JP5206600B2 - Epoxy resin composition, prepreg, laminate, resin sheet, multilayer printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin composition, a prepreg, a laminate, a resin sheet, a multilayer printed wiring board, and a semiconductor device.

  With the recent diversification, miniaturization, and thinning of electronic components and electronic devices, multilayer printed wiring boards used for them have been miniaturized and thinned, and various configurations have been developed. Has been. In general, multilayer printed wiring boards are manufactured by forming a circuit on a double-sided metal foil-clad laminate using an etching method, laminating an insulating layer, forming a circuit on the surface of the insulating layer, and then laminating the insulating layer. Then, it is manufactured by alternately laminating a circuit and an insulating layer (for example, described in Patent Document 1).

  Double-sided metal foil-clad laminates are generally laminated on both sides of an insulating layer called a prepreg in which a base material such as glass cloth is immersed and impregnated with a thermosetting resin such as epoxy resin or phenol resin, or a plurality of prepregs are stacked. It is configured by laminating metal foils such as copper foils on both sides and heating and pressing them (for example, described in Patent Document 2). In recent years, with the trend of thinning of multilayer printed wiring boards, it has been studied to make the prepreg of the double-sided metal foil-clad laminate thin or not to use prepreg.

  However, when a semiconductor device is manufactured using a thin multilayer printed wiring board, stress due to a difference in linear thermal expansion occurs at the connection between the semiconductor element and the multilayer printed wiring board, which may affect the reliability of the semiconductor device. is there. Therefore, the resin composition used for the prepreg and the insulating layer of the multilayer printed wiring board is required to have low thermal expansion. An epoxy resin is generally used for the resin composition (for example, described in Patent Document 3). However, the reduction of the expansion coefficient of the resin composition can be achieved by adding an inorganic filler and a cyanate resin (for example, a resin composition containing an epoxy resin). , Patent Documents 4 and 5).

  In addition, it is known that drill workability and flame retardancy can be improved by blending aluminum hydroxide into a resin composition for multilayer printed wiring boards (for example, described in Patent Document 6), but low heat If a large amount of inorganic filler with a relatively large specific surface area such as aluminum hydroxide is added for expansion, the fluidity will be reduced, resulting in poor workability such as voids and poor solder heat resistance. There was a problem that occurred.

JP 2002-305374 A JP 2003-64198 A JP 2006-274236 A Japanese Patent Application Laid-Open No. 2002-299834 Japanese Patent Laid-Open No. 2003-128928 JP 2007-51267 A

  The present invention relates to an epoxy resin composition having a low coefficient of thermal expansion and excellent fluidity, a prepreg having no poor appearance such as stripes, a laminate having excellent moldability and workability, and a multilayer printed wiring board having excellent moldability and solder resistance. In addition, a semiconductor device having excellent reliability is provided.

Such an object is achieved by the following present invention [1] to [15].
[1] An epoxy resin composition comprising (A) an epoxy resin having a structure represented by the following general formula (1), (B) aluminum hydroxide and (C) a cyanate resin as essential components.

[Wherein X is hydrogen or an epoxy group (glycidyl ether group), R ₁ and R ₂ are independent of each other, and are hydrogen, methyl group, ethyl group, propyl group, butyl group, phenyl group, and benzyl group. 1 type selected from. n is an integer of 1 or more, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. ]
[2] The epoxy resin composition according to [1], wherein the (B) aluminum hydroxide has a BET specific surface area of 1.0 m ² / g or more.
[3] The epoxy resin composition according to [1] or [2], wherein the (B) aluminum hydroxide has an average particle size of 10.0 μm or less.
[4] The epoxy resin composition according to any one of [1] to [3], wherein the content of (B) aluminum hydroxide is 5 to 60% by weight of the entire epoxy resin composition.
[5] The epoxy resin composition according to any one of [1] to [4] further includes at least one inorganic filler selected from the group consisting of magnesium hydroxide, silica, talc, calcined talc, and alumina. An epoxy resin composition to be contained.
[6] The content of the epoxy resin having the structure represented by the general formula (1) (A) is 1 to 40% by weight of the whole epoxy resin composition. The epoxy resin composition as described.
[7] The (C) cyanate resin is at least one selected from the group consisting of a phenol novolac type cyanate resin, a cresol novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol F type cyanate resin, and a dicyclopentadiene type cyanate resin. The epoxy resin composition according to any one of [1] to [6], which is a kind.
[8] The epoxy resin composition according to any one of [1] to [7], wherein the content of the (C) cyanate resin is 3 to 50% by weight of the entire epoxy resin composition.
[9] The epoxy resin composition according to any one of [1] to [8] is an epoxy resin composition further comprising (D) an onium salt compound as an essential component.
[10] The epoxy resin composition according to [9], wherein the (D) onium salt compound is a compound represented by the following general formula (2).

(Wherein P is a phosphorus atom, R 1, R 2, R 3 and R 4 are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, independently of each other. A − represents an anion of an n (n ≧ 1) -valent proton donor having at least one proton that can be released outside the molecule, or a complex anion thereof. Is shown.)
[11] A prepreg obtained by impregnating a base material with the epoxy resin composition according to any one of [1] to [10].
[12] A laminate having a metal foil on at least one side of a laminate obtained by superposing at least one prepreg according to [11].
[13] A resin sheet obtained by forming an insulating layer made of the epoxy insulating resin composition according to any one of [1] to [10] on a film or a metal foil.
[14] A multilayer printed wiring board produced by using at least one selected from the group consisting of the prepreg according to [11], the laminate according to [12], and the resin sheet according to [13].
[15] A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to [14].

  The epoxy resin composition of the present invention is excellent in fluidity and has a low coefficient of linear thermal expansion when formed into a cured product. Moreover, the prepreg using the said epoxy resin composition does not have appearance defects, such as a stripe, and can provide the laminated board which is excellent in a moldability and workability. Furthermore, the present invention provides a multilayer printed wiring board excellent in moldability and solder resistance using the resin composition, and a semiconductor device excellent in reliability.

  The epoxy resin composition, prepreg, laminate, resin sheet, multilayer printed wiring board, and semiconductor device of the present invention will be described in detail below.

