JP5625430B2 - Adhesive for semiconductor and semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor adhesive and a semiconductor device.

  In recent years, the speed of semiconductor devices has been remarkably increased, and transmission delay due to a decrease in signal propagation speed due to wiring resistance and parasitic capacitance between wirings has become a problem. Such a problem tends to become more prominent because the wiring resistance increases and the parasitic capacitance increases as the wiring width and the wiring interval become finer due to higher integration of semiconductor devices. Therefore, in order to prevent signal delay due to increase in wiring resistance and parasitic capacitance, copper wiring is introduced instead of the conventional aluminum wiring, and the relative dielectric constant of the interlayer insulating film is 3.9 of the silicon dioxide film. A small low dielectric constant insulating film has been applied. In particular, the relative dielectric constant of the interlayer insulating film is strongly demanded to be about 2.0 or less as the design standard is reduced from 65 nm to 45 nm. There is a need for a porous insulating film having a reduced dielectric constant by increasing the porosity.

  Such a porous insulating film generally has a problem that mechanical strength is lowered due to its structure. That is, it becomes more sensitive to internal stress caused by an external force than a semiconductor element using a conventional insulating film, and the insulating film may be destroyed even by stress that has not been a problem so far. Therefore, in order to reduce the stress generated in the semiconductor, a material capable of reducing the stress is required as a semiconductor constituent material such as a sealing material and a die attach material, and the semiconductor production process is being reviewed.

  The semiconductor element is bonded to a support such as a lead frame, a glass epoxy substrate (glass fiber reinforced epoxy resin substrate), a BT substrate (a BT resin substrate made of cyanate monomer and oligomer thereof and bismaleimide), and an organic substrate such as a polyimide film. In the die attach process, warpage occurs due to the difference in thermal expansion coefficient between the semiconductor element and the support after die attach. However, excessive warpage causes damage to the interlayer insulating film, and thus warpage is unlikely to occur. There is a need for touch materials.

  On the other hand, while lead elimination from semiconductor products is being promoted as part of environmental measures, lead-free solder is also used for mounting on the board, so the reflow temperature must be higher than that for tin-lead solder. is there. Since the reflow process at high temperature increases stress inside the semiconductor package, during reflow, the semiconductor product may be subjected to an inter-member (eg, semiconductor element / encapsulant, semiconductor element / die attach layer, die attach layer / solder resist (substrate surface ), Peeling of the inside of the substrate (solder resist / copper trace), lead frame / die attach layer, lead frame / sealing material, etc.) and cracks of the sealing material are likely to occur. From this point of view, a material having a suitable low stress property is hardly desired as a die attach material.

In response to such a request, (1) a method of adding a liquid low stress agent (see, for example, Patent Document 1),
(2) A method of adding a solid low stress agent (for example, see Patent Document 2),
(3) A method of reducing the crosslinking density (for example, see Patent Document 3),
(4) A method of introducing a flexible structure into the resin skeleton (see, for example, Patent Document 4),
(5) A method of adding a polymer having a low glass transition temperature (Tg) (for example, see Patent Document 5) has been studied. For example, in the method of (1), the liquid low-stress agent itself has a high viscosity. Therefore, when a blending amount capable of obtaining a sufficiently low elastic modulus is added, it tends to be difficult to handle due to high viscosity. In the method (2), since the ratio of solid content in the liquid resin composition increases, the viscosity is high. In the method (3), mechanical properties such as strength at high temperatures tend to deteriorate. In the method (4), the viscosity of the resin into which the flexible skeleton is introduced is high. In the method of (5), the liquid resin composition cannot be obtained unless a solvent is used, and the solvent needs to be volatilized during curing of the liquid resin composition, so that the warp is caused. Chip size that can be a problem ( Most warp in the case Ppusaizu is small has been left also disadvantages, such as is not suitable to become not) a problem.
Thus, a resin composition having excellent workability and small warpage and sufficient low stress is desired as a die attach material, but none has been sufficiently satisfied.
On the other hand, if it is a die attach film, adding a low stress material has little effect on workability and is useful as a die attach material that is less likely to warp. However, when bonding semiconductor elements to organic substrates, There is a drawback that the embedding in the irregularities on the surface of the substrate due to the presence or absence of wiring in the organic substrate is poor and causes voids.

Japanese Patent Laid-Open No. 05-120914

JP 2003-347322 A

Japanese Patent Laid-Open No. 06-084974

Japanese Patent Laid-Open No. 08-176409

JP 2005-154687 A

  The present invention is a resin composition having excellent workability, small warpage and sufficient low stress, and by using the resin composition as a die attach material, peeling occurs even when high temperature reflow and temperature cycle tests are performed. There is no need to provide a highly reliable semiconductor device.

