JP5499454B2 - Photosensitive adhesive composition, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a photosensitive adhesive composition, an adhesive sheet, an adhesive pattern, a semiconductor wafer with an adhesive layer, a semiconductor device, and a manufacturing method thereof.

  2. Description of the Related Art Semiconductor packages having various forms have been proposed with the recent enhancement of performance and functionality of electronic components. In a semiconductor package, an adhesive for bonding a semiconductor element and a support base for mounting a semiconductor element is required to have low stress properties, low-temperature adhesiveness, moisture resistance reliability, and solder reflow resistance. Depending on the function and form of the semiconductor package and the method of simplifying the assembly process, it may be required to have a photosensitive function capable of forming a pattern. Photosensitivity is a function in which a portion irradiated with light is chemically changed and insolubilized or solubilized in an aqueous solution or an organic solvent. When this photosensitive photosensitive adhesive is used, a high-definition adhesive pattern can be formed by performing exposure and development processing through a photomask.

As a photosensitive material, a material based on a polyimide resin precursor (polyamic acid) or a polyimide resin has been used in addition to a photoresist (see Patent Documents 1 to 3).
JP 2000-290501 A JP 2001-329233 A Japanese Patent Laid-Open No. 11-24257

  Many of the conventional photosensitive materials have not been designed assuming a function as an adhesive after development. It is difficult for a general photoresist to secure the heat resistance required as an adhesive. Although the polyimide resin precursor and the polyimide resin are excellent in heat resistance, the former requires a high temperature of 300 ° C. or more at the time of thermal ring-closing imidization in the former case and the processing in the latter case. There were problems such as large thermal damage and easy occurrence of thermal stress. For this reason, attempts have also been made to improve low-temperature workability and solder heat resistance by blending and crosslinking a thermosetting resin in an adhesive using a polyimide resin or the like.

  However, according to conventional photosensitive resins including polyimide resins, it has been difficult to simultaneously achieve a high level of both pattern formability with an alkali developer and adhesion to an adherend at a low temperature. . Moreover, it has been difficult to impart re-adhesiveness that can maintain a sufficiently high adhesive force even at high temperatures when thermocompression bonding is performed after exposure.

  The present invention has been made in view of the above-described problems of the prior art. In a photosensitive adhesive composition for a semiconductor element used for adhering a semiconductor element to a support member, pattern formation by an alkaline developer and re-use are possible. The main purpose is to improve the heat resistance after bonding and the low temperature sticking property when formed into a film.

  The present invention includes (A) an alkali-soluble polymer that is a copolymer containing a maleimide monomer having a maleimide group and a monofunctional vinyl monomer as monomer units, (B) a thermosetting resin, and (C) a radiation polymerizable compound. (D) It is related with the photosensitive adhesive composition for semiconductor elements containing a photoinitiator.

  According to the photosensitive adhesive composition of the present invention, it is possible to improve the pattern formability with an alkali developer, the heat resistance after re-adhesion, and the low-temperature sticking property when formed into a film.

  The alkali-soluble polymer is preferably a copolymer having a carboxyl group and / or a phenolic hydroxyl group. In particular, the maleimide monomer preferably contains a compound having a carboxyl group and / or a phenolic hydroxyl group. By introducing a carboxyl group and / or a phenolic hydroxyl group into the alkali-soluble polymer, the solubility of the uncured photosensitive adhesive composition in the alkali developer is further increased, and a better pattern forming property is obtained.

  The thermosetting resin is preferably an epoxy resin. By using an epoxy resin, workability and productivity are further improved.

  The radiation polymerizable compound preferably has an acrylate group and / or a methacrylate group. A radiation-polymerizable compound having an acrylate group or the like contributes to more excellent pattern formability when used in combination with an alkali-soluble polymer.

  The glass transition temperature (Tg) of the alkali-soluble polymer is preferably 150 ° C. or lower. When the Tg of the alkali-soluble polymer is low, it can be attached to the adherend at a lower temperature, and thermal damage to the peripheral member can be suppressed.

  The adhesive sheet according to the present invention includes a film-like adhesive layer made of the photosensitive adhesive composition according to the present invention. The adhesive sheet according to the present invention may further include a base material, and an adhesive layer may be provided on one surface of the base material.

  According to these adhesive sheets, it is possible to improve the pattern formability with an alkali developer, the heat resistance after re-adhesion, and the low-temperature stickability when formed into a film. Moreover, by providing the film-like adhesive layer, the adhesive sheet can contribute to the efficiency of the semiconductor device assembly process.

  The adhesive pattern which concerns on this invention exposes the film-form adhesive layer which consists of the photosensitive adhesive composition which concerns on the said invention, and develops the said adhesive layer after exposure using an alkali developing solution. Is formed.

  This adhesive pattern can have a high-definition pattern and is excellent in re-adhesion.

  The semiconductor wafer with an adhesive layer according to the present invention includes a semiconductor wafer and an adhesive layer made of the photosensitive adhesive composition according to the present invention provided on one surface of the semiconductor wafer.

  The present invention also relates to a semiconductor device including a support member, a semiconductor element mounted on the support member, and an adhesive layer interposed between the support member and the semiconductor element. The adhesive layer is formed by the photosensitive adhesive composition according to the present invention.

  The semiconductor device according to the present invention has excellent heat resistance and moisture resistance reliability since the semiconductor element is bonded to the support member using the photosensitive adhesive composition according to the present invention.

  The present invention also includes a step of forming an adhesive pattern by exposing an adhesive layer comprising the photosensitive adhesive composition according to the present invention and developing the exposed adhesive layer using an alkaline developer. And a method of manufacturing a semiconductor device comprising a step of bonding a semiconductor element and a support member on which the semiconductor element is mounted via an adhesive pattern.

  The semiconductor device according to the present invention and the semiconductor device obtained by the manufacturing method according to the present invention are excellent because the semiconductor element is bonded to the support member using the photosensitive adhesive composition according to the present invention. It has heat resistance and moisture resistance reliability.

  According to the present invention, in a photosensitive adhesive composition for a semiconductor element used for adhering a semiconductor element to a support member, the film is formed into a film with pattern forming properties by an alkali developer and heat resistance after re-adhesion. It is possible to improve the low-temperature sticking property.

