JP6244088B2 - Adhesive composition, adhesive film and laminate - Google Patents

Description

  The present invention relates to an adhesive composition, an adhesive film, and a laminate.

  Patent Document 1 discloses a method for bonding thermoplastic saturated norbornene polymers having a cycloolefin structure to each other or a material different from the molded product, and using an ultraviolet curable adhesive as an adhesive. Have been described.

Japanese Patent Laid-Open No. 3-160079 (published July 10, 1991)

  A polymer having a cycloolefin structure is excellent in transmittance and is used as an optical member. However, since the polymer has low polarity and low adhesion to a substrate such as glass, peeling of the polymer from the substrate gradually increases due to thermal shock caused by a heat cycle after the substrate is attached. Therefore, there exists a subject that the polymer which has a cycloolefin structure cannot be used as a permanent adhesive.

  The present invention has been made in view of the above problems, and can improve the heat cycle characteristics after substrate pasting, for example, an adhesive composition that can be used as a permanent adhesive for an optical member, and adhesion The main purpose is to provide a film and a laminate.

  The adhesive composition according to the present invention is characterized by containing a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer in order to solve the above-described problems.

  The adhesive composition according to the present invention can improve heat cycle characteristics, and has an effect that it can be used as a permanent adhesive for an optical member such as a CMOS image sensor.

  Hereinafter, embodiments of the present invention will be described in detail.

<Adhesive composition>
The adhesive composition according to the present invention includes a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer.

  The adhesive composition according to the present invention can be used for bonding a substrate (wafer) and a support. Moreover, a laminated body may be formed by forming an adhesive layer on a substrate or a support using the adhesive composition, and bonding the substrate and the support through the adhesive layer.

  The substrate is subjected to processes such as thinning and mounting while being supported by the support. The board | substrate with which the laminated body which concerns on this invention is not limited to a wafer, Arbitrary board | substrates, such as a thin film board | substrate and a flexible substrate, are employable. Further, a fine structure of an electronic element such as an electric circuit may be formed on the surface on the adhesive layer side of the substrate.

  The support body supports the substrate and may have a strength necessary for preventing the substrate from being damaged or deformed during processes such as thinning, transporting, and mounting the substrate. From the above viewpoint, examples of the support include those made of glass, silicon, and acrylic resin.

  Examples of the glass include low alkali glass, and specific examples thereof include TEMPAX manufactured by SCHOTT, EAGLE XG or EAGLE 2000 manufactured by Corning.

  After applying the adhesive composition according to the present invention to a substrate or a support to form an adhesive layer, the adhesive layer is heated. Thereby, the polymerization of the (meth) acrylate monomer forming the adhesive layer occurs, and the adhesion is improved by the interaction with the substrate or the support surface. As a result, the adhesive composition according to the present invention has improved heat cycle characteristics and can be used, for example, as a permanent adhesive for optical members.

(Polymer having cycloolefin structure)
The adhesive composition according to the present invention includes a polymer having a cycloolefin structure. Since the polymer having a cycloolefin structure is excellent in transmittance and the like, the adhesive composition according to the present invention can be used as a permanent adhesive for optical members.

  Specific examples of the cycloolefin polymer (polymer having a cycloolefin structure) include a ring-opening (co) polymer of a monomer component containing a cycloolefin monomer and a monomer component containing a cycloolefin monomer. Examples include addition (co) polymerized resins.

  Examples of the cycloolefin monomer include bicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydroxypentadiene, tetracyclics such as tetracyclododecene, and pentacycles such as cyclopentadiene trimer. , Heptacycles such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.), alkenyl (vinyl, etc.), alkylidene (ethylidene, etc.), aryl (phenyl) , Tolyl, naphthyl and the like) and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are more preferable.

  The polymer having a cycloolefin structure may contain another monomer copolymerizable with the above-described cycloolefin monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include alkene monomers having 2 to 10 carbon atoms, and examples include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. The alkene monomer may be linear or branched.

  Moreover, since the polymer which has a cycloolefin structure contains a cycloolefin monomer, it has high heat resistance (low thermal decomposition and thermal weight reduction property). The ratio of the cycloolefin monomer to the whole monomer component constituting the polymer having a cycloolefin structure is preferably 5 mol% or more, more preferably 10 mol% or more, and 20 mol% or more. Is more preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the polymer having a cycloolefin structure is not particularly limited, but may be 80 mol% or less from the viewpoint of solubility and stability over time in a solution. Preferably, it is 70 mol% or less.