Such an object is achieved by the present invention described in the following [1] to [6].
[1] A semiconductor adhesive comprising a compound (A) having a glycidyl group, a compound (B) having a functional group capable of reacting with a glycidyl group, and a phosphorus atom-containing compound (C), the adhesive having the glycidyl group The compound (A) contains the following component (a) in a proportion of 95% by weight or more based on the total weight of the compound (A).
[Component (a): Component in which the number of glycidyl groups contained in one molecule is 2]

[2] In the compound (B) having a functional group capable of reacting with the glycidyl group, the proportion of the following component (b1) is 50% by weight to 90% by weight, and the proportion of the following component (b2) is 10% by weight to 50%. The adhesive for semiconductors according to [1], which is less than% by weight.
[Component (b1): Component in which the number of functional groups capable of reacting with the glycidyl group contained in the molecule is 2]
[Component (b2): Component in which the number of functional groups capable of reacting with the glycidyl group contained in the molecule is 3 or more]

[3] The functional group capable of reacting with the glycidyl group of the compound (B) having a functional group capable of reacting with the glycidyl group is at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an amino group. [1] The adhesive for semiconductors according to [2].

[4] The semiconductor adhesive according to any one of [1] to [3], wherein the content of the organic compound having a molecular weight of 5000 or more is 10% by weight or less based on the total weight of the semiconductor adhesive.

[5] The number p of glycidyl groups contained in the compound (A) having the glycidyl group and the number of functional groups capable of reacting with the glycidyl group contained in the compound (B) having a functional group capable of reacting with the glycidyl group The adhesive for semiconductors according to [1], wherein q and the number r of functional groups capable of reacting with the glycidyl group contained in compound (C) satisfy the following conditional expression 1.
[Condition 1: 0.9 ≦ p / (q + r) ≦ 1.2]

[6] A semiconductor device obtained by placing a semiconductor element on a support via a die attach material, wherein the die attach material is an adhesive for a semiconductor according to any one of [1] to [5]. A semiconductor device characterized by being an agent.

  The adhesive for semiconductors of the present invention has excellent workability, low warpage and sufficient low stress, so that it can be used as a die attach material with high reliability that does not cause peeling even when subjected to high temperature reflow and temperature cycle tests. An excellent semiconductor device can be provided.

The adhesive for semiconductors of this invention contains the compound (A) which has a glycidyl group, the compound (B) which has a functional group which can react with a glycidyl group, and the phosphorus atom containing compound (C), and has the said glycidyl group ( In A), the ratio of the component having 2 glycidyl groups contained in one molecule is 95% or more, and it is excellent in workability due to the characteristics, has low warpage and sufficient low stress property. It will be a thing.
Hereinafter, the present invention will be described in detail.

(Compound having glycidyl group (A))
The adhesive for semiconductors according to the present invention includes a compound (A) having a glycidyl group, and the compound (A) contains a component (a) having 2 glycidyl groups based on the total weight of the compound (A). In a proportion of 95% by weight or more.

  When the ratio of the component (a) in the compound (A) is 95% by weight or more, the ratio of reacting with the compound (B) to form a linear structure is increased, and a cured product having low stress properties is obtained. can get. On the other hand, when the component having more than 2 glycidyl groups contained in one molecule is excessive, a three-dimensional cross-linked portion is increased, and a cured product having a small warpage and sufficient low stress cannot be obtained. In addition, when the number of glycidyl groups contained in one molecule is less than 2, the rate of termination reaction with the compound (B) increases, the molecule does not grow sufficiently, and the cured product has low cohesive force. It is not preferable.

  Here, the ratio of the component (a) is a component in which the number of glycidyl groups contained in one molecule is 2 out of all peak areas measured by GPC (gel permeation chromatography) and detected by an RI detector. The ratio of the peak area.

  The compound (A) having a glycidyl group used in the present invention contains a component (a) in which the number of glycidyl groups contained in one molecule is 2 in a proportion of 95% by weight or more based on the total weight of the compound (A). It is preferable that By containing the component (a) in the above range or more, the polymer with the compound (B) having a functional group capable of reacting with a glycidyl group becomes substantially linear. Examples of such a compound (A) include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and shijirohexane. Difunctional having alicyclic structure such as diethanol or derivatives thereof, bifunctional epoxidized aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol or derivatives thereof, and bifunctional glycidyl Examples thereof include bifunctional glycidyl-modified thermoplastic resins such as modified acrylic resins, bifunctional glycidyl-modified polybutadiene, and the like. Among these, particularly from the viewpoint of the cohesive strength of the cured product, bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, A diol having an alicyclic structure such as shijirohexanediethanol or a derivative thereof is preferable.