First, the epoxy resin composition of the present invention will be described.
The epoxy resin used for the epoxy resin composition contains (A) an epoxy resin represented by the following general formula (1).

Wherein X is hydrogen or an epoxy group (glycidyl ether group), and R ₁ and R ₂ are selected from hydrogen, methyl group, ethyl group, propyl group, butyl group, phenyl group, and benzyl group 1 type is represented. n is an integer of 1 or more, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. ]

By using the epoxy resin represented by the general formula (1), the compatibility between the epoxy resin represented by the general formula (1) and the cyanate resin (C) is good. In addition, the dispersibility of (B) aluminum hydroxide in the resin component becomes good, and high filling becomes possible. Further, the resin component and (B) aluminum hydroxide are not separated. Thus, by using the cyanate resin (C) and (B) aluminum hydroxide, the linear expansion coefficient can be lowered, and the generation of voids and streak irregularities when a sheet-like material such as a prepreg is produced. And the surface can be smoothed.
In addition, by using the epoxy resin represented by the general formula (1), the melt viscosity can be lowered even when (B) aluminum hydroxide having a relatively large specific surface area is contained. Therefore, it becomes excellent in workability when manufacturing a laminated board or the like.
In the case where the epoxy resin represented by the general formula (1) is not used and an epoxy resin having another structure is used and the melt viscosity is lowered, a sheet such as a prepreg is used. When formed into a shape, the resin component and the inorganic filler such as aluminum hydroxide are easily separated, and uneven stripes are likely to occur.

  The content of the epoxy resin represented by (A) the general formula (1) is not particularly limited, but is preferably 1 to 40% by weight, and more preferably 2 to 35% by weight of the entire epoxy resin composition. Most preferably, 5-30% by weight is most preferred. If it is less than the lower limit value, the inorganic filler component and the resin component may be separated from each other. If the upper limit value is exceeded, the relative amount of the cyanate resin and the inorganic filler is reduced, so the low thermal expansion. May become difficult.

  The epoxy resin composition contains (B) aluminum hydroxide. By containing aluminum hydroxide, it can be excellent in drill workability, flame retardancy, and low thermal expansion. When silica that is generally used as an inorganic filler is used, low thermal expansion is obtained, but the hardness of silica is high and drill workability is poor. When relatively soft talc is used, sufficient flame retardancy and low thermal expansion cannot be obtained.

The (B) aluminum hydroxide preferably has a BET specific surface area of 1.0 m ² / g or more. More preferably, it is 1.5-10.0 m < ² > / g, Most preferably, it is 2.0-7.0 m < ² > / g. If the BET specific surface area is less than the lower limit value, the particle size becomes too large, so that dispersion into the varnish may be difficult. If the upper limit value is exceeded, the viscosity of the resin varnish becomes too high and the filling is increased. It becomes difficult to do. When using a normal epoxy resin, it is difficult to achieve a high filling with such a large BET specific surface area. However, by using the epoxy resin represented by the general formula (1), the high filling can be achieved. Can be realized. The BET specific surface area can be measured by using a specific surface area measuring device such as Tristar 3000 manufactured by Micromeritics.

  The average particle diameter of (B) aluminum hydroxide is preferably 0.5 to 10 μm. More preferably, it is 1.0-5.0 micrometers, Most preferably, it is 1.5-3.0 micrometers. If the average particle size is less than the lower limit, it is difficult to uniformly disperse the filler, and problems such as aggregation occur, which is not preferable. If the upper limit is exceeded, the resin component and aluminum hydroxide particles are separated. This is not preferable because it becomes easy to cause streaks during prepreg production or resin sheet production. An average particle diameter can be performed using laser diffraction type particle size distribution measuring apparatuses, such as Shimadzu Corporation SALD-7100, for example.

Wherein (B) is not particularly limited as the type of aluminum hydroxide, such as boehmite and the like represented by the gibbsite and _{Al 2 O} 3 · _H 2 _O as represented by, for example _{Al 2 O 3 · 3H 2 O} . Since these aluminum hydroxides cause a dehydration reaction at a high temperature, the flame retardancy of the epoxy resin composition can be improved.

  Although it does not specifically limit as content of the said (B) aluminum hydroxide, 5 to 60 weight% is preferable in an epoxy resin composition, Furthermore, 10 to 50 weight% is preferable. Most preferably, it is 15 to 40% by weight. If the content of aluminum hydroxide is less than the lower limit, effects such as flame retardancy and low thermal expansion cannot be obtained, and if the content exceeds the upper limit, dispersion in the resin becomes difficult and the particles aggregate. This is not preferable because it may cause a malfunction.

The epoxy resin composition of the present invention can further contain an inorganic filler in addition to aluminum hydroxide. Although it does not specifically limit as a kind of inorganic filler, For example, magnesium hydroxide, a silica, a talc, a baking talc, an alumina etc. are mentioned. Among these, silica is particularly preferable because of its excellent low thermal expansion.

  The total content of aluminum hydroxide and other inorganic fillers in the epoxy resin composition of the present invention is not particularly limited, but is preferably 20 to 85% by weight, more preferably 30 to 75% by weight in the epoxy resin composition. . Most preferably, it is 40 to 70% by weight. When the content of the inorganic filler is less than the lower limit value, the effect of low thermal expansion cannot be obtained, and when the content exceeds the upper limit value, the fluidity of the resin composition is lowered and the moldability is deteriorated.

  By containing the (C) cyanate resin, the epoxy resin composition of the present invention can impart heat resistance and low thermal expansion that cannot be achieved by the epoxy resin alone. When the cyanate resin is not contained, sufficient heat resistance and low thermal expansion cannot be obtained, and the reliability is lowered, which is not preferable. Here, the cyanate resin can be obtained by, for example, reacting a halogenated cyanide compound with a phenol and prepolymerizing it by a method such as heating as necessary. Specifically, phenol novolac type cyanate resin, novolak type cyanate resin such as cresol novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin, and the like Examples include dicyclopentadiene type cyanate resin. Since a printed wiring board made of a resin composition using these cyanate resins is excellent in rigidity particularly during heating, it is excellent in reliability when mounting a semiconductor element.