  Moreover, you may contain the linear or branched alkene monomer as a monomer component of the polymer which has a cycloolefin structure. The ratio of the alkene monomer to the entire monomer component constituting the polymer having a cycloolefin structure is preferably 10 to 90 mol%, and preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. More preferably, it is more preferably 30 to 80 mol%.

  The polymer having a cycloolefin structure is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer. It is preferable for suppressing the generation of gas below.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be set as appropriate according to conventional methods.

  The weight average molecular weight of the polymer having a cycloolefin structure is preferably in the range of 50,000 to 150,000, more preferably in the range of 80,000 to 120,000. When the polymer having a cycloolefin structure has a weight average molecular weight of 50,000 or more, the softening temperature of the polymer can be set to a temperature suitable for bonding to glass. When the polymer having a cycloolefin structure has a weight average molecular weight of 120,000 or less, appropriate solvent solubility can be imparted to the polymer.

  Examples of commercially available products that can be used as a polymer having a cycloolefin structure include “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and “ “ZEONEX”, “ARTON” manufactured by JSR Corporation, and the like.

  The glass transition point (Tg) of the polymer having a cycloolefin structure is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition point of the polymer having a cycloolefin structure is 60 ° C. or higher, softening of the adhesive layer can be suppressed when exposed to a high temperature environment.

((Meth) acrylate monomer)
Moreover, the adhesive composition which concerns on this invention contains the (meth) acrylate monomer.

  The (meth) acrylate monomer is preferably a monofunctional (meth) acrylate monomer or a polyfunctional (meth) acrylate monomer. That is, the (meth) acrylate monomer is preferably at least one (meth) acrylate monomer selected from a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer. After the adhesive composition is applied to a substrate or the like, the (meth) acrylate monomer is polymerized by heating, and the adhesion is improved by the interaction between the substrate and the (meth) acrylate polymer.

  Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-hydroxyethyl. (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin Mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, , 2,3,3-tetrafluoro propyl (meth) acrylate, a half (meth) acrylate of phthalic acid derivatives. These monofunctional (meth) acrylate monomers may be used alone or in combination of two or more.

  Examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di ( (Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecanedi Methanol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A di (meth) acrylate, Limethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate Ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, ureta (Meth) acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  Among the above (meth) acrylate monomers, a (meth) acrylate monomer having a cyclic group is particularly preferable, and tricyclodecane dimethanol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclode At least one selected from the group consisting of candimethanol di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, and propoxylated bisphenol A di (meth) acrylate Is more preferable.

  The adhesive composition according to the present invention preferably contains (meth) acrylate monomer in the range of 1 part by weight to 30 parts by weight with respect to 100 parts by weight of the polymer having a cycloolefin structure. As mentioned above, it is more preferable to include in 15 weight part or less. When the (meth) acrylate monomer is 1 part by weight or more with respect to 100 parts by weight of the polymer having a cycloolefin structure, adhesion to a substrate such as silicon can be enhanced. When the amount of the (meth) acrylate monomer is 30 parts by weight or less with respect to 100 parts by weight of the polymer having a cycloolefin structure, it is possible to prevent a decrease in adhesion due to the excess monomer oozing out to the adhesive interface.

(Low molecular polymer having cycloolefin structure)
The adhesive composition according to the present invention may further include a low molecular polymer having a cycloolefin structure. By including the low molecular weight polymer having a cycloolefin structure, the temperature for thermoplasticizing the adhesive composition can be lowered, and the substrate and the support can be bonded at a lower temperature.

  The weight average molecular weight of the low molecular weight polymer having a cycloolefin structure is preferably in the range of 5,000 or more and 20,000 or less.

  Furthermore, the adhesive composition according to the present invention may further include a low-molecular polymer having a cycloolefin structure in a range of 10 parts by weight to 30 parts by weight with respect to 100 parts by weight of the polymer having a cycloolefin structure. preferable.

(Thermal polymerization initiator)
The adhesive composition according to the present invention may further contain a thermal polymerization initiator that accelerates the polymerization reaction of the (meth) acrylate monomer.