(Compound (B) having a functional group capable of reacting with a glycidyl group)
The semiconductor adhesive according to the present invention includes a compound (B) having a functional group capable of reacting with a glycidyl group. The compound (B) can react with the compound (A) to obtain a semiconductor adhesive having low stress. Here, examples of the functional group capable of reacting with the glycidyl group include a carboxyl group, a hydroxyl group, an amino group, a mercapto group, and an acid anhydride. In particular, from the viewpoint of enhancing the reactivity with the compound (A) and long-term storage stability. A carboxyl group, a phenolic hydroxyl group and an amino group are preferred. Examples of the compound having a carboxyl group include various phthalic acids, dimer acids, trimellitic acid, cyclohexanedicarboxylic acid, carboxyl group-terminated butadiene-acrylonitrile copolymers, and the like. Examples of the compound having a phenolic hydroxyl group include bisphenol F, bisphenol A, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethylbiphenol, ethylidene bisphenol, methyl ethylidene bis ( Bisphenols such as methylphenol), cyclohexylidene bisphenol, and biphenol and their derivatives, trifunctional phenols such as tri (hydroxyphenyl) methane and tri (hydroxyphenyl) ethane and their derivatives, phenol novolac, cresol novolac, etc. A compound obtained by reacting phenols with formaldehyde. Such as and derivatives thereof down and the like. Examples of the compound having an amino group include aliphatic amines, aromatic amines, dicyandiamide, and dihydrazide compounds. Of these, it is preferable to use a compound having a phenolic hydroxyl group from the viewpoint of achieving both long-term storage and heat-curing properties.

  In the compound (B), the component in which the number of functional groups capable of reacting with a glycidyl group per molecule is 2 (b1) is 50% by weight or more and 90% by weight based on the total weight of the compound (B). The following is preferable. Thereby, the ratio which reacts with a compound (A) and becomes a linear structure becomes high, and the hardened | cured material which has low-stress property is obtained. In addition, it is preferable that the component (b2) having 3 or more functional groups capable of reacting with a glycidyl group in one molecule is 10% by weight or more and less than 50% by weight based on the total weight of the compound (B). As a result, it is possible to partially crosslink three-dimensionally and have a suitable cohesive force. When the component (b2) having 3 or more functional groups capable of reacting with a glycidyl group contained in one molecule is 50% by weight or more, the three-dimensional cross-linked portion is increased, warping is large, and sufficient low stress property is obtained. I cannot get a cured product. In addition, when the component (b2) having 3 or more functional groups capable of reacting with a glycidyl group contained in one molecule is less than 10% by weight, a sufficient cross-linking structure cannot be obtained, and the adhesion for semiconductors has low cohesive force. It becomes unpreferable because it becomes an agent

  Here, the ratio of the component (b1) is measured by GPC (gel permeation chromatography), and the functional group capable of reacting with the glycidyl group contained in one molecule out of the total peak area detected by the RI detector. It was set as the ratio of the peak area of the component whose number is 2. The ratio of the component (b2) was also determined as the ratio of the peak area of the component having 3 or more functional groups capable of reacting with the glycidyl group contained in one molecule by the same measurement.

(Compound (C))
The adhesive for semiconductors according to the present invention contains a phosphorus atom-containing compound (C). The phosphorus atom-containing compound (C) works as a curing accelerator for the compound (A) having a glycidyl group and has excellent storage stability.

  Specific examples of the phosphorus atom-containing compound (C) include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds. It is preferable to use a tetra-substituted phosphonium compound from the viewpoint of achieving both long-term storage and heat-curing properties.

  Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine.

Examples of the tetra-substituted phosphonium compound include compounds represented by the following general formulas (1), (2), and (3).
(However, in the said General formula (1), P represents a phosphorus atom. R1, R2, R3, and R4 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.
(In the general formula (2), P represents a phosphorus atom and Si represents a silicon atom. R5, R6, R7 and R8 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Wherein X1 is an organic group bonded to the groups Y1 and Y2, and X2 is an organic group bonded to the groups Y3 and Y4. Y2 represents a group formed by releasing a proton from a proton donating group, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure.Y3 and Y4 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y3 and Y4 in the same molecule are bonded to a silicon atom to form a chelate structure.X1 and X2 are the same or different from each other. Y1, Y , Y3, and Y4 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

  In the general formula (2), as R5, R6, R7 and R8, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (2), X1 is an organic group couple | bonded with Y1 and Y2. Similarly, X2 is an organic group bonded to the groups Y3 and Y4. Y1 and Y2 are groups formed by proton-donating groups releasing protons, and groups Y1 and Y2 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y3 and Y4 are groups formed by proton-donating groups releasing protons, and groups Y3 and Y4 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X1 and X2 may be the same as or different from each other, and the groups Y1, Y2, Y3, and Y4 may be the same as or different from each other. The groups represented by -Y1-X1-Y2- and -Y3-X2-Y4- in general formula (2) are composed of groups in which a proton donor releases two protons. Examples of proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, and salicylic acid. 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (2) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions such as aliphatic hydrocarbon groups such as octyl group and aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

(However, in the said General formula (3), P represents a phosphorus atom. R9, R10, R11, and R12 represent an aromatic group or an alkyl group. B represents a boron atom. R13, R14, R15, and R16 are Represents an organic group.)