The weight average molecular weight of the (C) cyanate resin is not particularly limited, but the weight average molecular weight is preferably 5.0 × 10 ^{2 to} 4.5 × 10 ³ , particularly 6.0 × 10 ^{2 to} 3.0 × 10 ^3. Is preferred. If the weight average molecular weight is less than the lower limit, tackiness may occur when the prepreg is produced, and the prepreg may adhere to each other or transfer of the resin may occur. Moreover, when a weight average molecular weight exceeds an upper limit, reaction will become quick too much, and when it uses for a laminated board especially, a shaping | molding defect may arise.
The weight average molecular weight of the (C) cyanate resin and the like can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

In addition, as said (C) cyanate resin, what prepolymerized can also be used. That is, a cyanate resin may be used alone, a cyanate resin having a different weight average molecular weight may be used in combination, or a cyanate resin and a prepolymer thereof may be used in combination.
Here, the prepolymer is usually obtained by, for example, trimerizing the cyanate resin by a heat reaction or the like, and is preferably used for adjusting the moldability and fluidity of the epoxy resin composition. It is.
Although a prepolymer is not specifically limited, For example, it is preferable to use what a trimerization rate is 20 to 50 weight%. This trimerization rate can be determined using, for example, an infrared spectroscopic analyzer.
Further, the (C) cyanate resin is not particularly limited, but one kind can be used alone, two or more kinds having different weight average molecular weights can be used in combination, or one kind or two kinds or more of the cyanate resin can be used. These prepolymers can also be used in combination.

The content of the (C) cyanate resin is not particularly limited, but is preferably 3 to 50% by weight of the entire epoxy resin composition, and more preferably 5 to 40% by weight. In the case of preparing a prepreg, etc. Furthermore, 10 to 30% by weight is preferable. If the content is less than the lower limit, the heat resistance improvement effect of the cyanate resin may not be sufficient, and if it exceeds the upper limit, the strength of a molded product such as a prepreg may be reduced.
When (A) the epoxy resin represented by the general formula (1) is not used and another epoxy resin and a cyanate resin are used in combination, 3% by weight or more of the cyanate resin is contained with respect to the entire resin composition. In such a case, it has been found that the occurrence of streaks becomes prominent during prepreg production and resin sheet production.

The epoxy resin composition of the present invention can be used in combination with a thermosetting resin (substantially free of halogen). Examples of the thermosetting resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin. Bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, etc. novolak type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin , Phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy Epoxy resins such as Si resin, urea (urea) resin, triazine ring resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having benzoxazine ring, etc. Can be mentioned.
One of these can be used alone, or two or more can be used in combination.

  The epoxy resin composition of this invention can use a phenol resin or a hardening accelerator as needed. Moreover, you may use together a phenol resin and a hardening accelerator.

  The phenol resin is not particularly limited. For example, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, an arylalkylene type novolak resin or other novolak type phenol resin, an unmodified resole phenol resin, tung oil, linseed oil, walnut oil And resol type phenolic resins such as oil-modified resol phenolic resins modified with the above. One of these may be used alone, or two or more having different weight average molecular weights may be used in combination, or one or more of the above-described resins may be used in combination with their prepolymer. You can also. Among these, arylalkylene type phenol resins are particularly preferable. Thereby, moisture absorption solder heat resistance can be improved further.

The curing accelerator is not particularly limited. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III). , Tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl- 5-hide Imidazole compounds such as xylimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenolic compounds such as phenol, bisphenol A and nonylphenol, acetic acid, benzoic acid Examples thereof include acids, organic acids such as salicylic acid and p-toluenesulfonic acid, and mixtures thereof. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.
Among these curing accelerators, imidazole compounds are particularly preferable. Thereby, the insulation and solder heat resistance when the resin composition is used as a prepreg for a semiconductor device can be improved.

Examples of the imidazole compound include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl) -ethyl-s-triazine, 2,4-diamino- 6- [2′-ethyl-4-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Can be mentioned.
Among these, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-ethyl-4-methylimidazole are preferable. These imidazole compounds have particularly excellent compatibility with the resin component, whereby a highly uniform cured product can be obtained.

The epoxy resin composition of the present invention preferably contains the (D) onium salt compound represented by the following general formula (2) together with the curing accelerator or together with the curing accelerator.

(Wherein P represents a phosphorus atom, R ¹ , R ² , R ³ and R ⁴ each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. May be the same as or different from each other, and A ⁻ represents an anion of an n (n ≧ 1) -valent proton donor having at least one proton that can be released outside the molecule, or a complex anion thereof. Is shown.)

  The compound represented by the general formula (2) can be synthesized, for example, by the method described in JP-A-2004-231765. For example, 4,4'-bisphenol S, tetraphenylphosphonium bromide, and ion-exchanged water are added, and an aqueous sodium hydroxide solution is added dropwise while stirring with heating. The precipitated crystals can be purified by filtration, washing with water and vacuum drying.

  The (D) onium salt compound is preferably a compound represented by the following general formula (3).

(In the formula, P represents a phosphorus atom, R ¹ , R ² , R ³ and R ⁴ each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. And X ¹ is an organic group bonded to the substituents Y ¹ and Y ^{2. In the} formula, X ² is bonded to the substituents Y ³ and Y ⁴ . Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are combined with a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. in a .X ^1, and ^{X 2} are identical with each other things May be ^{different, Y 1, Y 2, Y} 3, and Y ⁴ is good .Z ¹ also being the same or different organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring or, (Represents a substituted or unsubstituted aliphatic group.)

  The compound represented by the general formula (3) can be synthesized by, for example, a method described in JP-A-2007-246671. For example, 2,3-dihydroxynaphthalene, 3-mercaptopropyltrimethoxysilane, and methanol are uniformly dissolved under stirring, and an acetonitrile solution of triethylamine is dropped into the stirring flask. Next, a methanol solution of tetraphenylphosphonium bromide is gradually dropped into the flask, and the precipitated crystals can be purified by filtration, washing with water and vacuum drying.

  The (D) onium salt compound is preferably a compound represented by the following general formula (4).

