TW201609947A - Epoxy resin composition, resin sheet, prepreg and metal-clad laminated sheet, printed circuit board, and semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide an epoxy resin composition capable of forming a resin board in which warping, which may occur in a heating step of a board manufacturing process and/or a mounting process, is suppressed, a resin sheet, a prepreg, a metal-clad laminated sheet, a printed circuit board, and a semiconductor device which are obtained using said epoxy resin composition. The epoxy resin composition according to the present invention includes, as essential components, an epoxy resin represented by the following general formula (1) and a cyanate ester compound having two or more cyanato groups in its molecule. (In the formula, the ratio of (a) to (b), i.e., (a)/(b)=1-3. G represents a glycidyl group. n is 0-5, which is the number of repetitions.)

Description

Epoxy resin composition, resin sheet, prepreg and metal-clad laminate, printed wiring board, and semiconductor device

The present invention relates to an epoxy resin composition, a resin sheet obtained by coating the same on a surface of a support, a prepreg impregnated on a fiber substrate, a metal-clad laminate, a printed wiring board, and a semiconductor device .

With the recent demand for high functionality and lightness and thinness of electronic devices, high-density integration of electronic components and high-density mounting have progressed, and the miniaturization of semiconductor devices used in such electronic devices has progressed rapidly.

Therefore, there is a tendency for the printed wiring board on which the electronic component including the semiconductor element is mounted to be thinner, and the resin substrate used for the printed wiring board has a thickness of about 0.8 mm.

Further, recently, a package-on-package (hereinafter referred to as POP) is mounted on a mobile device (for example, a mobile phone, a smart phone, a tablet PC, etc.), and the package is packaged in a semiconductor package using a resin substrate of 0.4 mm or less. Stack each other. It is clear that this tendency is further accelerated and the thinning progresses year by year (Non-Patent Document 1).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-43958

Non-Patent Document 1: Semiconductor Technology Blueprint Special Committee 2009 Annual Report Chapter 8 WG7 Installation

Non-Patent Document 2: Hitachi Chemical Technical No. 56, [online], December 2013, [Search July 29, 2014], Internet <URL: http://www.hitachi-chem.co. Jp/japanese/report/056/56_tr02.pdf>

Non-Patent Document 3: Lichang Industrial RISHO NEWS Technical Report No91, [online], [Search July 29, 2014], Internet <URL: http://www.risho.co.jp/rishonews/technical_report/tr91 /r180_tr91.pdf>

When the miniaturization of the semiconductor device progresses as described above, there are many cases in which the substrate is subjected to a high temperature exceeding 200 ° C. If the thickness of the substrate is thin, the rigidity becomes insufficient, and the step is bent or deformed. Therefore, productivity is deteriorated (Non-Patent Document 2).

Further, the thickness of the semiconductor element and the sealing material which have largely assumed the rigidity of the semiconductor device has become extremely thin, and it has become easy to cause warpage of the semiconductor device in the mounting step. In addition, the proportion of the resin substrate as the constituent member is increased, and the physical properties and behavior of the resin substrate greatly affect the warpage of the semiconductor device (Non-Patent Document 3).

On the other hand, in the case of the global environmental protection, the highest temperature in the reflow process performed when the semiconductor element is mounted on the printed wiring board or the semiconductor package is mounted on the mother board becomes the lead-free progress of the solder. very high. Generally, the lead-free solder frequently used has a melting point of about 210 degrees, so that the maximum temperature in the reflow step is more than 260 degrees.

In general, the difference between the thermal expansion of the semiconductor element and the printed wiring board on which the semiconductor element is mounted Very big. Therefore, in the reflow step performed when the semiconductor element is mounted on the printed wiring board, there is a case where the resin substrate is greatly warped. Moreover, even in the reflow soldering step performed when the semiconductor package is mounted on the mother board, the resin substrate is largely warped.