  The thermal polymerization initiator is not particularly limited as long as it can promote the polymerization reaction of the (meth) acrylate monomer, and examples thereof include peroxides and azo polymerization initiators. These thermal polymerization initiators generate radicals when heated to promote the polymerization reaction of the (meth) acrylate monomer.

  Examples of the peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and peroxy ester. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butyl cumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1 Hydroperoxide, tert-butyl perphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, 4-methoxyacetic acid tert-butyl, per-N (3-toluyl) carbamic acid tert- butyl and the like. Examples of commercially available peroxides include trade name “Park Mill (registered trademark)” and trade name “Perbutyl (registered trademark)” manufactured by Nippon Oil & Fats Co., Ltd.

  Examples of the azo polymerization initiator include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2 ' -Azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile , 4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4- Dimethyl cyanovalerate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azo Biscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis- 1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1′-azobiscumene, 4-nitrophenylazo Ethyl cyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4 -Cyanopentanoate), poly (tetraethylene glycol-2,2'-azobisisobutyrate) and the like.

  The ratio of the thermal polymerization initiator to 100 parts by weight of the (meth) acrylate monomer is preferably 0.5 parts by weight or more and 5 parts by weight or less, and more preferably 1 part by weight or more and 3 parts by weight or less.

〔solvent〕
The solvent contained in the adhesive composition according to the present invention may be any solvent as long as it has a function of dissolving a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer, for example, nonpolar carbonization. Hydrogen solvents, polar and nonpolar petroleum solvents, and the like can be used.

  Preferably, the solvent can comprise a condensed polycyclic hydrocarbon. When the solvent contains a condensed polycyclic hydrocarbon, it is possible to avoid white turbidity that may occur when the adhesive composition is stored in a liquid form (especially at a low temperature), thereby improving product stability. .

  Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. For example, straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc., branched hydrocarbons having 4 to 15 carbon atoms; p-menthane, o-menthane, m -Saturated aliphatic hydrocarbons such as menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tujang, kalan, longifolene, α-terpinene, β-terpinene, γ-terpinene, α -Pinene, β-pinene, α-tujon, β-tujon and the like.

  Examples of the petroleum solvent include cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and the like.

  The condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by two or more monocycles supplying only one side of each ring to each other, and is a carbon obtained by condensing two monocycles. It is preferable to use hydrogen.

  Such hydrocarbons include combinations of 5-membered rings and 6-membered rings, or combinations of two 6-membered rings. Examples of hydrocarbons combining 5-membered and 6-membered rings include indene, pentalene, indane, tetrahydroindene and the like. Examples of hydrocarbons combining two 6-membered rings include naphthalene, tetrahydronaphthalene ( Tetralin) and decahydronaphthalene (decalin).

  Further, when the solvent contains the condensed polycyclic hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, or contains other components such as saturated aliphatic hydrocarbon, for example. You may do it. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more, more preferably 60 parts by weight or more based on the entire hydrocarbon solvent. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more of the entire hydrocarbon solvent, high solubility in the resin can be exhibited. If the mixing ratio of the condensed polycyclic hydrocarbon and the saturated aliphatic hydrocarbon is within the above range, the odor of the condensed polycyclic hydrocarbon can be alleviated.

  In addition, the content of the solvent in the adhesive composition of the present invention may be appropriately adjusted according to the thickness of the adhesive layer formed using the adhesive composition. When the total amount is 100 parts by weight, it is preferably in the range of 20 to 90 parts by weight. If the content of the solvent is within the above range, the viscosity can be easily adjusted.

(Thermal polymerization inhibitor)
In the present invention, the adhesive composition may contain a thermal polymerization inhibitor. The thermal polymerization inhibitor has a function of preventing radical polymerization reaction due to heat. Specifically, since the thermal polymerization inhibitor is highly reactive to radicals, it reacts preferentially over the monomer and inhibits polymerization of the monomer. In the adhesive composition containing such a thermal polymerization inhibitor, the polymerization reaction is suppressed under a high temperature environment (particularly, 250 ° C. to 350 ° C.).