  In addition, the photosensitive adhesive composition according to the present invention is also prevented from causing unreacted components to volatilize and cause peeling of the adherend and element contamination during the heat treatment after being pressure-bonded to the adherend. . This is also advantageous with respect to the polyimide resin that easily causes volatilization of unreacted components.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  1, 2 and 3 are schematic cross-sectional views each showing an embodiment of an adhesive sheet. The adhesive sheet 100 shown in FIG. 1 is comprised from the adhesive bond layer 1 which is the photosensitive adhesive composition shape | molded by the film form. The adhesive sheet 110 shown in FIG. 2 is comprised from the base material 3 and the adhesive bond layer 1 provided on one surface of this. The adhesive sheet 120 shown in FIG. 3 includes a base material 3, an adhesive layer 1 provided on one surface of the base material 3, and a cover film 2. The photosensitive adhesive composition that forms the adhesive layer 1 includes (A) an alkali-soluble polymer that is a copolymer including a monomer unit derived from a maleimide monomer having a maleimide group and a monomer unit derived from a monofunctional vinyl monomer; , (B) a thermosetting resin, (C) a radiation polymerizable compound, and (D) a photoinitiator. Details of the photosensitive adhesive composition will be described later.

  The adhesive sheet 100 of FIG. 1 mixes the photosensitive adhesive composition which concerns on below-mentioned embodiment in an organic solvent, knead | mixes a liquid mixture, prepares a varnish, and forms the layer of this varnish on the base material 3 The base material 3 can be obtained by drying the varnish layer by heating. The adhesive layer 1 can be stored and used in the state of the adhesive sheet 110 or 120 without removing the base material 3.

  The above mixing and kneading can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. In addition, it dries on the conditions which (B) thermosetting resin does not fully react during drying, and the solvent fully volatilizes. Specifically, the varnish layer is dried by heating at 60 to 180 ° C. for 0.1 to 90 minutes. The preferred thickness of the varnish layer before drying is 1 to 100 μm. If this thickness is less than 1 μm, the adhesive fixing function tends to be impaired, and if it exceeds 100 μm, the residual volatile matter described later tends to increase.

  The preferred residual volatile content of the adhesive layer 1 is 10% by mass or less. If this residual volatile content exceeds 10% by mass, voids tend to remain inside the adhesive layer due to foaming due to solvent volatilization during assembly heating, and the moisture resistance reliability tends to be impaired. There is a tendency that the possibility of contamination of surrounding materials or members due to the generated volatile components is increased. In addition, the measurement conditions of said residual volatile component are as follows. That is, the initial mass of the adhesive layer cut to a size of 50 mm × 50 mm is M1, the mass after being heated in an oven at 160 ° C. for 3 hours is M2, and {(M1-M2) / M1} × 100 = remaining It is a value calculated by volatile content (%).

  Specifically, the temperature at which the thermosetting resin does not sufficiently react is determined by using DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.) The temperature is equal to or lower than the peak temperature of the heat of reaction when measured under the conditions of temperature rate: 5 ° C./min and measurement atmosphere: air.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as the material can be uniformly dissolved or dispersed. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone.

  The substrate 3 is not particularly limited as long as it can withstand the above drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, or a methylpentene film can be used as the substrate 3. The film as the substrate 3 may be a multilayer film in which two or more kinds are combined, or the surface may be treated with a release agent such as a silicone or silica.

  An adhesive layer and a dicing sheet can also be laminated. The dicing sheet is a sheet in which a pressure-sensitive adhesive layer is provided on a substrate, and the pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation curable type. The base material is preferably a base material that can be expanded. By using such an adhesive sheet, a dicing / die bonding integrated adhesive sheet having both a function as a die bond film and a function as a dicing sheet can be obtained.

  Specific examples of the dicing / die bonding integrated adhesive sheet include an adhesive sheet 130 in which a base material 7, an adhesive layer 6 and an adhesive layer 1 are formed in this order, as shown in FIG.

  FIG. 5 is a top view showing an embodiment of a semiconductor wafer with an adhesive layer, and FIG. 6 is an end view taken along line VI-VI in FIG. A semiconductor wafer 20 with an adhesive layer shown in FIGS. 5 and 6 includes a semiconductor wafer 8 and an adhesive layer 1 similar to the adhesive sheet provided on one surface of the semiconductor wafer 8.

  The semiconductor wafer 20 with an adhesive layer is obtained by laminating the adhesive layer 1 on the semiconductor wafer 8 while heating. Since the adhesive layer 1 is a sheet made of a photosensitive adhesive composition, which will be described later, it can be attached to the semiconductor wafer 8 at a low temperature of about room temperature (25 ° C.) to 150 ° C., for example.

  7 and 9 are top views showing an embodiment of the adhesive layer pattern. 8 is an end view taken along line VIII-VIII in FIG. 7, and FIG. 10 is an end view taken along line XX in FIG. The adhesive patterns 1a and 1b shown in FIGS. 7, 8, 9, and 10 are formed on a semiconductor wafer 8 as an adherend so as to have a pattern along a substantially square side or a square pattern.

  The adhesive patterns 1a and 1b are obtained by forming an adhesive layer 1 made of a photosensitive adhesive composition on a semiconductor wafer 8 as an adherend to obtain a semiconductor wafer 20 with an adhesive layer. It is formed by exposing through a mask and developing the exposed adhesive layer 1 with an alkaline developer. Thereby, semiconductor wafers 20a and 20b with an adhesive layer in which adhesive patterns 1a and 1b are formed are obtained.

  Embodiments of a semiconductor device will be specifically described with reference to the drawings. In recent years, semiconductor devices having various structures have been proposed, and the use of the photosensitive adhesive composition of the present invention is not limited to the semiconductor devices having the structures described below.

  FIG. 11 is a schematic cross-sectional view showing an embodiment of a semiconductor device. In the semiconductor device 200 shown in FIG. 11, the semiconductor element 12 is bonded to the semiconductor element mounting support member 13 via the adhesive layer 1, and the connection terminal of the semiconductor element 12 is electrically connected to the external connection terminal via the wire 14. It is connected. The semiconductor element 12 is sealed with a sealing material 15.