On the other hand, Patent Document 1 discloses a phenolic novolak resin having a biphenyl skeleton and a phenol novolak epoxy resin obtained by epoxidation, and is described as useful for the use of a semiconductor encapsulant. Sex. However, the characteristics of the composition containing the epoxy resin and the cyanate compound are not described, and the usefulness of the use of the printed wiring board is also not described.

Therefore, an object of the present invention is to provide an epoxy resin composition, a resin sheet obtained using the same, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device, and the epoxy resin composition can be used for substrate production. The resin substrate in which the warpage occurring in the heating step of the step and/or the mounting step is suppressed.

The inventors of the present invention have diligently studied in order to solve the above problems, and as a result, have completed the present invention.

In other words, the present invention provides (1) an epoxy resin composition comprising an epoxy resin represented by the following formula (1) and a cyanate compound having two or more cyanooxy groups in the molecule as essential components. ,

(wherein the ratio of (a)(b) is (a)/(b)=1~3; G is a glycidyl group; n is a repeat number, 0 to 5); (2) a prepreg The prepreg according to the above (2), wherein the fiber base material is a glass fiber base material; (4) The prepreg according to the above (3), wherein the glass fiber base material contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass; A metal-clad laminate having a metal foil in at least one area of the prepreg according to the above (2) to (4); (6) a resin sheet comprising the epoxy described in the above (1) An insulating layer composed of a resin composition is formed on a film or a metal foil; (7) A printed wiring board obtained by using the metal-clad laminate according to (5) above for an inner layer circuit board, and (8) a printed wiring board obtained by any one of the above (2) to (4) The prepreg according to the invention, wherein the resin sheet according to the above (6) is cured, and the semiconductor device is mounted on the printed wiring board according to the above (7) or (8). to make.

The epoxy resin composition of the present invention is a material useful for producing a laminated board such as a printed wiring board or a build-up board because the cured product has high heat resistance and excellent high bending modulus in a high temperature region.

According to the present invention, there is provided an epoxy resin composition, a resin sheet obtained using the same, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device, wherein the epoxy resin composition can obtain a substrate fabrication step and / or a resin substrate in which the warpage occurring in the heating step of the mounting step is suppressed.

The epoxy resin composition of the present invention will be described.

The epoxy resin composition of the present invention contains an epoxy resin represented by the following formula (1) as an essential component.

(In the formula, the ratio of (a) to (b) is (a)/(b) = 1 to 3; G represents a glycidyl group; and n is a repeating number of 0 to 5).

The epoxy resin represented by the above formula (1) can be described in JP-A-2011-252037, JP-A-2008-156553, JP-A-2013-043958, and International Publication No. WO2012/053522, WO2007/007827. The method is synthesized, but any method can be used if it has the structure of the above formula (1).

In the present invention, in particular, the ratio (polyfunctionalization ratio) of the above formula (a) to the above formula (b) is (a)/(b) = 1 to 3. When the structure of (a) is large, the heat resistance is improved, but accordingly, not only the water absorption property is deteriorated, but also the brittleness becomes hard. Therefore, those having a polyfunctionalization rate within the above range are used.

The softening point (ring and ball method) of the epoxy resin used is preferably 50 to 150 ° C, more preferably 52 to 100 ° C, and particularly preferably 52 to 95 ° C. If it is 50 ° C or less, there is a case where the viscosity is strong, the operation is difficult, and there is a problem in productivity. Further, in the case of 150 ° C or more, there is a case where the temperature is close to the molding temperature, and fluidity at the time of molding cannot be ensured, so And not good.

The epoxy equivalent of the epoxy resin used is preferably from 180 to 350 g/eq. Especially preferred is 190~300g/eq. When the epoxy equivalent is less than 180 g/eq., since there are too many functional groups, the water absorption rate of the cured product after hardening becomes high, and it tends to become brittle. When the epoxy equivalent exceeds 350 g/eq., it is considered that the softening point becomes very large, or the epoxidation is not carried out at the same time, and the amount of chlorine derived from epichlorohydrin used as a raw material becomes very large, and thus owes good.