Examples of the phosphobetaine compound include compounds represented by the following general formula (4).
(However, in the said General formula (14), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. F is an integer of 0-5, and g is an integer of 0-3.)

Examples of the adduct of a phosphine compound and a quinone compound include compounds represented by the following general formula (5).
(However, in the said General formula (5), P represents a phosphorus atom. R17, R18, and R19 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R20, R21 and R22 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R20 and R21 are bonded to form a cyclic structure. May be.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group or an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.

(Regarding the number of functional groups of the compounds (A), (B) and (C))
As described above, the resin composition according to the present invention includes the compound (A) having a glycidyl group containing the component (a) in a predetermined ratio, the compound (B) having a functional group capable of reacting with the glycidyl group, and the compound (C ), But p represents the number of glycidyl groups contained in compound (A), q represents the number of functional groups capable of reacting with glycidyl groups contained in compound (B), and reacted with glycidyl groups contained in compound (C). When the number of possible functional groups is r, it is preferable that the following relational expression 1 is satisfied from the viewpoint of improving the cohesive force of the cured product and reducing the warpage of the cured product.
Relational expression 1: 0.9 ≦ p / (q + r) ≦ 1.2

  When the number of functional groups is in the relationship of p / (q + r) ≧ 0.9, the cohesive force after curing of the resin composition becomes suitable, and when p / (q + r) ≦ 1.2, the cured product is obtained. It can suppress that the elasticity modulus of this becomes high too much, and can suppress the curvature of hardened | cured material.

(Other ingredients)
The adhesive for a semiconductor according to the present invention comprises a compound (A) having a glycidyl group, a compound (B) having a functional group capable of reacting with a glycidyl group, and a phosphorus atom-containing compound (C) as essential components. However, a curing accelerator of a compound (A) having a glycidyl group other than the phosphorus atom-containing compound (C), a filler, a thermosetting resin other than the compound (A) having a glycidyl group, etc. are used in an arbitrary ratio. It doesn't matter. Moreover, in order to improve the reflow resistance of hardened | cured material, combined use with cyanate resin, an acrylic resin, and a maleimide resin is also preferable.

  Examples of the curing accelerator for the compound (A) having a glycidyl group other than the phosphorus atom-containing compound (C) include amine compounds such as imidazoles and diazabicycloundecene, and salts thereof.

  Examples of fillers that can be used in the present invention include silver powder, gold powder, copper powder, aluminum powder, nickel powder, palladium powder, and other metal powders, alumina powder, titania powder, aluminum nitride powder, boron nitride powder, and silica powder. It is possible to use polymer powder such as ceramic powder, polyethylene powder, polyacrylate powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, polysiloxane powder, and the like. In particular, silver powder is preferably used when electrical conductivity and thermal conductivity are required, and reduced powder, atomized powder, and the like are available as long as they are usually commercially available for electronic materials. Note that silver powder for non-electronic materials may contain a large amount of ionic impurities.

The filler preferably has an average particle size of 1 μm or more and 30 μm or less. By being more than the said lower limit, the viscosity increase of a resin composition can be suppressed and suitable workability | operativity can be obtained.
Further, for example, when using a semiconductor adhesive as a die attach material, the semiconductor adhesive may be discharged using a nozzle. In such a case, the particle size of the filler is set to the upper limit value or less. By doing so, it is possible to prevent clogging of the nozzle.

  Further, the shape of the filler that can be used in the present invention is not particularly limited, such as flakes and spheres. For example, in the case of silver powder, it is preferable to use flakes in terms of improving storage stability and workability. .

  In the present invention, the blending amount of the filler can be appropriately adjusted according to the purpose. For example, when silver powder is used, it is usually 70% by weight or more and 95% by weight or less in the resin composition. preferable. By setting it to the lower limit value or more, suitable conductivity can be obtained, and by setting the upper limit value or less, a viscosity suitable for work can be obtained.

  The adhesive for semiconductors according to the present invention can be used in combination with a thermosetting resin as necessary. The thermosetting resin is a general thermosetting resin that forms a three-dimensional network structure by heating. Although this thermosetting resin is not specifically limited, It is preferable that it is a material which forms a liquid resin composition, and it is desirable that it is liquid at room temperature. For example, cyanate resin, radical polymerizable acrylic resin, maleimide resin and the like can be mentioned.