  For example, in a semiconductor manufacturing process, there is a high temperature process in which a wafer to which a support is bonded is heated at 250 ° C. for 1 hour. At this time, when the polymerization of the adhesive composition occurs at a high temperature, the solubility in a peeling solution for peeling the support from the wafer after the high-temperature process is lowered, and the support cannot be peeled well from the wafer. However, in the adhesive composition of the present invention containing a thermal polymerization inhibitor, since the oxidation due to heat and the polymerization reaction accompanying it are suppressed, the support plate can be easily peeled off even after a high temperature process, Generation of residue can be suppressed.

  Although it will not specifically limit if it is effective in preventing the radical polymerization reaction by heat | fever as a thermal-polymerization inhibitor, The thermal-polymerization inhibitor which has a phenol is preferable. Thereby, good solubility can be ensured even after high temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, it is possible to use a hindered phenol antioxidant, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, Amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 ′-(1-methylethylidene) bis (2-methylphenol), 4,4 ′-(1-methylethylidene) bis (2,6 -Dimethylphenol), 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidene tris (2- Methylphenol), 4,4 ', 4 "-ethylident Sphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 3,9 -Bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5 , 5) Undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n Octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name) IRGANOX 1010 (manufactured by BASF), tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like Can be mentioned. Only one type of thermal polymerization inhibitor may be used, or two or more types may be used in combination.

  The content of the thermal polymerization inhibitor may be appropriately determined according to the type of polymer having a cycloolefin structure, the type of (meth) acrylate monomer compatible with the polymer, and the use and use environment of the adhesive composition. However, for example, when the amount of the polymer having a cycloolefin structure is 100 parts by weight, it is preferably 0.1 parts by weight or more and 10 parts by weight or less. If the content of the thermal polymerization inhibitor is within the above range, the effect of suppressing the polymerization due to heat is satisfactorily exerted, and the decrease in the solubility of the adhesive composition in the stripping solution can be further suppressed after the high temperature process. .

(Additive solvent)
The adhesive composition according to the present invention has a composition different from a solvent for dissolving a thermal polymerization inhibitor and dissolving a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer. The structure containing an additive solvent may be sufficient. Although it does not specifically limit as an additive solvent, The organic solvent which melt | dissolves the component contained in an adhesive composition can be used.

  As an organic solvent, for example, each component of the adhesive composition may be dissolved to form a uniform solution, and any one kind or a combination of two or more kinds may be used.

  Specific examples of the organic solvent include, for example, a terpene solvent having an oxygen atom, a carbonyl group or an acetoxy group as a polar group, for example, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonon, thuyon, For example, camphor. Lactones such as γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol Polyhydric alcohols such as: ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, etc., compounds having an ester bond, monohydric ethers of the above polyhydric alcohols or compounds having an ester bond , Monoalkyl ethers such as monoethyl ether, monopropyl ether, monobutyl ether or ethers such as monophenyl ether Derivatives of polyhydric alcohols such as compounds having a combination (in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, and methyl lactate Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether And aromatic organic solvents such as dibenzyl ether, phenetole, and butyl phenyl ether.

  The content of the additive solvent may be appropriately determined according to the type of the thermal polymerization inhibitor and the like. For example, a solvent (main solvent) that dissolves the polymer having a cycloolefin structure and a solvent that dissolves the thermal polymerization inhibitor ( 1 part by weight and 50 parts by weight or less are preferable, and 1 part by weight or more and 30 parts by weight or less are more preferable. When the content of the additive solvent is within the above range, the thermal polymerization inhibitor can be sufficiently dissolved.

(Other ingredients)
The adhesive composition may further contain other miscible materials as long as the essential characteristics of the present invention are not impaired. For example, various commonly used additives such as an additional resin for improving the performance of the adhesive, a plasticizer, an adhesion aid, a stabilizer, a colorant, and a surfactant can be further used.

<Adhesive film>
The adhesive composition according to the present invention can employ various usage forms depending on the application. For example, a method of applying an adhesive layer on a workpiece such as a semiconductor wafer in a liquid state may be used, or an adhesive film according to the present invention, that is, a film such as a flexible film in advance. A method (adhesive film method) in which an adhesive layer containing any one of the above-described adhesive compositions is formed and then dried and this film (adhesive film) is attached to a workpiece and used. Good.