  FIG. 12 is a schematic cross-sectional view showing another embodiment of the semiconductor device. In the semiconductor device 210 shown in FIG. 12, the first-stage semiconductor element 12a is bonded via the adhesive layer 1 to the semiconductor-element mounting support member 13 on which the terminals 16 are formed, and on the first-stage semiconductor element 12a. Further, the second-stage semiconductor element 12 b is bonded via the adhesive layer 1. The connection terminals of the first-stage semiconductor element 12 a and the second-stage semiconductor element 12 b are electrically connected to the external connection terminals via the wires 14. The semiconductor elements 12 a and 12 b are sealed with a sealing material 15. Thus, the photosensitive adhesive composition of the present embodiment can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

  In the semiconductor device (semiconductor package) shown in FIGS. 11 and 12, for example, the semiconductor wafer 20b with an adhesive layer shown in FIG. 9 is diced along the broken line D, and the semiconductor element with the adhesive layer after dicing is mounted on the semiconductor element. It can be obtained by thermocompression bonding to the supporting member 13 and bonding them together, followed by steps such as a wire bonding step and, if necessary, a sealing step with a sealing material. The heating temperature in the thermocompression bonding is usually 20 to 250 ° C., the load is usually 0.01 to 20 kgf, and the heating time is usually 0.1 to 300 seconds.

  The photosensitive adhesive composition for a semiconductor device of the present invention includes (A) an alkali-soluble polymer that is a copolymer containing a maleimide monomer having a maleimide group and a monofunctional vinyl monomer as monomer units, and (B) a thermosetting resin. And (C) a radiation polymerizable compound and (D) a photoinitiator.

  The alkali-soluble polymer is not particularly limited as long as it is a copolymer containing a maleimide monomer having a maleimide group and a monofunctional vinyl monomer having one carbon-carbon double bond in the molecule as monomer units.

  Examples of the maleimide monomer include N-alkylmaleimides having a linear or branched alkyl group having 1 to 10 carbon atoms, such as N-methylmaleimide and N-ethylmaleimide, N- (2 -Cyanoethyl) maleimide, N-methoxycarbonylmaleimide and N-ethoxycarbonylmaleimide represented by N-alkoxycarbonylmaleimide having a linear or branched alkoxy group having 1 to 7 carbon atoms, N- (2-carboxyethyl) maleimide N- (3-carboxypropyl) maleimide, N- (4-carboxybutyl) maleimide, N- (5-carboxypentyl) maleimide, N- (6-carboxyhexyl) maleimide, N-furfurylmaleimide, N-cyclohexyl Maleimide, -Cyclopentylmaleimide, N-benzylmaleimide, N- (1-phenylethyl) maleimide, N- (1-naphthyl) -maleimide, N-methoxypolyethyleneglycolmaleimide, 2-fluorenylmaleimide, N- (9-acridinyl) Maleimide, 4- (N-maleimido) benzophenone, 4- (N-maleimido) azobenzene, N- [4- (2-benzimidazolyl) phenyl] maleimide, N- (1-pyrenylmaleimide), 3-maleimidobenzoic acid It is selected from the group consisting of N-hydroxysuccinimide ester, 6-maleimidohexanoic acid N-hydroxysuccinimide ester, and a compound represented by the following general formula (1). These maleimide monomers may be used alone or as a mixture of two or more compounds.

Ｒ^１及びＲ^２はベンゼン環に結合する置換基を示し、それぞれ独立に、水素、炭素数１〜７の直鎖状アルキル基、炭素数１〜７の分岐したアルキル基、炭素数１〜７のアルコキシ基、フェニル基、水酸基、カルボキシル基、フッ素、シアノ基、イソシアネート基、ニトロ基、メルカプト基、炭素数１〜５のアルキルチオ基、トリフルオロメチル基、炭素数１〜７のエステル基、フェノキシ基、又は炭素数１〜７のアルキルカルボニル基を示す。式（１）の化合物のＲ^１及びＲ^２のうち一方は水酸基又はカルボキシル基であることが好ましい。式（１）の化合物の例としては、２−メチル−Ｎ−フェニルマレイミドがある。

R ¹ and R ² each represent a substituent bonded to the benzene ring, and each independently represents hydrogen, a linear alkyl group having 1 to 7 carbon atoms, a branched alkyl group having 1 to 7 carbon atoms, or 1 to 7 carbon atoms. Alkoxy group, phenyl group, hydroxyl group, carboxyl group, fluorine, cyano group, isocyanate group, nitro group, mercapto group, alkylthio group having 1 to 5 carbon atoms, trifluoromethyl group, ester group having 1 to 7 carbon atoms, phenoxy Group or an alkylcarbonyl group having 1 to 7 carbon atoms. One of R ¹ and R ^{2 in} the compound of formula (1) is preferably a hydroxyl group or a carboxyl group. An example of a compound of formula (1) is 2-methyl-N-phenylmaleimide.

  As the monofunctional vinyl monomer, a known compound can be used without particular limitation as long as it is a compound copolymerizable with a maleimide monomer by thermal radical polymerization or thermal anion polymerization. The monofunctional vinyl monomer is selected from, for example, a styrene derivative, an allyl derivative, and a (meth) acrylic acid derivative having an acryloyl group or a methacryloyl group (hereinafter referred to as a (meth) acryloyl group).

  For example, it has a C1-C18 linear alkyl group represented by methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate-2-ethylhexyl ( (Meth) acrylic acid ester, (meth) acrylic acid ester having a C1-C18 cyclic alkyl group, EO-modified or PO-modified (meth) acrylic acid ester, (meth) acrylic acid, itaconic acid, maleic acid, Unsaturated carboxylic acid derivatives such as fumaric acid and unsaturated carboxylic acid ester derivatives thereof, unsaturated nitrile derivatives such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-methylol acrylamide, and unsaturated nitrile such as N-methylol methacrylamide Amide derivatives, vinyl acetate, vinyl propionate Any vinyl ester derivative, vinyl ether derivatives such as methyl vinyl ether and ethyl vinyl ether, olefin derivatives such as ethylene and propylene, styrene, p-hydroxystyrene, α-methylstyrene, 4-acetoxystyrene, 4-t-butylstyrene, 4-methoxy Use styrene derivatives such as styrene, 4-t-butoxystyrene, 4-vinylbenzoic acid, and nitrogen-containing vinyl derivatives such as N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole, vinylcarbazole as monofunctional vinyl monomers. Can do. These can be used alone or in combination of two or more, and in order to develop solubility in an alkaline developer, a vinyl compound having a carboxyl group or a phenolic hydroxyl group in the molecule and other vinyl compounds Can be used in combination.