Further, the amount of chlorine in the epoxy resin used in the present invention is preferably from 200 to 1,500 ppm, more preferably from 200 to 900 ppm, based on the total chlorine (hydrolysis method). According to the JPCA standard, it is expected that the amount of chlorine does not exceed 900 ppm even for epoxy monomers. Further, if the amount of chlorine is large, the electrical reliability is affected correspondingly, which is not preferable. In the case where the amount of chlorine is less than 200 ppm, there is an excessive purification step, which is problematic in terms of productivity, and thus is not preferable.

Furthermore, the epoxy resin used in the present invention has a melt viscosity of preferably 0.05 to 5 Pa at 150 ° C. s, especially good is 0.05~2.0Pa. s. If the melt viscosity is higher than 5Pa. s, there is a problem of fluidity, and the fluency or embedding during pressurization causes problems. The melt viscosity is less than 0.05Pa. In the case of s, there is a case where the molecular weight is too small, so that heat resistance is insufficient.

The ratio of (a) to (b) in the above formula is (a) / (b) = 1 to 3. That is, it is characterized in that half or more of the glycidyl ether structure is a resorcinol structure. This ratio is important for the precipitation of crystals and the improvement of heat resistance, and it is preferred that (a)/(b) exceeds 1. Further, by (a)/(b) being 3 or less, the amount of the resorcinol structure of the glycidyl ether is restricted, whereby the water absorption and the toughness can be improved.

In the above formula, n is a repeating unit and is 0 to 5. The fluency or fluidity when the prepreg or the resin sheet is formed is controlled by n not exceeding 5. When n exceeds 5, not only does liquidity arise? And the solubility in the solvent also causes problems.

In the present invention, the solubility of the epoxy resin into the solvent becomes important. For example, in the case where an epoxy resin having a biphenyl aralkyl type having the same skeleton is used in combination, solubility in a solvent such as methyl ethyl ketone or toluene or propylene glycol monomethyl ether is also required for the resins.

In the present invention, the solubility in methyl ethyl ketone is particularly important, and it is required that crystals are not precipitated at 5 ° C, room temperature, or the like for 2 months or longer. The ratio of the above (a)/(b) is also related. If the value of (a) is large, the crystals are easily precipitated. Therefore, it is important that (a)/(b) is 1 or more.

The epoxy resin composition of the present invention contains a cyanate compound having two or more cyanooxy groups in the molecule as an essential component.

As the cyanate ester compound, a previously known cyanate compound can be used. Specific examples of the cyanate ester compound include a polycondensate of a phenol and various aldehydes, a polymer of a phenol and various diene compounds, a polycondensate of a phenol and a ketone, and a bisphenol. Cyanide obtained by reacting various aldehyde condensates, phenols and aromatic dimethanols, phenols and aromatic dichloromethyls, phenols and aromatic bisalkoxymethyl groups with a halogenated cyano group The acid ester compound is not limited to these. These may be used alone or in combination of two or more.

Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.

Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde.

Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, and divinylene. Base benzene, diisopropenylbiphenyl, butadiene, isoprene, and the like.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.

Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S, biphenol, and bisphenol AD.

Examples of the aromatic dimethanol include benzenedimethanol and biphenyl dimethanol. Examples of the aromatic dichloromethyl group include α,α'-dichloroxylene and bischloromethylbiphenyl. Examples of the aromatic bisalkoxymethyl group include bismethoxymethylbenzene, bismethoxymethylbiphenyl, and bisphenoxymethylbiphenyl.

Specific examples of the cyanate compound to be used in the epoxy resin composition of the present invention include compounds represented by the following formulas (2) to (4), but are not limited thereto.

(wherein R ₁ represents a structure of the following formula (2'), and R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different).

(In the formula, a plurality of R exist independently, and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. n is an average value, and represents 1 < n ≦ 20).

In the present invention, it is particularly preferred to use an epoxy resin composition using a compound of the above formula (2) wherein R ₁ is a methylene group, an isopropylidene group or a tricyclodecane structure, and the above formula (4) is used. Structure of the compound.