(Wherein P is a phosphorus atom, B is a boron atom, R ¹ , R ² , R ³ , and R ⁴ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted group. R ⁵ , R ⁶ , R ⁷ and R ⁸ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or N (n ≧ 1) -valent proton donors having at least one substituted or unsubstituted aliphatic group or at least one proton capable of being released outside the molecule, which may be the same or different Good.)

  The compound represented by the general formula (4) can be synthesized, for example, by the method described in JP-A-2000-246113. For example, boric acid, 3-hydroxy-2-naphthoic acid, methyl cellosolve and pure water were uniformly dissolved under stirring, and then tetraphenylphosphonium bromide was uniformly dissolved in a methanol / pure water mixed solvent. The solution can be purified by dropping it into a stirred flask and filtering the precipitated crystals by filtration, washing with water and vacuum drying.

  The content of the (D) onium salt compound is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably, based on the total amount of (A) epoxy resin and (B) cyanate resin. It is 0.1 to 5 weight%, Most preferably, it is 0.2 to 2.5 weight%. Thereby, the outstanding sclerosis | hardenability, fluidity | liquidity, and hardened | cured material characteristic can be expressed.

  The epoxy resin composition of the present invention may further contain a resin component that improves the adhesion between the epoxy resin composition and the conductor layer. For example, phenoxy resin, polyamide resin, polyvinyl alcohol resin, and the like can be given. Among these, it is preferable to add a phenoxy resin in terms of excellent adhesion to a metal and little influence on the curing reaction rate. Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a novolak skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

The epoxy resin composition of the present invention is not particularly limited, but a coupling agent can be used. The coupling agent improves the wettability of the interface between the thermosetting resin and the inorganic filler. And a thermosetting resin etc. and an inorganic filler can be uniformly fixed with respect to a fiber base material, and heat resistance, especially the solder heat resistance after moisture absorption can be improved.
The coupling agent is not particularly limited, and is specifically selected from an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent. It is preferred to use one or more coupling agents. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

  Although the addition amount of the coupling agent is not particularly limited, it is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the inorganic filler. If the content is less than 0.05 parts by weight, the effect of improving the heat resistance may be reduced because the inorganic filler cannot be sufficiently coated. If the content exceeds 3 parts by weight, the reaction will be affected, and the bending strength will be May decrease.

  If necessary, the epoxy resin composition may further contain additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers. May be added.

Next, the prepreg will be described.
A prepreg using the above-described epoxy resin composition is obtained by impregnating a base material with the epoxy resin composition. Thereby, a prepreg suitable for manufacturing a printed wiring board excellent in various characteristics such as dielectric characteristics, mechanical and electrical connection reliability under high temperature and high humidity can be obtained.

  The base material is not particularly limited, but glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber substrate, kraft paper, cotton linter composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, etc. Examples thereof include organic fiber base materials such as paper base materials mainly composed of paper, mixed paper of linter and kraft pulp, and the like. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of a prepreg can improve, a water absorption can be lowered | hung, and a thermal expansion coefficient can be made small.

  Although the glass which comprises the said glass fiber base material is not specifically limited, For example, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned. Among these, E glass, T glass, or S glass is preferable. Thereby, the high elasticity of a glass fiber base material can be achieved and a thermal expansion coefficient can also be made small.

  The method for producing the prepreg is not particularly limited. For example, a resin varnish is prepared using the epoxy resin composition described above, the substrate is immersed in the resin varnish, the coating method is applied by various coaters, and sprayed. Methods and the like. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

The solvent used in the resin varnish desirably exhibits good solubility in the resin component in the resin composition, but a poor solvent may be used within a range that does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, and carbitol.
The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 50 to 80% by weight, and particularly preferably 60 to 78% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved. Although it does not specifically limit the predetermined temperature which impregnates the said resin composition to the said base material, A prepreg can be obtained by drying at 90-220 degreeC etc., for example.

Next, a laminated board is demonstrated.
The lamination of the present invention can be obtained by laminating metal foil on both upper and lower surfaces of at least one or a plurality of the prepregs laminated, and heating and pressing. The heating temperature is not particularly limited, but is preferably 120 to 230 ° C, particularly preferably 150 to 210 ° C. Moreover, the pressure to pressurize is not particularly limited, but is preferably 1 to 5 MPa, and particularly preferably 2 to 4 MPa. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.

  The metal foil is not particularly limited. For example, copper and copper-based alloy, aluminum and aluminum-based alloy, silver and silver-based alloy, gold and gold-based alloy, zinc and zinc-based alloy, nickel and nickel-based alloy, tin and tin And metal foils such as iron alloys, iron and iron alloys.

Next, the resin sheet will be described.
The resin sheet using the epoxy resin composition described above is obtained by forming an insulating layer made of the epoxy resin composition on a carrier film or a metal foil. First, the epoxy resin composition of the present invention for forming an insulating layer is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, Various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method in organic solvents such as cellsolve, carbitol, and anisole A resin varnish is prepared by dissolving, mixing, and stirring using the above.

  Although content of the resin composition in the said resin varnish is not specifically limited, 45 to 85 weight% is preferable and 55 to 75 weight% is especially preferable.

Next, the resin varnish is coated on a carrier film or a metal foil using various coating apparatuses, and then dried. Or after spray-coating a resin varnish on a carrier film or metal foil with a spray apparatus, this is dried. A resin sheet can be produced by these methods.
Although the said coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the resin sheet which does not have a void and has the thickness of a uniform insulating layer can be manufactured efficiently.

  Since the carrier film forms an insulating layer on the carrier film, it is preferable to select one that is easy to handle. Moreover, since the carrier film is peeled after laminating the insulating layer of the resin sheet on the inner layer circuit board surface, it is preferable that the resin sheet is easily peeled after being laminated on the inner layer circuit board. Therefore, it is preferable to use a thermoplastic resin film having heat resistance such as a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a fluorine-based resin, or a polyimide resin, for example. Among these carrier films, a film made of polyester is most preferable. This facilitates peeling from the insulating layer with an appropriate strength.