  The alkali-soluble polymer, which is a copolymer containing the maleimide monomer and the monofunctional vinyl monomer as monomer units, can be prepared by a known method such as thermal radical polymerization or thermal anion polymerization. Radical polymerization is more preferred because the method is simple and there are few functional group restrictions. For example, a maleimide monomer and a monofunctional vinyl monomer are dissolved in an organic solvent, and a peroxide represented by benzoyl peroxide or an azo represented by azobisisobutyronitrile (AIBN) in an inert atmosphere such as nitrogen. It can be obtained by adding a compound and stirring while heating.

  The weight average molecular weight of the alkali-soluble polymer is preferably controlled within a range of 5,000 to 800,000, more preferably 10,000 to 100,000. When the weight average molecular weight is within this range, the strength, flexibility, and tackiness of a sheet or film are appropriate, the handleability is good, and the alkali developer is well dissolved. Showing gender. When the said weight average molecular weight is less than 5000, there exists a tendency for the film formation of the photosensitive adhesive composition to fall. Moreover, when the said weight average molecular weight exceeds 800,000, the fluidity | liquidity of a photosensitive adhesive composition will fall, adhesive force will fall, and there exists a tendency for the solubility with respect to an alkali developing solution also to fall.

  When a film-like adhesive layer using the photosensitive adhesive composition of the present invention is attached to the back side of the wafer, the above-mentioned attaching temperature is preferably 20 to 200 ° C. from the viewpoint of suppressing the warpage of the semiconductor wafer. 20-150 degreeC is still more preferable, and 25-100 degreeC is still more preferable. In order to enable attachment at the above temperature, it is preferable to set the Tg of the adhesive layer to 150 ° C. or lower, and to that end, it is desirable to set the Tg of the alkali-soluble polymer to 150 ° C. or lower, -20-100 degreeC is more preferable. When the Tg exceeds 150 ° C., there is a high possibility that the bonding temperature on the back surface of the wafer exceeds 200 ° C., and warpage after bonding to the back surface of the wafer tends to occur, and Tg is −20. When the temperature is lower than 0 ° C., the surface tack of the adhesive layer becomes too strong, and the handleability tends to deteriorate. In addition, you may use a thermoplastic resin as (A) alkali-soluble polymer.

  By setting the weight-average molecular weight and Tg of the alkali-soluble polymer within the above ranges, not only can the temperature for attaching to the backside of the wafer be kept low, but also the semiconductor element is adhesively fixed to the semiconductor element mounting support member. The heating temperature (die bonding temperature) at the time can also be lowered, and an increase in warpage of the semiconductor element can be suppressed. Further, fluidity and pattern formability during die bonding can be effectively imparted. The above-mentioned Tg is the main dispersion peak temperature when the photosensitive adhesive composition of the present invention is formed into a film, and using a rheometric viscoelasticity analyzer RSA-2, the heating rate is 5 ° C./min. The frequency was 1 Hz and the measurement temperature was −150 to 300 ° C., and the tan δ peak temperature in the vicinity of Tg was measured. Moreover, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using the high performance liquid chromatography (C-R4A) by Shimadzu Corporation.

  The photosensitive adhesive composition of the present invention further comprises (B) a thermosetting resin. In the present invention, the thermosetting resin refers to a reactive compound capable of causing a crosslinking reaction by heat. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, Xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, thermosetting resin synthesized from cyclopentadiene, aromatic Examples thereof include a thermosetting resin by trimerization of dicyanamide. Among these, epoxy resins, cyanate resins, and bismaleimide resins are preferable because they can have excellent adhesive strength at high temperatures, and epoxy resins are particularly preferable from the viewpoint of workability and productivity. These thermosetting resins can be used alone or in combination of two or more.

  As said epoxy resin, what contains at least 2 or more epoxy group in a molecule | numerator is more preferable, and the glycidyl ether type epoxy resin of phenol is very preferable from the point of sclerosis | hardenability and hardened | cured material property. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolac resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used alone or in combination of two or more. In addition, for these epoxy resins, it is possible to use a high-purity product in which impurity ions, alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less, It is preferable for preventing electromigration and preventing corrosion of metal conductor circuits.

  The epoxy resin is preferably 0.1 to 200 parts by mass, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble polymer. When the amount of the epoxy resin exceeds 200 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the pattern formability tends to be lowered. If it is less than 0.1 parts by mass, the high-temperature adhesiveness tends to be low.

  When using said epoxy resin, a hardening | curing agent can also be used as needed. Examples of such curing agents include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, Examples include organic acid dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. Among them, phenolic compounds are preferable, and phenolic compounds having at least two phenolic hydroxyl groups in the molecule are more preferable. Examples of such compounds include phenol novolak, cresol novolak, t-butylphenol novolak, dicyclopentagen cresol novolak, dicyclopentagen phenol novolak, xylylene modified phenol novolak, naphthol compound, trisphenol compound, tetrakisphenol novolak. Bisphenol A type novolak, poly-p-vinylphenol, phenol aralkyl resin and the like. Among these, those having a number average molecular weight in the range of 400 to 30,000 are preferable. Thereby, the outgas at the time of heating which causes the contamination of the semiconductor element or the device at the time of assembling the semiconductor device can be suppressed.

  The amount of the curing agent used is determined by the ratio between the total amount of epoxy groups (epoxy equivalent) in the epoxy resin and the total amount of functional groups reactive with the epoxy group (for example, the hydroxyl group equivalent of a phenolic compound). It is more preferable that the ratio is 0.2 / 1.0 to 1.8 / 1.0 in terms of the total amount of epoxy / total amount of epoxy groups (equivalent ratio). When this ratio is less than 0.2 / 1.0 and more than 1.8 / 1.0, a large amount of unreacted epoxy groups and functional groups remain in the cured product. There is a tendency to reduce mechanical properties.