  The cyanate resin is a compound having an —NCO group in the molecule, and forms a three-dimensional network structure by the reaction of the —NCO group by heating, and is cured. Specifically, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1, 6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo -4-Cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) And ruthenes, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and cyanates obtained by reacting novolak resins with cyanogen halides. A prepolymer having a triazine ring formed by trimerizing a cyanate group can also be used. This prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate resin monomer using, for example, an acid such as mineral acid or Lewis acid, a base such as sodium alcoholate or tertiary amine, or a salt such as sodium carbonate as a catalyst. It is done.

As the cyanate resin curing accelerator, generally known ones can be used. Examples include organometallic complexes such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate and acetylacetone iron, metal salts such as aluminum chloride, tin chloride and zinc chloride, and amines such as triethylamine and dimethylbenzylamine. However, it is not limited to these. These curing accelerators can be used alone or in combination.
In addition, the cyanate resin can be used in combination with other resins such as an epoxy resin, an oxetane resin, an acrylic resin, and a maleimide resin.

The radical-polymerizable acrylic resin is a compound having a (meth) acryloyl group in the molecule, and is a resin that forms a three-dimensional network structure by the reaction of the (meth) acryloyl group and cures. Although it is necessary to have at least one (meth) acryloyl group in the molecule, it is preferable that at least two (meth) acryloyl groups are included. Specifically, the acrylic resin has a molecular weight of 500 to 10,000, such as polyether, polyester, polycarbonate, poly (Meth) acrylate, polybutadiene, butadiene acrylonitrile copolymer, and a compound having a (meth) acryl group.

  As said polyether, what a C3-C6 organic group repeated via the ether bond is preferable, and the thing which does not contain an aromatic ring is preferable. It can be obtained by reacting a polyether polyol with (meth) acrylic acid or a derivative thereof.

  As said polyester, the thing in which the C3-C6 organic group repeated via the ester bond is preferable, and the thing which does not contain an aromatic ring is preferable. It can be obtained by reacting a polyester polyol with (meth) acrylic acid or a derivative thereof.

  As the polycarbonate, those in which an organic group having 3 to 6 carbon atoms is repeated via a carbonate bond are preferable, and those having no aromatic ring are preferable. It can be obtained by reacting a polycarbonate polyol with (meth) acrylic acid or a derivative thereof.

  Examples of the poly (meth) acrylate include a copolymer of (meth) acrylic acid and (meth) acrylate or a copolymer of (meth) acrylate having a hydroxyl group and (meth) acrylate having no polar group. preferable. In the case of reacting these copolymers with a carboxy group, it can be obtained by reacting an acrylate having a hydroxyl group, and in the case of reacting with a hydroxyl group, (meth) acrylic acid or a derivative thereof.

  The polybutadiene can be obtained by a reaction between a polybutadiene having a carboxy group and a (meth) acrylate having a hydroxyl group, a reaction between a polybutadiene having a hydroxyl group and (meth) acrylic acid or a derivative thereof, and maleic anhydride. It is also possible to obtain it by the reaction of polybutadiene to which is added and (meth) acrylate having a hydroxyl group.

  The butadiene acrylonitrile copolymer can be obtained by a reaction between a butadiene acrylonitrile copolymer having a carboxy group and a (meth) acrylate having a hydroxyl group.

  The maleimide resin is a compound containing one or more maleimide groups in one molecule, and forms a three-dimensional network structure by the reaction of the maleimide groups by heating, and is cured. For example, N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl ] A bismaleimide resin such as propane may be mentioned. More preferred maleimide resins are compounds obtained by reaction of dimer acid diamine and maleic anhydride, and compounds obtained by reaction of maleimidated amino acids such as maleimide acetic acid and maleimide caproic acid with polyols. The maleimidated amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid. As the polyol, polyether polyol, polyester polyol, polycarbonate polyol, poly (meth) acrylate polyol is preferable, and an aromatic ring is formed. What does not contain is especially preferable. Since the maleimide group can react with an allyl group, the combined use with an allyl ester resin is also preferable. The allyl ester resin is preferably an aliphatic one, and particularly preferred is a compound obtained by transesterification of a cyclohexane diallyl ester and an aliphatic polyol. Moreover, combined use with cyanate resin, an epoxy resin, and an acrylic resin is also preferable.

  The semiconductor adhesive according to the present invention can be used in combination with the following compounds as required. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,2-cyclohexanediol mono (meth) acrylate, 1,3-cyclohexanediol mono (meth) acrylate, 1,4-cyclohexanediol mono (meth) acrylate, 1,2-cyclohexanedimethanol mono (Meth) acrylate, 1,3-cyclohexanedimethanol mono (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1,2-cyclohexanediethanol mono (meth) acrylate 1,3-cyclohexanediethanol mono (meth) acrylate, 1,4-cyclohexanediethanol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate, tri (Meth) acrylate having a hydroxyl group such as methylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, Examples thereof include (meth) acrylates having a carboxy group obtained by reacting these (meth) acrylates having a hydroxyl group with dicarboxylic acid or a derivative thereof. Examples of dicarboxylic acids that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid and derivatives thereof.