  Although the thickness of the said carrier film is not specifically limited, 1-100 micrometers is preferable and 3-50 micrometers is especially preferable. When the thickness of the carrier film is within the above range, handling is easy and the flatness of the surface of the insulating layer is excellent.

  Similar to the carrier film, the metal foil may be used after peeling a resin sheet on an inner circuit board and may be used after peeling the metal foil as a conductor circuit. The metal foil is not particularly limited. For example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, gold and gold-based alloy, Metal foils such as zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys can be used.

The thickness of the metal foil is not particularly limited, but is preferably 0.1 μm or more and 70 μm or less. Further, it is preferably 1 μm or more and 35 μm or less, more preferably 1.5 μm or more and 18 μm or less. If the thickness of the metal foil is less than the above lower limit, the metal foil is scratched, pinholes are generated, and when the metal foil is etched and used as a conductor circuit, plating variations, circuit disconnection, etching during circuit pattern molding There is a risk of infiltration of chemicals such as liquid and desmear liquid. When the upper limit is exceeded, the thickness variation of the metal foil increases or the surface roughness variation of the metal foil roughened surface increases. There is a case.
The metal foil may be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. Since an ultra-thin metal foil layer can be formed on both sides of the insulating layer by using an ultra-thin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, etc. By electroplating the metal foil directly as the power feeding layer, the ultrathin copper foil can be flash etched after the circuit is formed. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do. The thickness of the ultrathin metal foil is preferably 0.1 μm or more and 10 μm or less. Furthermore, it is preferably 0.5 μm or more and 5 μm or less, more preferably 1 μm or more and 3 μm or less. When the thickness of the ultrathin metal foil is less than the lower limit, the ultrathin metal foil is damaged after peeling the carrier foil, the pinhole of the ultrathin metal foil is generated, and the circuit pattern is formed by the generation of the pinhole. Plating variation, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid, etc. may occur. If the above upper limit is exceeded, the thickness variation of the ultrathin metal foil will increase or the ultrathin metal foil There may be a case where the roughness of the roughened surface becomes large.
Usually, an ultrathin metal foil with a carrier foil peels off the carrier foil before forming a circuit pattern on the press-molded laminate.

Next, a multilayer printed wiring board will be described.
A laminated board having copper foil on both sides obtained above is prepared, a through hole is formed by a drill or the like, and after filling the through hole by plating, a predetermined conductor circuit ( The inner layer circuit board is manufactured by forming the inner layer circuit) and subjecting the conductor circuit to a roughening process such as a blackening process.
Next, the above-described resin sheet or the above-described prepreg is formed on the upper and lower surfaces of the inner layer circuit board, and is heated and pressed.
Specifically, the resin sheet or prepreg and the inner layer circuit board are combined and subjected to vacuum heating and pressing using a vacuum pressurizing laminator apparatus or the like. Thereafter, the insulating layer can be formed on the inner circuit board by heat-curing with a hot air drying device or the like.
Although it does not specifically limit as conditions to heat-press form here, if an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 MPa. Moreover, it is although it does not specifically limit as conditions to heat-harden, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.
Alternatively, the insulating layer can be formed on the inner layer circuit board by superimposing the resin sheet or prepreg on the inner layer circuit board and subjecting the resin sheet or prepreg to heat pressing using a flat plate press apparatus or the like.
Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.

  The substrate obtained by the above-described method can form a new conductive wiring circuit by metal plating after roughening the surface of the insulating layer with an oxidizing agent such as permanganate or dichromate.

Thereafter, the insulating layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be made to harden | cure in the range of 100 to 250 degreeC. Preferably it is made to harden | cure at 150 to 200 degreeC.
Next, an opening is provided in the insulating layer by using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.
After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

Next, a semiconductor device will be described.
A semiconductor device can be manufactured by mounting a semiconductor element on a multilayer printed wiring board manufactured by the method described above. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a semiconductor element and a multilayer printed wiring board are used, and a flip-chip bonder or the like is used to align the connection electrode portions on the multilayer printed wiring board and the solder bumps of the semiconductor element. Thereafter, the solder bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the multilayer printed wiring board and the solder bump are connected by fusion bonding. And a semiconductor device can be obtained by filling and hardening a liquid sealing resin between a multilayer printed wiring board and a semiconductor element.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

The raw materials used in Examples and Comparative Examples are as follows.
(1) Aluminum hydroxide A / Gibsite; BE-033 manufactured by Nippon Light Metal Co., Ltd. Average particle size 2.2 μm BET specific surface area 3.6 m ² / g
(2) Aluminum hydroxide B / Gibsite; Showa Denko HP-360 average particle size 2.7 μm BET specific surface area 1.3 m ² / g
(3) Aluminum hydroxide C / boehmite; C-20 manufactured by Daimyo Chemical Co., Ltd. Average particle size 2.0 μm BET specific surface area 4.0 m ² / g
(4) Inorganic filler A / spherical silica; manufactured by Admatechs Co., Ltd. “SO-25R”, average particle size 0.5 μm
(5) Inorganic filler B / spherical silica; manufactured by Admatechs Co., Ltd. “SO-32R”, average particle size 1.0 μm
(6) Inorganic filler C / spherical silica; manufactured by Denki Kagaku Kogyo Co., Ltd. “SFP-20M”, average particle size 0.3 μm
(7) Inorganic filler D / magnesium hydroxide; “Kisuma 5Q” manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.8 μm
(8) Inorganic filler E / talc; manufactured by Fuji Talc “LMS-200”, average particle size 5.0 μm
(9) Epoxy resin A / Methoxynaphthalene dimethylene type epoxy resin; “HP-5000” manufactured by DIC, epoxy equivalent 250
(10) Epoxy resin B / methoxynaphthalene dimethylene type epoxy resin; “EXA-9900” manufactured by DIC, epoxy equivalent 274
(11) Epoxy resin C / Methoxynaphthalene dimethylene type epoxy resin; “EXA-7320L” manufactured by DIC, epoxy equivalent 246
(12) Epoxy resin D / biphenyl dimethylene type epoxy resin: Nippon Kayaku Co., Ltd. “NC-3000”, epoxy equivalent 275
(13) Cyanate resin A / Novolak type cyanate resin: Lonza Japan Co., Ltd. “Primaset PT-30”, cyanate equivalent 124
(14) Cyanate resin B / bisphenol A type cyanate resin: Lonza Japan Co., Ltd. “Primaset BA-200”, cyanate equivalent 139
(15) Cyanate resin C / bisphenol A type cyanate resin: Lonza Japan Co., Ltd. “Primaset BA-230”, cyanate equivalent 232
(16) Cyanate resin D / dicyclopentadiene type cyanate resin: manufactured by Lonza Japan Co., Ltd. “Primaset DT-4000”, cyanate equivalent 174
(17) Phenoxy resin / copolymer of bisphenol A type epoxy resin and bisphenol F type epoxy resin: “jER4275” manufactured by Japan Epoxy Resin Co., Ltd., weight average molecular weight 60000
(18) Phenol-based curing agent / biphenylalkylene type novolak resin: “MEH-7851-3H” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 220
(19) Curing accelerator / imidazole compound: “Cureazole 1B2PZ (1-benzyl-2-phenylimidazole)” manufactured by Shikoku Kasei Kogyo Co., Ltd.
(20) (D) Onium salt compound compound (D1) and compound (D2): The synthesis method is shown below.