  The photosensitive adhesive composition according to this embodiment contains (C) a radiation polymerizable compound. The radiation-polymerizable compound is not particularly limited as long as it is a compound that can be polymerized and / or cured by irradiation with radiation such as ultraviolet rays and electron beams. Specific examples of radiation polymerizable compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, diethylene glycol di- (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Tylene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, 1,2- (meta ) Acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, tris (β-hydroxyethyl) isocyanurate tri (meth) acrylate, epoxy (meth) acrylate oligomer, urethane ( Oligomers such as (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyethylene glycol di (meth) acrylate, polyalkylene glycol Di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meta ) Acrylate, isocyanuric acid-modified trifunctional (meth) acrylate, bisphenoxyethanol fluorene (meth) acrylate, epoxy (meth) acrylate with bisphenol fluorenediglycidyl ether glycidyl group added with (meth) acrylic acid, bisphenol fluorenediglycidyl ether A compound obtained by adding a (meth) acryloyloxy group to a compound obtained by adding ethylene glycol or propylene glycol to a glycidyl group of the following general formula (2) or ( Polyfunctional (meth) acrylate compounds such as compounds represented by) a compound represented by the following general formula (4), urethane acrylates or urethane methacrylates, and urea (meth) acrylate and the like.

［Ｒ^３は水素又はメチル基、Ｒ^４は水素又はメチル基、ｋは１〜８の整数、ｌは１〜８の整数を表す。］

[R ³ is hydrogen or a methyl group, R ⁴ is hydrogen or a methyl group, k is an integer of 1 to 8, and l is an integer of 1 to 8. ]

［Ｒ^５は水素又はメチル基、Ｒ^６は水素又はメチル基、ｍは１〜８の整数、ｎは０〜８の整数を表す。］

[R ⁵ represents hydrogen or a methyl group, R ⁶ represents hydrogen or a methyl group, m represents an integer of 1 to 8, and n represents an integer of 0 to 8. ]

［Ｒ^７は水素原子又はメチル基を示し、ｑ及びｒは各々独立に１以上の整数を示す。］

[R ⁷ represents a hydrogen atom or a methyl group, and q and r each independently represents an integer of 1 or more. ]

  Urethane acrylate and urethane methacrylate are produced, for example, by reaction of a diol, an isocyanate compound represented by the following general formula (5), and a compound represented by the following general formula (6).

［Ｒ^８は炭素原子数が１〜３０の２価又は３価の有機基であり、ｓは０又は１を示す。］

[R ⁸ is a divalent or trivalent organic group having 1 to 30 carbon atoms, and s represents 0 or 1. ]

［Ｒ^９は水素原子又はメチル基を示し、Ｒ^１０はエチレン基又はプロピレン基を示す。］

[R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an ethylene group or a propylene group. ]

  Urea (meth) acrylate is produced, for example, by a reaction between a diamine represented by the following general formula (7) and a compound represented by the following general formula (8).

［Ｒ^１１は炭素原子数が２〜３０の２価の有機基を示す。］

[R ¹¹ represents a divalent organic group having 2 to 30 carbon atoms. ]

［Ｒ^１２は水素原子又はメチル基、Ｒ^１３は炭素原子数が２〜３０の２価の有機基を示す。］

[R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a divalent organic group having 2 to 30 carbon atoms. ]

  (C) As a radiation-polymerizable compound, in addition to the above compounds, a vinyl copolymer containing a functional group, at least one ethylenically unsaturated group, an oxirane ring, an isocyanate group, a hydroxyl group, and a carboxyl group A radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain, obtained by addition reaction of a compound having a functional group such as, etc. can be used.

  These radiation polymerizable compounds can be used alone or in combination of two or more. Especially, the radiation polymerization compound shown by the said General formula (4) is preferable at the point which can provide the solvent resistance after hardening, and urethane acrylate and urethane methacrylate are preferable at the point which can provide the high adhesiveness after hardening.

  (C) The content of the radiation-polymerizable compound is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble polymer. When the amount of the radiation-polymerizable compound exceeds 200 parts by mass, the fluidity at the time of heat melting decreases due to polymerization, and the adhesiveness at the time of thermocompression bonding tends to decrease. If it is less than 10 parts by mass, the solvent resistance after photocuring by exposure tends to be low, and it tends to be difficult to form a pattern.

  The adhesive composition according to this embodiment contains (D) a photoinitiator. Examples of the photoinitiator include a photopolymerization initiator that generates free radicals upon irradiation, a photobase generator that generates a base upon irradiation, and the like. As a photoinitiator, in order to improve sensitivity, those having an absorption band at 300 to 500 nm are preferable. Specific examples of the photoinitiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4 '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl -Aromatic ketones such as phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, benzoin methyl Ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ether, benzoin such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 -Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) 2,4,5-triarylimidazole dimer such as -4,5-diphenylimidazole dimer, 9-pheny Acridine derivatives such as acridine, 1,7-bis (9,9′-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,4) Bisacylphosphine oxide such as 6, -trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], (E) -1 -(1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) ethylideneaminooxy) ethanone and the like. These can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the quantity of a photoinitiator, Usually, it is 0.01-30 mass parts with respect to 100 mass parts of (A) alkali-soluble polymer.

  The photobase generator is not particularly limited as long as it is a compound that generates a base upon irradiation with radiation. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed. In general, a pKa value that is a logarithm of an acid dissociation constant is used as a basic index, and a base having a pKa value in an aqueous solution of 7 or more is preferable, and a base of 9 or more is more preferable.

  Examples of such photobase generators exhibiting basicity include imidazole derivatives such as imidazole, 2,4-dimethylimidazole and 1-methylimidazole, piperazine derivatives such as piperazine and 2,5-dimethylpiperazine, piperidine, 1 Piperidine derivatives such as 2-dimethylpiperidine, proline derivatives, trialkylamine derivatives such as trimethylamine, triethylamine, triethanolamine, 4-methylaminopyridine, 4-dimethylaminopyridine and the like, an amino group or an alkylamino group is at the 4-position Substituted pyridine derivatives, pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, alicyclic amine derivatives such as triethylenediamine and 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzylmethylamine, benzi Dimethylamine, and the like benzylamine derivatives such as benzyl diethylamine.

  Examples of the compounds generated by irradiation with the above-mentioned strongly basic compounds include, for example, Journal of Photopolymer Science and Technology 12, 313-314 (1999) and Chemistry of Materials 11, 170-176 (1999). The quaternary ammonium salt derivatives described in the above can be used. Since these produce strong basic trialkylamines by irradiation with actinic rays, they are optimal for curing epoxy resins.

  The carbamic acid derivatives described in Journal of American Chemical Society 118, 12925 (1996), Polymer Journal 28, 795 (1996), and the like can also be used.