  In addition to the above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, Tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenol Xylethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluoro Butyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1 , 10-decanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyalkylene glycol mono (meth) acrylate , Octoxy polyalkylene glycol mono (meth) acrylate, Lauroxy polyalkylene glycol mono (meth) acrylate, Stearoxy polyalkylene glycol mono (meth) acrylate, Allyloxy polyalkyl Lenglycol mono (meth) acrylate, nonylphenoxypolyalkylene glycol mono (meth) acrylate, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, 1,2-di (meth) Acrylamide ethylene glycol, di (meth) acryloyloxymethyl tricyclodecane, N- (meth) acryloyloxyethyl maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl phthalimide , N-vinyl-2-pyrrolidone, styrene derivatives, α-methylstyrene derivatives and the like can also be used.

  Furthermore, a thermal radical polymerization initiator is preferably used as a polymerization initiator in the semiconductor adhesive according to the present invention. Although it is not particularly limited as long as it is normally used as a thermal radical polymerization initiator, it is desirable that the decomposition start temperature in the rapid heating test (when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min) Is preferably 40 to 140 ° C. When the decomposition temperature is less than 40 ° C., the storage stability of the conductive paste at room temperature is deteriorated, and when it exceeds 140 ° C., the curing time becomes extremely long, which is not preferable.

  Specific examples of the thermal radical polymerization initiator that satisfies the decomposition initiation temperature include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3, 3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t- Butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (T-butylperoxy) valerate, 2,2-bis (t-butyl) -Oxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , T-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy) diisopropylbenzene, t -Butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl Peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid Oxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexylper Oxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α′-bis (Neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecano Eat, t-he Silperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoyl) Peroxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2 -Ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy -3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocar Nate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylper Oxy-m-toluoyl benzoate, t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, t-butyl peroxyallyl monocarbonate, 3,3 ′, 4,4′-tetra (t-butyl Peroxycarbonyl) benzophenone and the like. These may be used alone or in combination of two or more in order to control curability. The radical polymerizable acrylic resin is also preferably used in combination with a cyanate resin, an epoxy resin, or a maleimide resin.

  You may use another additive for the adhesive agent for semiconductors of this invention as needed. Other additives include silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, sulfide silane, titanate coupling agent, aluminum coupling agent, aluminum / zirconium coupling agent, etc. Coupling agents, colorants such as carbon black, low stress components such as silicone oil and silicone rubber, inorganic ion exchangers such as hydrotalcite, antifoaming agents, surfactants, various polymerization inhibitors, antioxidants Various additives may be appropriately blended.

  Further, a solvent may be used for the purpose of adjusting workability. Examples of the solvent include ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, dimethyl maleate, diethyl maleate, ethylene glycol monobutyrate, propylene carbonate, N-methylpyrrolidone, 2- (Hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethyl glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. It is done. Particularly preferred solvents are those having a boiling point of 210 ° C. or more and 250 ° C. or less, and particularly preferred are ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, diethyl maleate, ethylene Examples thereof include glycol monobutyric acid ester, propylene carbonate, diethylene glycol, diethylene glycol monobutyl ether, triethyl glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

(Production method of resin composition)
The adhesive for semiconductors of the present invention can be produced, for example, by premixing each component, kneading using three rolls, and degassing under vacuum.

(Usage method of resin composition)
The adhesive for semiconductors according to the present invention can be used as an adhesive, but a more specific example is that it is used as a die attach material for manufacturing a semiconductor device. In this case, the semiconductor adhesive according to the present invention can be used by a publicly known method. Hereinafter, a specific example of manufacturing a semiconductor device using the semiconductor adhesive of the present invention will be described.

(Method for manufacturing semiconductor device)
Using a commercially available die bonder, dispense the semiconductor adhesive of the present invention as a conductive paste on a predetermined part of a support such as a lead frame or a substrate, then mount a semiconductor element such as a chip, and heat cure. Can do. Here, the support is a printed circuit board such as a lead frame, an organic substrate, or a flexible substrate, and a semiconductor element is mounted on the organic substrate and electrically connected by a gold wire. The support substrate may be a semiconductor element itself or another substrate. Moreover, it can also be used by printing on the support body which mounts a semiconductor element, printing the adhesive agent for semiconductors on a semiconductor wafer, and cutting | disconnecting it after that to a semiconductor element, and using it for a support body. As a printing method of the liquid resin composition, screen printing, stencil printing, and the like are possible, but printing (coating) is preferably performed by a stencil printing method using a stencil mask from the viewpoint of surface smoothness. The stencil printing method can be performed by a known method. Thereafter, wire bonding is performed, and transfer molding is performed using an epoxy resin to manufacture a semiconductor device. Alternatively, a conductive paste is dispensed on the back surface of a chip such as a flip chip BGA (Ball Grid Array) sealed with an underfill material after flip chip bonding, and a heat dissipation component such as a heat spreader or lid is mounted and cured. Is possible.