The (D) onium salt compound was obtained by the following method.

1. (D) Synthesis of Onium Salt Compound An example of a method for synthesizing the (D) onium salt compound used in the present invention is shown, but the synthesis method is not limited thereto.

(1) Synthesis of Compound (D1) In a three-necked separable flask equipped with a thermometer, a stirrer and a Dimroth condenser, tetraphenylphosphonium tetraphenylborate (manufactured by Hokuko Chemical Co., Ltd., TPP-K) 32. 9 g (0.05 mol) and 1-naphthoic acid 34.4 g (0.20 mol) were charged, and the mixture was stirred at 260 ° C. for 5 hours in a nitrogen atmosphere. At that time, by-product benzene was removed from the system. After cooling, the obtained crystal was washed with methanol, dried, and further purified by vacuum drying to obtain 47.0 g of a compound (D1) represented by the following structural formula (5). The yield was 91%.

(5) Synthesis of compound (D2) In a three-necked separable flask equipped with a stirrer and a Dimroth condenser, 32.0 g (0.20 mol) of 2,3-dihydroxynaphthalene, 19.8 g of phenyltrimethoxysilane (0 .10 mol) and 150 mL of methanol were charged and uniformly dissolved under stirring. A solution prepared by previously dissolving 18.5 g (0.10 mol) of tri-n-butylamine in 20 mL of acetonitrile was dropped into a stirred flask, and then 41.9 g (0.10 mol) of tetraphenylphosphonium bromide was added in advance to 100 mL. A solution dissolved in methanol was gradually added dropwise into the flask to precipitate crystals. The precipitated crystals were purified by filtration, washing with water, and vacuum drying to obtain 70.0 g of a compound (D2) represented by the following structural formula (5). The yield was 92%.

<Example 1>
(1) Preparation of resin varnish Dissolve and disperse 24.8 parts by weight of epoxy resin A, 30.0 parts by weight of cyanate resin A, 5.0 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator (imidazole compound) in methyl ethyl ketone. It was. Further, 40.0 parts by weight of aluminum hydroxide A was added, and the mixture was stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.

(2) Preparation of prepreg The above resin varnish was impregnated into a glass woven fabric (thickness 94 μm, manufactured by Nitto Boseki Co., Ltd., WEA-116E), dried in a heating furnace at 150 ° C. for 2 minutes, and varnish solid content in the prepreg About 50% by weight of prepreg was obtained.

(3) Fabrication of laminated plate Two prepregs are stacked, 12 μm copper foil (made by Mitsui Kinzoku Co., Ltd.) is stacked on both sides, and heated and pressed at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours. A laminated board having a thickness of 0.2 mm having a copper foil was obtained.

(4) Production of Multilayer Printed Wiring Board After the through hole processing was performed on the laminated board obtained above using a 0.1 mm drill bit, the through hole was filled by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. The prepreg obtained above was superposed on the front and back of the inner layer circuit board, and this was subjected to vacuum heating and press molding at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressurizing laminator apparatus. This was heated and cured at 170 ° C. for 60 minutes in a hot air drying apparatus to obtain a multilayer printed wiring board.

(5) Fabrication of semiconductor device As described above, an opening is provided in the insulating layer of the multilayer printed wiring board using a carbonic acid laser device, an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating, and conduction between the outer layer circuit and the inner layer circuit is performed. I planned. Note that the outer layer circuit was provided with a connection electrode part for mounting a semiconductor element.
Thereafter, a solder resist (manufactured by Taiyo Ink Co., PSR4000 / AUS308) is formed on the outermost layer, the connection electrode portion is exposed so that a semiconductor element can be mounted by exposure and development, and a nickel gold plating process is performed, and the size is 50 mm × 50 mm. A multilayer printed wiring board was obtained by cutting.
Thereafter, in the semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm), the solder bump is formed of a eutectic of Sn / Pb composition, and the circuit protective film is a positive photosensitive resin (CRC- manufactured by Sumitomo Bakelite Co., Ltd.). 8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on the package substrate by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes.

<Example 2>
Epoxy resin A 8.0 parts by weight, cyanate resin A 15.0 parts by weight, and phenolic curing agent 7.0 parts by weight were dissolved and dispersed in methyl ethyl ketone. Furthermore, 20.0 parts by weight of aluminum hydroxide A and 50.0 parts by weight of inorganic filler B were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Example 3>
Epoxy resin B 5.0 parts by weight, cyanate resin B 10.0 parts by weight, and phenolic curing agent 5.0 parts by weight were dissolved and dispersed in methyl ethyl ketone. Further, 30.0 parts by weight of aluminum hydroxide B and 50.0 parts by weight of inorganic filler A were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Example 4>
(1) Preparation of resin varnish 19.8 parts by weight of epoxy resin C, 15.0 parts by weight of cyanate resin C, 5.0 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 20.0 parts by weight of aluminum hydroxide B and 40.0 parts by weight of inorganic filler C were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.