  Thus, the adhesive film which concerns on this invention is equipped with the contact bonding layer containing one of the said adhesive composition on a film.

  The adhesive film may be used by further covering the adhesive layer with a protective film. In this case, the protective film on the adhesive layer is peeled off, the exposed adhesive layer is overlaid on the workpiece, and then the film is peeled off from the adhesive layer so that the adhesive layer is easily formed on the workpiece. Can be provided.

  Therefore, when this adhesive film is used, an adhesive layer with good film thickness uniformity and surface smoothness can be formed compared to the case where the adhesive composition is applied directly on the workpiece to form the adhesive layer. Can be formed.

  As said film used for manufacture of an adhesive film, the mold release film which can peel the adhesive layer formed on the film from the said film, and can transfer an adhesive layer on to-be-processed surfaces, such as a protective substrate and a wafer There is no particular limitation as long as it is sufficient. For example, the flexible film which consists of synthetic resin films, such as a polyethylene terephthalate with a film thickness of 15-125 micrometers, polyethylene, a polypropylene, a polycarbonate, and a polyvinyl chloride, is mentioned. It is preferable that a release treatment is performed on the film as necessary to facilitate transfer.

  As a method of forming the adhesive layer on the film, a dry film thickness of the adhesive layer on the film is 10 to 1000 μm using a known method as appropriate according to the desired thickness and uniformity of the adhesive layer. Thus, the method of apply | coating the adhesive composition which concerns on this invention is mentioned.

  Moreover, when using a protective film, as a protective film, although not limited as long as it can peel from an contact bonding layer, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable, for example. Each protective film is preferably coated or baked with silicon. This is because peeling from the adhesive layer is facilitated. Although the thickness of a protective film is not specifically limited, 15-125 micrometers is preferable. This is because the flexibility of the adhesive film provided with the protective film can be ensured.

  The method of using the adhesive film is not particularly limited. For example, when a protective film is used, the adhesive layer exposed on the work piece is overlaid on the film after peeling it off. The method of thermocompression-bonding an adhesive layer to the surface of a to-be-processed body by moving a heating roller from (the back surface of the surface in which the adhesive layer was formed) is mentioned. At this time, the protective film peeled off from the adhesive film can be stored and reused by winding it in a roll with a roller such as a winding roller.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention.

(Preparation of adhesive composition)
Example 1
APL8008T manufactured by Mitsui Chemicals, Inc. (the following chemical formula (I), Mw = 100,000, Mw / Mn = 2.1, m: n = 80: 20 (molar ratio)) 5 parts by weight of ADCP (tricyclodecane dimethanol diacrylate) manufactured by company was added, dissolved with decahydronaphthalene, and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 made from BASF was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of Example 1 was prepared.

(Example 2)
5 parts by weight of DCP (tricyclodecane dimethanol dimethacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. was added to 100 parts by weight of APL8008T, dissolved in decahydronaphthalene, and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of Example 2 was prepared.

(Example 3)
TOPAS8007 (the following chemical formula (II), Mw = 95,000, Mw / Mn = 1.9, m: n = 35: 65 (molar ratio)) manufactured by Polyplastics Co., Ltd. 5 parts by weight of ADCP A portion was added and dissolved with decahydronaphthalene and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of Example 3 was prepared.

Example 4
To 100 parts by weight of APL8008T, 5 parts by weight of ADCP and 3 parts by weight of Permicle D manufactured by NOF Corporation were added, dissolved in decahydronaphthalene, and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of Example 4 was prepared.

(Example 5)
5 parts by weight of ADCP and 3 parts by weight of perbutyl C manufactured by NOF Corporation were added to 100 parts by weight of APL8008T, dissolved in decahydronaphthalene, and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of Example 5 was prepared.

(Examples 6 to 8)
Based on the composition ratios shown in Table 1 below, adhesive compositions of Examples 6 to 8 were prepared. The values of ADCP, DCP, permicle D and perbutyl C shown in Table 1 represent parts by weight with respect to 100 parts by weight of the resin (APL8008T).

(Comparative Example 1)
100 parts by weight of APL8008T was dissolved with decahydronaphthalene and further dissolved in butyl acetate. And 1 weight part of IRGANOX1010 was added with respect to the resin part, the viscosity adjustment was performed, and the adhesive composition of the comparative example 1 was prepared.