  EXAMPLES The present invention will be specifically described below using examples, but is not limited thereto. The blending ratio is expressed in parts by weight.

[Example 1]
Bisphenol F type epoxy resin (manufactured by Tohto Kasei Co., Ltd., YDF870GS, epoxy equivalent) as a compound (A) having a glycidyl group in which the ratio of the component having 2 glycidyl groups contained in one molecule is 95% or more 160, bisphenol F (DIC Co., Ltd.) as a compound (B) having a functional group capable of reacting with a glycidyl group, 95% by weight of the component having 2 glycidyl groups contained in one molecule, hereinafter 95% by weight. DIC-BPF, hydroxyl group equivalent of about 100, the proportion of the component having 2 functional groups capable of reacting with the glycidyl group contained in one molecule (hereinafter referred to as component b1) 89% by weight, contained in one molecule A proportion of 11% by weight of a component having the number of functional groups capable of reacting with a glycidyl group of 3 or more (hereinafter referred to as component b2), hereinafter referred to as compound B1) as a compound (C) is tetrapheni. Phosphonium 4,4' sulfonyl distearate phenolate with (Sumitomo Bakelite Co., C03-MB, hydroxyl equivalent weight of about 238, less compound C1). (The number p of glycidyl groups contained in the compound (A) having a glycidyl group used in Example 1 and the functionality capable of reacting with the glycidyl group contained in the compound (B) having a functional group capable of reacting with the glycidyl group) The ratio p / (q + r) between the number q of groups and the number r of functional groups capable of reacting with the glycidyl group contained in the compound (C) is shown in Table 1. (The same applies to Examples 2 to 6 and Comparative Examples below). ).

  3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503P, hereinafter referred to as coupling agent 1) as a coupling agent, and flaky silver powder having an average particle size of 8 μm and a maximum particle size of 30 μm as a filler ( Hereinafter, silver powder) was used. The said raw material was mixed according to the mixture ratio shown in Table 1, knead | mixed using 3 rolls, and the resin composition was obtained by defoaming. Here, the blending ratio in Table 1 is parts by weight.

[Examples 2 to 6]
As compounds other than Example 1, the following compounds were used.
As a compound (B) having a functional group capable of reacting with a glycidyl group, phenol / xylylene resin (Maywa Kasei Co., Ltd., MEH-7800SS, hydroxyl group equivalent: about 175, b1 component ratio: 24 wt%, b2 component ratio: 76 wt% Compound B2), imidazole (Shikoku Kasei Kogyo Co., Ltd., 2P4MHZ, hereinafter Curing Accelerator 1), methacrylic terminal oligomer (Ube Industries, UM90 (1/3) DM, Methacrylate 1) 1,6 hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., 1.6HX, hereinafter methacrylate 2), dicumyl peroxide (manufactured by NOF Corporation, Park Mill D, rapid heating test) as a radical initiator Decomposition temperature: 126 ° C., hereinafter radical initiator 1), average particle size 0.6 μm as filler, specific surface area .0m ² / g amorphous silica (hereinafter silica), a phenoxy resin as a low stress agent (manufactured by Tohto Kasei (Inc.), YP-50 U, weight average molecular weight 40000-45000, less phenoxy resin 1).
The compound selected from these was mix | blended as Table 1, knead | mixed using 3 rolls similarly to Example 1, and the resin composition was obtained by defoaming. The blending ratio is parts by weight. The obtained resin composition was evaluated by the following methods. The evaluation results are shown in Table 1.

[Comparative Examples 1-3]
The resin composition was obtained in the same manner as in Example 1 by blending at the ratio shown in Table 1.
As compounds other than Examples, the following compounds were used.
Bisphenol F type epoxy resin as a compound having a glycidyl group (manufactured by Nippon Kayaku Co., Ltd., SB-403S, epoxy equivalent of about 165, ratio of component having 2 glycidyl groups in one molecule, 75% or less Compound A2).
The obtained resin composition was evaluated by the following methods. The evaluation results are shown in Table 1.

Evaluation Method Viscosity: Using an E-type viscometer (3 ° cone), the value at 25 ° C. and 2.5 rpm was measured immediately after producing the resin composition. A case where the viscosity immediately after the production was in the range of 10 to 50 Pa · s was regarded as acceptable. (In Table 1, “OK” is indicated as “OK”, and “X” is indicated as “FAIL”.)