(2) Preparation of Prepreg Glass woven fabric (thickness 94 μm, Nitto Boseki Co., Ltd., WEA-116E) is impregnated with the above resin varnish, dried in a heating furnace at 150 ° C. for 2 minutes, and varnish solid content in the prepreg About 50% by weight of prepreg was obtained.

(3) Preparation of laminated plate Two sheets of the above prepreg are stacked, 12 μm copper foil (made by Mitsui Kinzoku Co., Ltd.) is stacked on both sides, and heated and pressed at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours. A laminate having a thickness of 0.2 mm was obtained.

(4) Production of Resin Sheet Using the above-described resin varnish on a PET film (thickness 38 μm, manufactured by Mitsubishi Plastics Polyester, SFB38) using a comma coater device, the thickness of the epoxy resin layer after drying is 40 μm. This was coated and dried for 5 minutes with a drying apparatus at 150 ° C. to produce a resin sheet.

(5) Production of multilayer printed wiring board After the through-hole processing was performed on the laminated board obtained above using a 0.1 mm drill bit, the through-hole was filled by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. The resin sheet obtained above was superposed with the epoxy resin surface facing inward, and this was vacuum heated and pressure molded at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressure laminator device. After peeling the PET film as the base material from the resin sheet, the substrate was heated and cured at 170 ° C. for 60 minutes with a hot air dryer to obtain a multilayer printed wiring board.

(6) Fabrication of semiconductor device As described above, an opening is provided in the insulating layer of the multilayer printed wiring board using a carbonic acid laser device, an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating, and conduction between the outer layer circuit and the inner layer circuit is performed. I planned. Note that the outer layer circuit was provided with a connection electrode part for mounting a semiconductor element.
Thereafter, a solder resist (manufactured by Taiyo Ink Co., PSR4000 / AUS308) is formed on the outermost layer, the connection electrode portion is exposed so that a semiconductor element can be mounted by exposure and development, and a nickel gold plating process is performed, and the size is 50 mm × 50 mm. A multilayer printed wiring board was obtained by cutting.
Thereafter, in the semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm), the solder bump is formed of a eutectic of Sn / Pb composition, and the circuit protective film is a positive photosensitive resin (CRC- manufactured by Sumitomo Bakelite Co., Ltd.). 8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on the package substrate by thermocompression bonding using a flip chip bonder device. Next, after melt-bonding solder bumps in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-415S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes.

<Example 5>
9.8 parts by weight of epoxy resin A, 20.0 parts by weight of epoxy resin D, 45.0 parts by weight of cyanate resin A, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 20.0 parts by weight of aluminum hydroxide C and 5.0 parts by weight of inorganic filler D were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
Using this resin varnish, a prepreg, a laminate, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 4.

<Example 6>
19.8 parts by weight of epoxy resin A, 10.0 parts by weight of cyanate resin D, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 10.0 parts by weight of aluminum hydroxide A, 50.0 parts by weight of inorganic filler A, and 10.0 parts by weight of inorganic filler E were added and stirred for 10 minutes using a high-speed stirrer to obtain a solid content of 60 weights. % Resin varnish was prepared.
Using this resin varnish, a prepreg, a laminate, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 4.

<Example 7>
23.0 parts by weight of epoxy resin A, 14.0 parts by weight of cyanate resin A, 2.0 parts by weight of phenoxy resin, and 1.0 part by weight of compound (D1) were dissolved and dispersed in methyl ethyl ketone. Further, 30.0 parts by weight of aluminum hydroxide A and 30.0 parts by weight of inorganic filler A were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Example 8>
19.0 parts by weight of epoxy resin A, 19.5 parts by weight of cyanate resin A, and 1.5 parts by weight of compound (D2) were dissolved and dispersed in methyl ethyl ketone. Further, 20.0 parts by weight of aluminum hydroxide C and 40.0 parts by weight of inorganic filler B were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
Using this resin varnish, a prepreg, a laminate, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 4.

<Comparative Example 1>
29.8 parts by weight of epoxy resin D, 15.0 parts by weight of cyanate resin A, 5.0 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 50.0 parts by weight of aluminum hydroxide A was added, and the mixture was stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Comparative example 2>
39.8 parts by weight of epoxy resin A, 10.0 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 50.0 parts by weight of aluminum hydroxide A was added, and the mixture was stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Comparative Example 3>
24.8 parts by weight of epoxy resin A, 20.0 parts by weight of cyanate resin A, 5.0 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 50.0 parts by weight of inorganic filler B was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish, a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

  The characteristics of the laminates, multilayer printed wiring boards and semiconductor devices obtained in the examples and comparative examples were evaluated. The results are shown in Tables 1 and 2.

(1) Coefficient of thermal expansion The copper foil of the laminated board having a thickness of 0.2 mm was etched on the whole surface, a test piece of 4 mm × 20 mm was cut out from the obtained laminated board, and the condition was 50 ° C./minute using TMA. The linear expansion coefficient (average linear expansion coefficient) in the plane direction at from ℃ to 150 ℃ was measured. Each code | symbol is as follows.
A: Linear expansion coefficient of less than 10 ppm B: Linear expansion coefficient of 10 ppm or more and less than 15 ppm X: Linear expansion coefficient of 15 ppm or more

(2) Molded state of laminated board The obtained double-sided copper-clad laminated board was subjected to copper foil etching, the appearance was observed, and the length of streaks due to separation of the inorganic component and the resin component found in the peripheral portion was measured. Each code | symbol is as follows.
◎: The length of the stripe is less than 5 mm ○: The length of the stripe is 5 to 10 mm
X: The length of the stripe is 10 mm or more

(3) Drill workability The state of the cutting edge was evaluated after making a hole of 2000 times at 300,000 rotations using a 0.1 mm drill blade on a 0.2 mm thick laminate. Each code | symbol is as follows.
○: The cutting edge remains sufficiently, and it is possible to regenerate the drill blade by regrinding ×: The cutting edge is rounded and the drill blade cannot be regenerated.