  An oxime derivative that generates a primary amino group upon irradiation with actinic rays, a commercially available 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropan-1-one (Ciba) as a photo radical generator Irgacure 907 from Specialty Chemicals, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 from Ciba Specialty Chemicals), hexaarylbisimidazole derivative (halogen, alkoxy group) In addition, a substituent such as a nitro group or a cyano group may be substituted with a phenyl group), a benzoin oxazolone derivative, or the like can also be used.

  In addition to the photobase generator by the actinic ray, a basic compound is also generated by photo-Fries rearrangement, photo-Claisen rearrangement (photo-Cleisen rearrangement), Curtius rearrangement (Curtius rearrangement), and Stevens rearrangement (Stevens rearrangement) Curing can be performed.

  As the photobase generator, a low molecular compound having a molecular weight of 500 or less may be used, or a compound introduced into the main chain and side chain of a polymer may be used. The molecular weight in this case is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 30,000 from the viewpoints of adhesiveness and fluidity as an adhesive.

  Since these compounds do not show reactivity with the epoxy resin in a state where they are not irradiated with radiation at room temperature (25 ° C.), they have a feature of excellent storage stability at room temperature (25 ° C.).

  The photosensitive adhesive composition according to this embodiment may further contain a curing accelerator as necessary. The curing accelerator is not particularly limited as long as it cures the (B) thermosetting resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2- Examples include ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate.

  The photosensitive adhesive composition according to the present embodiment may further contain a sensitizer for the purpose of increasing the absorption and sensitivity of irradiated light. As the sensitizer to be used, known singlet sensitizers and triplet sensitizers can be used as long as they do not adversely affect the (B) thermosetting resin. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. The amount of the sensitizer used should refer to the absorption wavelength and molar extinction coefficient of the sensitizer, but is generally 0.01 to 5 parts by mass with respect to 1 part by mass of the (D) photoinitiator. Yes, 0.1-2 mass parts is preferable. If the sensitizer is less than 0.01 parts by mass, the light absorption efficiency is low, and if it exceeds 5 parts by mass, the light may not reach the entire photosensitive adhesive composition.

  The photosensitive adhesive composition according to this embodiment can also contain a filler. Examples of the filler include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Inorganic fillers such as aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramics, and organic fillers such as carbon and rubber fillers are included. Regardless, it can be used without any particular restrictions.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the adhesive composition, and the nonmetallic inorganic filler is thermally conductive, low thermal expansion, low hygroscopicity to the adhesive layer. The organic filler is added for the purpose of imparting toughness to the adhesive layer. These metal fillers, inorganic fillers or organic fillers can be used alone or in combination of two or more. Among them, a metal filler, an inorganic filler, or an insulating filler is preferable, and an inorganic filler or an insulating filler is preferable in that it can provide conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, and the like required for an adhesive material for a semiconductor device. Among the fillers, the silica filler is more preferable in that it has good dispersibility with respect to the resin varnish and can impart a high adhesive force when heated.

  The average particle diameter of the filler is preferably 10 μm or less, the maximum particle diameter is 30 μm or less, the average particle diameter is 5 μm or less, and the maximum particle diameter is more preferably 20 μm or less. When the average particle diameter exceeds 10 μm and the maximum particle diameter exceeds 30 μm, the effect of improving fracture toughness tends to be not obtained. Although there is no restriction | limiting in particular in a lower limit, Usually, both are 0.001 micrometer.

  The filler preferably satisfies both an average particle size of 10 μm or less and a maximum particle size of 30 μm or less. If a filler having a maximum particle size of 30 μm or less but an average particle size exceeding 10 μm is used, it becomes difficult to obtain high adhesive strength. Further, when a filler having an average particle size of 10 μm or less but having a maximum particle size exceeding 25 μm is used, the particle size distribution is widened and the adhesive strength tends to vary. Moreover, when processing and using a photosensitive adhesive composition in the shape of a thin film, the surface becomes rough and there exists a tendency for adhesive force to fall.

  Examples of the method for measuring the average particle size and the maximum particle size of the filler include a method of measuring the particle size of about 200 fillers using a scanning electron microscope (SEM). As a measuring method using SEM, for example, a sample obtained by adhering a semiconductor element and a semiconductor mounting support member using an adhesive layer and then heat-curing (preferably at 150 to 200 ° C. for 1 to 10 hours) is used. The method of producing, cutting the center part of this sample, and observing the cross section by SEM etc. is mentioned. At this time, it is preferable that the existence probability of the filler is 80% or more of the total filler.

  Although the usage-amount of the said filler is decided according to the characteristic to give or a function, it is 1-50 mass% normally with respect to the sum total of a resin component and a filler, Preferably it is 2-40 mass%, More preferably, it is 5-5. 30% by mass. By increasing the amount of filler, a high elastic modulus can be achieved, and dicing performance (cutability by a dicer blade), wire bonding performance (ultrasonic efficiency), and adhesive strength during heating can be effectively improved. If the amount of the filler is increased more than necessary, the thermocompression bonding property tends to be impaired. Therefore, the amount of the filler used is preferably within the above range. The optimal filler content is determined to balance the required properties. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

  Various coupling agents can be added to the adhesive composition of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective. The amount of the coupling agent used is a co-polymer containing a monomer unit derived from a maleimide monomer having (A) a maleimide group and a monomer unit derived from a monofunctional vinyl monomer, in terms of its effect, heat resistance and cost. It is preferable to set it as 0.01-20 mass parts with respect to 100 mass parts of alkali-soluble polymers which are coalescence.

  In the adhesive composition of the present invention, an ion scavenger may be further added in order to adsorb ionic impurities and improve insulation reliability at the time of moisture absorption. There are no particular restrictions on such ion scavengers, for example, triazine thiol compounds, bisphenol reducing agents, etc., compounds known as copper damage inhibitors to prevent ionization and dissolution, zirconium-based, antimony, etc. Examples thereof include inorganic ion adsorbents such as bismuth-based magnesium aluminum compounds. The amount of the ion scavenger used is a co-polymer containing a monomer unit derived from a maleimide monomer having a maleimide group and a monomer unit derived from a monofunctional vinyl monomer from the viewpoint of the effect of addition, heat resistance, cost, etc. 0.01-10 mass parts is preferable with respect to 100 mass parts of alkali-soluble polymers which are coalescence.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Examples 1-4 and Comparative Examples 1-3)
Each of the following polymers (A to G) was used, and a film coating varnish was prepared as shown in the formulation table of Table 1 below.