Chip warpage: Using the resin compositions of Examples and Comparative Examples, a silicon chip of 10 × 10 mm (thickness 200 μm) was used as an organic substrate (substrate: ELC-4781 manufactured by Sumitomo Bakelite Co., Ltd.), solder resist: Taiyo It was mounted on PSR-4000-AUS308 manufactured by Ink Manufacturing Co., Ltd.) and further cured in an oven at 175 ° C. for 15 minutes to obtain a test semiconductor device. About the obtained semiconductor device, the chip | tip surface curvature in 25 degreeC was measured using the non-contact laser surface roughness meter. The warpage was expressed as the maximum value when the diagonal of 10 × 10 mm was zero, and 20 μm or less was accepted. (In Table 1, “OK” is indicated as “OK”, and “X” is indicated as “FAIL”.)

Reflow resistance: A silicon chip was mounted on the following lead frame using the resin compositions of Examples and Comparative Examples, and cured and adhered in an oven at 175 ° C. for 30 minutes. The mount was adjusted using a die bonder (manufactured by ASM) so that the coating thickness was about 25 μm immediately after coating the resin composition. The lead frame after the resin composition was cured was sealed using a sealing material (Sumicon EME-G700H, manufactured by Sumitomo Bakelite Co., Ltd.) to produce a semiconductor device. This semiconductor device was subjected to moisture absorption treatment at 85 ° C. and relative humidity 60% for 168 hours, followed by IR reflow treatment (260 ° C., 10 seconds, 3 times reflow). The degree of peeling of the treated semiconductor device was measured by an ultrasonic flaw detector (transmission type). The unit of the peeled area is%. The case where the peeling area of the die attach part was less than 10% was regarded as acceptable. (In Table 1, “OK” is indicated as “OK”, and “X” is indicated as “FAIL”.)
Semiconductor device: QFP (14 x 20 x 2.0 mm)
Lead frame: Silver-plated copper frame (silver-plated part)
Chip size: 6x6mm

  As is clear from Table 1, the resin compositions shown in Examples 1 to 6 have a viscosity within the target range, excellent workability, small chip warpage, and good reflow resistance. did it. On the other hand, the resin compositions shown in Comparative Examples 1 to 3 deviating from the present invention had a good viscosity, but the elastic modulus was high and the chip warp was rejected. Further, in the reflow resistance, a large amount of peeling occurred and it was rejected.

  The resin composition according to the present invention is excellent in workability and has low warpage and sufficient low stress, so that it can be used as a die attach material with high reliability that does not cause peeling even when subjected to high temperature reflow and temperature cycle tests. An excellent semiconductor device can be provided.

Claims (6)

A semiconductor comprising a compound (A) having a glycidyl group, a phosphorus atom-free compound (B) having a functional group capable of reacting with a glycidyl group , and a phosphorus atom-containing compound (C) having a functional group capable of reacting with a glycidyl group An adhesive for
The compound having a glycidyl group (A) is met semiconductor adhesive, wherein the following components (a) are those containing at a ratio of more than 95% by weight relative to total weight of the compound (A) And
[Component (a): Component in which the number of glycidyl groups contained in the molecule is 2]
The number p of glycidyl groups contained in the compound (A) having the glycidyl group in the semiconductor adhesive,
The number q of functional groups capable of reacting with the glycidyl group contained in the compound (B) having a functional group capable of reacting with the glycidyl group and the number r of functional groups capable of reacting with the glycidyl group contained in the compound (C) are as follows: A semiconductor adhesive that satisfies Conditional Expression 1.
[Condition 1: 0.9 ≦ p / (q + r) ≦ 1.2]
(However, p> 0, q> 0, r> 0.) In the compound (B) having a functional group capable of reacting with the glycidyl group, the proportion of the following component (b1) is 50 wt% or more and 90 wt% or less, and the proportion of the following component (b2) is 10 wt% or more and less than 50 wt%. The adhesive for semiconductor according to claim 1.
[Component (b1): Component in which the number of functional groups capable of reacting with the glycidyl group contained in the molecule is 2]
[Component (b2): Component in which the number of functional groups capable of reacting with the glycidyl group contained in the molecule is 3 or more] The compound having a glycidyl group functional groups capable of reacting with (B) a glycidyl group functional groups capable of reacting with the carboxyl group of a phenolic hydroxyl group, according to claim 1 or 2 is at least 1 Bareru independently from the group consisting of amino group The adhesive for semiconductors as described in 2. The adhesive for semiconductors according to any one of claims 1 to 3 , wherein the content of the organic compound having a molecular weight of 5000 or more is 10% by weight or less with respect to the total weight of the adhesive for semiconductors. The compound (C) is one or more selected from the group consisting of an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, and an adduct of a phosphine compound and a quinone compound. 5. The adhesive for semiconductors according to any one of 4 above. A semiconductor device obtained by placing a semiconductor element on a support via a die attach material,
Wherein a said die attach material is a semiconductor adhesive according to any one of claims 1 to 5.