C of 2 GPa or more, and a dynamic viscosity at 250 ° C of 1,000 Pa. s or more. The adhesive composition according to claim 18, wherein the polymerizable resin component is selected from the group consisting of a polymerizable resin component having an epoxy group, a polymerizable resin component having an ethylenically unsaturated double bond, and a silicon oxide containing a crosslinkable group. At least one of the groups formed by alkanes. For example, the adhesive composition of claim 18 or 19, wherein the dynamic viscosity of the adhesive composition before forming the cured product is 1 Pa. s or less.