  Table 1 shows the composition ratio of each component constituting the adhesive composition according to Examples 1 to 8 and Comparative Example 1, and the results of each test on the adhesive composition.

(Sample preparation for evaluation)
The above adhesive composition was spin-coated on a semiconductor wafer substrate (12 inches, silicon), baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each to evaporate the solvent and form an adhesive layer (film thickness) 50 μm). Next, the wafer on which the adhesive layer was formed was cured (cured) for 1 hour in a heating furnace in a nitrogen atmosphere at 200 ° C. to complete the curing of the monomer contained in the adhesive layer. Thereafter, before and after curing, a transmittance of 400 nm was measured with a spectrophotometer (instant multi-photometry system MCPD3000, manufactured by Otsuka Electronics Co., Ltd.). As a result, since the transmittance after curing was 98% or more in all the samples for evaluation, the results of the transmittance after curing were all “◯”.

(Heat-resistant transmittance test)
Each sample for evaluation was placed on a hot plate heated to 265 ° C. and heated for 10 minutes. Before and after heating, the transmittance at 400 nm was measured with a spectrophotometer. Since the transmittance after curing was 98% or more in all the samples for evaluation, the results of the heat-resistant transmittance test were all “◯”.

(Heat cycle test)
Samples for evaluation (Examples 1 to 8 and Comparative Example 1) were put into a thermal shock tester TSE-11-A (ESPEC Corp.), and the samples were each kept at −40 ° C. and 100 ° C. Moved between. The holding time of the sample in each thermostat was 30 minutes, and it was set as 1 heat cycle in 1 hour in total. After conducting the heat cycle test up to 100 cycles, the state of the adhesive layer was visually observed. After 100 cycles, a sample in which the adhesive layer was not peeled from the substrate was indicated as “◯”, and a sample in which the adhesive layer was peeled off from the substrate was indicated as “x”.

  From the results of the transmittance after curing and the heat-resistant transmittance test, it was found that the transmittance after heating hardly deteriorates even when the (meth) acrylate monomer is compatible with the polymer having a cycloolefin structure.

  From the result of the heat cycle test, it was found that the adhesive layer formed from the adhesive composition not containing (meth) acrylate may be peeled off from the substrate due to the thermal shock caused by the heat cycle after the substrate is attached. . On the other hand, it has been found that the adhesive layer formed from the adhesive composition containing (meth) acrylate is less likely to be peeled off from the substrate due to the thermal shock caused by the heat cycle after the substrate is attached.

  The adhesive composition according to the present invention can be used as a permanent adhesive for optical members such as CMOS image sensors.

Claims (8)

A polymer containing a cycloolefin monomer as a monomer component;
A (meth) acrylate monomer compatible with the polymer;
A thermal polymerization inhibitor that prevents radical polymerization reaction due to heat;
A solvent containing a condensed polycyclic hydrocarbon and dissolving the polymer and the (meth) acrylate monomer;
The polymer was dissolved the (meth) acrylate monomer, and the thermal polymerization inhibitor, made from a different composition as the solvent, and an additive solvent having a polar group, only contains,
For 100 parts by weight of the polymer,
An adhesive composition comprising the (meth) acrylate monomer in a range of 1 to 15 parts by weight (excluding 1000/70 parts by weight or more with respect to 100 parts by weight of the polymer) .   2. The adhesive according to claim 1, wherein the (meth) acrylate monomer is at least one (meth) acrylate monomer selected from a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer. Agent composition.   The adhesive composition according to claim 1, further comprising a thermal polymerization initiator that accelerates a polymerization reaction of the (meth) acrylate monomer.   The adhesive composition according to claim 3, wherein the thermal polymerization initiator is a peroxide. The weight average molecular weight of the said polymer is the range of 50,000 or more and 150,000 or less, The adhesive composition as described in any one of Claims 1-4 characterized by the above-mentioned. It is used in order to adhere | attach a board | substrate and a support body, The adhesive composition as described in any one of Claims 1-5 characterized by the above-mentioned. An adhesive film comprising the adhesive composition according to any one of claims 1 to 5 is formed on the film. A layered product formed by bonding a substrate and a support through an adhesive layer comprising the adhesive composition according to any one of claims 1 to 6 .