(Synthesis of polymer A)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen displacement device, 18.9 g of N- (4-hydroxyphenyl) maleimide (molecular weight 189) as a maleimide monomer and as a monofunctional vinyl monomer 25.6 g of n-butyl acrylate (molecular weight 128) was uniformly dissolved in 178 g of dimethylformamide (hereinafter abbreviated as “DMF”). To the solution in the flask, 0.74 g of 2,2′-azobisisobutyronitrile (molecular weight 164, hereinafter abbreviated as “AIBN”) was added little by little at room temperature (25 ° C.). After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer A”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 27000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 74 degreeC.

(Synthesis of polymer B)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen displacement device, 13.0 g of 4-maleimidobenzoic acid (molecular weight 217) as a maleimide monomer, 6.9 g of N-phenylmaleimide (molecular weight 173) In addition, 32.0 g of n-butyl acrylate as a monofunctional vinyl monomer was uniformly dissolved in 204 g of DMF. AIBN 0.86g was added little by little at room temperature (25 degreeC) to the solution in a flask. After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The resulting precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer B”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 33000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 60 degreeC.

(Synthesis of polymer C)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen displacement device, 17.9 g of N-cyclohexylmaleimide (molecular weight 179) as a maleimide monomer and 25.6 g of n-butyl acrylate as a monofunctional vinyl monomer Then, 3.6 g of acrylic acid (molecular weight 72) was uniformly dissolved in 188 g of DMF. AIBN 0.86g was added little by little at room temperature (25 degreeC) to the solution in a flask. After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The resulting precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer C”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 35000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 44 degreeC.

(Synthesis of polymer D)
In a 500 ml separable flask equipped with a stirrer, thermometer, condenser, and nitrogen displacement apparatus, 18.8 g of N-cyclohexylmaleimide as maleimide monomer, 19.2 g of n-butyl acrylate as monofunctional vinyl monomer and acrylic acid 5 .4 g was uniformly dissolved in 174 g of DMF. To the solution in the flask, 0.81 g of AIBN was added little by little at room temperature (25 ° C.). After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The resulting precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer D”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 29000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 68 degreeC.

(Synthesis of polymer E)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen displacement device, 19.2 g of n-butyl acrylate, 5.4 g of acrylic acid and 23.4 g of styrene (molecular weight 104) as a monofunctional vinyl monomer. Was uniformly dissolved in 192 g of DMF. 1.11 g of AIBN was added to the solution in the flask little by little at room temperature (25 ° C.). After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The resulting precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer E”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 42000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 52 degreeC.

(Synthesis of polymer F)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen displacement device, 12.8 g of n-butyl acrylate, 5.8 g of acrylic acid, 20.8 g of styrene, and cyclohexyl acrylate ( 15.4 g of molecular weight 154) was uniformly dissolved in 234 g of DMF. 1.18 g of AIBN was added to the solution in the flask little by little at room temperature (25 ° C.). After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer F”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 37000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 55 degreeC.

(Synthesis of polymer G)
In a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen displacement device, 12.8 g of n-butyl acrylate, 21.6 g of acrylic acid, and 15.4 g of cyclohexyl acrylate were added to 215 g of DMF as a monofunctional vinyl monomer. It was dissolved uniformly. To the solution in the flask, 1.24 g of AIBN was added little by little at room temperature (25 ° C.). After completion of the addition, a reflux condenser was attached to the flask, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes while blowing nitrogen gas. Next, the temperature of the flask was raised to 70 ° C. and stirring was continued for 6 hours. The solution thus obtained was cooled to room temperature (25 ° C.), and then poured into distilled water to cause reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polymer (hereinafter referred to as “polymer G”). When the weight average molecular weight of the obtained polymer was measured, it was Mw = 39000 in terms of polystyrene. Moreover, Tg of the obtained polymer was 66 degreeC.

In Table 1, various symbols mean the following.
BPE-100: Shin-Nakamura Chemical, ethoxylated bisphenol A dimethacrylate U-2PPA: Shin-Nakamura Chemical, urethane acrylate I-819: Ciba Specialty Chemicals, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide VG3101 : Printec, trifunctional epoxy resin BEO-60E: Shin Nippon Rika, bisphenol A bis (triethylene glycol glycidyl ether) ether TrisP-PA: Honshu Chemical, trisphenol compound (α, α, α'-tris (4-hydroxy) Phenols) -1-ethyl-4-isopropylbenzene)
R972: Nippon Aerosil, hydrophobic fumed silica (average particle size: about 16 nm)
NMP: Kanto Chemical, N-methyl-2-pyrrolidinone

  Each of these varnishes was applied to a substrate film (peeling agent-treated PET film) to a thickness of 40 μm, and heated in an oven at 80 ° C. for 30 minutes, followed by 120 ° C. for 30 minutes. And the adhesive sheet with a base film in which the adhesive bond layer was formed on the base film of Comparative Examples 1-3 was obtained.

  About the adhesive sheet of Examples 1-4 and Comparative Examples 1-3, the following characteristic evaluation was performed and the result was shown in Table 2.

Low temperature sticking property Adhesive sheets with base films of Examples 1 to 4 and Comparative Examples 1 to 3 are rolled onto a silicon wafer (6 inch diameter, thickness 400 μm) placed on a support base (temperature 100 ° C., linear pressure 4 kgf). / Cm, feed rate 0.5 m / min) was laminated by pressing. Subsequently, the base film was peeled off, and a polyimide film “Upilex” (trade name) having a thickness of 80 μm, a width of 10 mm, and a length of 40 mm was pressed and laminated on the adhesive layer with a roll under the same conditions as described above. The sample prepared in this manner was subjected to a 90 ° peel test at room temperature (25 ° C.) using a rheometer “Strograph ES” (trade name), and the peel strength between the adhesive film and the upilex was measured. . Samples having a peel strength of 2 N / cm or higher were designated as “A”, and samples having a peel strength of less than 2 N / cm were designated as “C”.