(4) Solder heat resistance A 50 mm square sample was cut out from the obtained multilayer printed wiring board, 3/4 etched, treated at 121 ° C. for 2 hours using a pressure cooker, immersed in 260 ° C. solder for 30 seconds, and swollen The presence or absence of was observed. Each code | symbol is as follows.
○: No abnormality ×: Swelling occurred

(5) Thermal shock test The obtained semiconductor device was processed in Fluorinert for 1000 cycles at −55 ° C. for 10 minutes, 125 ° C. for 10 minutes, and −55 ° C. for 10 minutes, and cracks occurred in the test piece. It was confirmed visually.
Each code is as follows.
○: No crack occurrence ×: Crack occurrence

(6) Insulation reliability test [1]
Using the obtained multilayer printed wiring board, an insulation reliability test between through-hole walls was performed. With a pattern of 150 μm between walls, 20 V was applied in an environment of 130 ° C./85%, a sample after 200 hours was taken out from the test tank, and the resistance value at normal temperature and humidity was measured. Each code is as follows.
◎: Resistance value of 10 ⁹ Ω or more ○: Resistance value of 10 ⁸ Ω or more and less than 109 △: Resistance value of 10 ⁷ Ω or more and less than 108 Ω ×: Resistance value of less than 10 ⁷ Ω

(7) Insulation reliability test [2]
The insulation reliability test was performed in the same manner as described above, and the resistance behavior in the humidity (at 130 ° C./85% environment) after 200 hours was observed. In the humidity, since the resistance value is measured under severe conditions as compared with the normal temperature and normal humidity environment, the resistance value generally tends to be low. Each code is as follows.
◎: Resistance value of 10 ⁹ Ω or more ○: Resistance value of 10 ⁸ Ω or more and less than 109 △: Resistance value of 10 ⁷ Ω or more and less than 108 Ω ×: Resistance value of less than 10 ⁷ Ω

  Examples 1 to 8 use the epoxy resin composition of the present invention. It was good throughout the evaluation, there was no molding failure of the laminate, and it was in a good molding state. On the other hand, since Comparative Example 1 did not use a methoxynaphthalenedi-methylene type epoxy resin, problems were observed during the molding of the laminate, and the reliability of the semiconductor device was also poor. Since the cyanate resin was not used for the comparative example 2, it was inferior to low thermal expansion property and heat resistance, and the reliability of the semiconductor device was not satisfactory. In Comparative Example 3, aluminum hydroxide was not used, and only silica was used, so that drillability was lowered. It has been found that the epoxy resin composition of the present invention is effective for satisfying all of moldability, low thermal expansibility, heat resistance, workability, and reliability.

In Reference Examples 1 to 4, curing acceleration (imidazole) (Reference Example 1), phenolic compound (Reference Example 2), compound (D1) (Reference Example 3), or compound (based on the formulation of Example 1 above) D2) A prepreg, a laminated board, a multilayer printed wiring board, and a semiconductor device were produced by replacing (Reference Example 4).
In the conventional insulation reliability test, it is a method of taking out from moisture and evaluating the insulation reliability. Therefore, although there is no difference in Reference Examples 1 to 4, insulation in moisture measurement is more severe evaluation. In the reliability test, those using the imidazole compound of Reference Example 1 had a relatively low resistance value of less than 10 ⁸ Ω after 200 hours. Moreover, what used the phenol type hardening | curing agent of the reference example 2 was maintaining 10 < ⁸ > (ohm) or more, and was favorable. The best results were obtained using the onium salt compounds of Reference Examples 3 and 4, and almost no decrease in resistance value was observed.

The epoxy resin composition of the present invention can be suitably used for a substrate called a package substrate used for a system-in-package (SiP) or the like that requires miniaturization, high-level wiring, and high reliability.

Claims (14)

An epoxy resin composition used for a prepreg or a resin sheet used for a multilayer printed wiring board,
(A) An epoxy resin having a structure represented by the following general formula (1), (B) aluminum hydroxide , (C) a cyanate resin, and (D) an onium salt compound as essential components Composition.

[Wherein X is hydrogen or an epoxy group (glycidyl ether group), and R1 and R2 are
Independent of each other, it represents one selected from hydrogen, methyl group, ethyl group, propyl group, butyl group, phenyl group, and benzyl group. n is an integer of 1 or more, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit. ] ^2. The epoxy resin composition according to claim 1, wherein the (B) aluminum hydroxide has a BET specific surface area of 1.0 m ² / g or more. The epoxy resin composition according to claim 1, wherein the (B) aluminum hydroxide has an average particle size of 10.0 μm or less. The epoxy resin composition according to any one of claims 1 to 3, wherein the content of the (B) aluminum hydroxide is 5 to 60% by weight of the entire epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 4 further contains at least one inorganic filler selected from the group consisting of magnesium hydroxide, silica, talc, fired talc, and alumina. Epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 5, wherein the content of the epoxy resin having the structure represented by (A) the general formula (1) is 1 to 40% by weight of the entire epoxy resin composition. object. The (C) cyanate resin is at least one selected from the group consisting of phenol novolac type cyanate resin, cresol novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol F type cyanate resin, and dicyclopentadiene type cyanate resin. The epoxy resin composition according to any one of claims 1 to 6. The epoxy resin composition according to any one of claims 1 to 7, wherein the content of the (C) cyanate resin is 3 to 50% by weight of the entire epoxy resin composition. The epoxy resin composition according to claim 1, wherein the (D) onium salt compound is a compound represented by the following general formula (2).
(Wherein P is a phosphorus atom, R 1, R 2, R 3 and R 4 are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, independently of each other. A − represents an anion of an n (n ≧ 1) -valent proton donor having at least one proton that can be released outside the molecule, or a complex anion thereof. Is shown.) It claims 1 to prepreg formed by impregnating the epoxy resin composition according to the substrate either 9. A laminate having a metal foil on at least one side of a laminate in which at least one prepreg according to claim 10 is laminated. It claims 1 to on the film an insulating layer made of an epoxy insulating resin composition according to any one of 9, or a resin sheet obtained by forming on a metal foil. A multilayer printed wiring board produced using at least one selected from the group consisting of the prepreg according to claim 10 , the laminate according to claim 11 , and the resin sheet according to claim 12 . A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 13 .