Pattern Formability The adhesive sheets with base film of Examples 1 to 4 and Comparative Examples 1 to 3 were pressed on a silicon wafer (6 inch diameter, thickness 400 μm) with a roll at 100 ° C. (linear pressure 4 kgf / cm And a feed rate of 0.5 m / min). A negative pattern mask (manufactured by Hitachi Chemical Co., Ltd .: No. G-2) was placed thereon, and exposed at 500 mJ / cm ² with a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd .: EXM-1172-B-∞). Then, it was left on an 80 ° C. hot plate for about 30 seconds. Thereafter, the base film was removed and spray developed with a conveyor developing machine (manufactured by Yako). The developer used was 2.38% by mass of tetramethylammonium hydride (TMAH) at 28 ° C., and the spray pressure was 0.18 MPa. Pure water and 23 ° C. were used for washing with water, and the spray pressure was 0.02 MPa. After development, it is confirmed whether pattern formation (line / space: 200 μm / 400 μm) is performed, and “A” indicates that the pattern is formed, and “B” indicates that the exposed portion of the pattern is open but also swells or dissolves. The case where the adhesive layer peeled off from the silicon wafer with development was designated as “C”.

260 ° C. Peel Strength A silicon wafer (6 inch diameter, 400 μm thickness) was half cut to a size of 5 mm × 5 mm to a depth of 180 μm. Thereafter, the adhesive sheets with base films of Examples 1 to 4 and Comparative Examples 1 to 3 were pressed on a half-cut silicon wafer with a roll at 100 ° C. (linear pressure 4 kgf / cm, feed rate 0.5 m). / Min). Subsequently, these samples were exposed at 500 mJ / cm ² with a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd .: EXM-1172-B-∞), and then left on a hot plate at 80 ° C. for about 30 seconds. Thereafter, the base film was removed, and each sample was separated into 5 mm × 5 mm pieces.

  The separated silicon wafer with an adhesive layer was placed on a glass substrate (10 mm × 10 mm × 0.55 mm) with the adhesive sheet side down, and was pressure-bonded at 120 ° C. for 10 seconds while being pressurized with 2 kgf. These test pieces were heated and cured in an oven at 170 ° C. for 3 hours, then heated on a hot plate at 260 ° C. for 10 seconds, and then measured using an adhesive force evaluation apparatus shown in FIG. The peel strength of the silicon chip was measured under the condition of 0.5 mm / second, and the value at this time was defined as the peel strength before moisture absorption. Moreover, after leaving the heat-cured sample in a constant temperature and humidity chamber of 85 ° C./60% RH for 48 hours, the peel strength was measured in the same manner as described above to obtain the peel strength after moisture absorption.

  As is clear from the results shown in Table 2, the adhesive sheets of Examples 1 to 4 are excellent in low-temperature sticking property and pattern formability as compared with the adhesive sheets of Comparative Examples 1 to 3, and have a 260 ° C. peel strength. It was confirmed to be high.

It is sectional drawing which shows one Embodiment of a single layer adhesive sheet. It is sectional drawing which shows one Embodiment of an adhesive sheet provided with a base film, an adhesive bond layer, and a cover film. It is sectional drawing which shows one Embodiment of an adhesive sheet provided with a base film, an adhesive bond layer, and a cover film. It is sectional drawing which shows one Embodiment of an adhesive sheet. It is a top view which shows one Embodiment of the semiconductor wafer with an adhesive bond layer. FIG. 6 is an end view taken along line VI-VI in FIG. 5. It is a top view which shows one Embodiment of an adhesive agent pattern. FIG. 8 is an end view taken along line VIII-VIII in FIG. 7. It is a top view which shows one Embodiment of an adhesive agent pattern. FIG. 10 is an end view taken along line XX in FIG. 9. It is a schematic cross section showing one embodiment of a semiconductor device of the present invention. It is a schematic cross section which shows other embodiment of the semiconductor device of this invention. It is the schematic which shows a peel strength measuring apparatus.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Adhesive layer, 1a, 1b ... Adhesive pattern, 2 ... Cover film, 3 ... Base film (base material), 6 ... Adhesive layer, 7 ... Base film (base material), 8 ... Semiconductor wafer, DESCRIPTION OF SYMBOLS 12, 12a, 12b ... Semiconductor element, 13 ... Supporting member for semiconductor element mounting, 14 ... Wire, 15 ... Sealing material, 16 ... Terminal, 20, 20a, 20b ... Semiconductor wafer with an adhesive layer, 100, 110, 120 , 130 ... Adhesive sheet, 200, 210 ... Semiconductor device, 31 ... Push-pull gauge, 32 ... Handle, 33 ... Support point, 34 ... Silicon wafer, 35 ... Glass substrate, 36 ... Hot plate, 300 ... Peel strength measuring device.

Claims (10)

(A) an alkali-soluble polymer that is a copolymer including a monomer unit derived from a maleimide monomer having a maleimide group and a monomer unit derived from a monofunctional vinyl monomer;
(B) a thermosetting resin;
(C) a radiation polymerizable compound;
(D) a photoinitiator;
Contain,
The maleimide monomer includes a compound having a phenolic hydroxyl group,
Photosensitive adhesive composition for semiconductor elements. Wherein the thermosetting resin is an epoxy resin, according to claim 1 photosensitive adhesive composition. The photosensitive adhesive composition of Claim 1 or 2 in which the said radiation polymerizable compound has an acrylate group and / or a methacrylate group. The photosensitive adhesive composition as described in any one of Claims 1-3 whose glass transition temperature of the said alkali-soluble polymer is 150 degrees C or less. An adhesive sheet provided with the film-form adhesive bond layer which consists of a photosensitive adhesive composition as described in any one of Claims 1-4 . The adhesive sheet according to claim 5 , further comprising a base material, wherein the adhesive layer is provided on one surface of the base material. It forms by exposing the film-form adhesive layer which consists of a photosensitive adhesive composition as described in any one of Claims 1-4 , and developing the said adhesive bond layer after exposure using an alkali developing solution. The adhesive pattern. A semiconductor wafer with an adhesive layer, comprising: a semiconductor wafer; and an adhesive layer made of the photosensitive adhesive composition according to any one of claims 1 to 4 provided on one surface of the semiconductor wafer. . A support member, a semiconductor element mounted on the support member, and an adhesive layer interposed between the support member and the semiconductor element, wherein the adhesive layer is any one of claims 1 to 4. A semiconductor device formed of the photosensitive adhesive composition described in the item. An adhesive pattern is formed by exposing an adhesive layer comprising the photosensitive adhesive composition according to any one of claims 1 to 4 and developing the exposed adhesive layer using an alkaline developer. Forming, and
Bonding the semiconductor element and the support member on which the semiconductor element is mounted via the adhesive pattern;
A method for manufacturing a semiconductor device comprising:

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