As a specific synthesis method of such a cyanate compound, for example, the synthesis method is described in JP-A-2005-264154.

The blending amount of the cyanate ester compound is not particularly limited, and in the case of mainly incorporating a cyanate ester and an epoxy resin, it is preferably blended with respect to the functional group equivalent (cyanate ester equivalent) of the cyanate ester compound. ~1.4 equivalents, more preferably 0.2 to 1.4, still more preferably 0.5 to 1.4 equivalents of epoxy resin.

With regard to the above blending amount, in particular, it also affects the catalyst to be used or the material to be blended. For example, in the case of a nitrogen-containing catalyst such as imidazole, it also causes anionic polymerization of the epoxy resins. Therefore, the above blending amount is particularly preferably 0.8 to 1.4 equivalents.

Further, in the case of blending the epoxy resin hardener, it is preferred to blend 0.5 to 1.4 equivalents of the epoxy resin with respect to the total functional group equivalent of the hardener and the cyanate ester. Further, in the case of blending a resin which can be hardened simultaneously with a maleimide resin or the like and which can be crosslinked with an epoxy resin or a cyanate ester, it is necessary to subtract the amount of the equivalent functional groups to determine the blending. More preferably, it has a functional group reactive with an epoxy group of 0.5 to 1.4 equivalents.

The epoxy resin composition of the present invention can be used in combination with other epoxy resins. Specific examples of other epoxy resins which can be used in combination with the epoxy resin used in the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or Phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkane) Polycondensate of aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.; the above phenols and various diene compounds (two Cyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, dibutyl a polymer of a olefin, an isoprene or the like; a polycondensate of the above phenols and a ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); a polycondensate of phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.); the above phenols and aromatic dichloromethyls (α,α'-dichloroxylene) Polycondensate of bischloromethylbiphenyl, etc.; the above phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethyl) a polycondensate of a phenyl group or the like; a glycidyl ether epoxy resin or an alicyclic epoxy resin obtained by subjecting a bisphenol to a polycondensate or an alcohol of various aldehydes to be epoxy-propylated The epoxy propylamine epoxy resin, the glycidyl ester epoxy resin, and the like are not limited thereto as long as they are commonly used epoxy resins. These may be used alone or in combination of two or more.

In the case of blending the epoxy resin composition of the present invention, a previously known epoxy resin hardener may be used in combination. Specific examples of the epoxy resin curing agent that can be used together include an amine compound, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, and tetrahydrophthalic anhydride. An acid anhydride compound such as methyltetrahydrophthalic anhydride, methylic acid anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride; bisphenols and phenols (phenol, alkyl substitution) Phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl a polycondensate that replaces benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.; phenols and various diene compounds (dicyclopentadiene, terpenes, Vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polymer; phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) Polycondensates, but are not limited to these. These may be used alone or in combination of two or more. The blending amount is preferably 2 times or less, preferably 1 time or less, based on the weight ratio of the epoxy resin.

In the epoxy resin composition of the present invention, the amount of the curing agent used in the case of using the curing agent is preferably 1 equivalent or less based on 1 equivalent of the epoxy group of the epoxy resin. When the reaction of the epoxy resin and the cyanate ester is carried out in the case where the reaction of the epoxy resin and the cyanate ester is carried out, the hardener remains and the hardening becomes incomplete, and the good hardenability property cannot be obtained. Especially good is 0.1~0.98. Further, in the present invention, as a preferred combination of the epoxy resin and the hardener, the epoxy resin having a softening point of 45 to 140 degrees (more preferably 50 to 100 ° C) and a softening point of 50 to 140 ° C (preferably 55 to 5) 120 ° C) hardener. A resin composition having characteristics of balance in fluidity, flame retardancy, and heat resistance is formed.

A maleic imine resin may also be added to the epoxy resin composition of the present invention. The commercially available maleic imine resin is not particularly limited, and examples thereof include: 1 to 4 hydrogens on the aromatic ring are substituted with an alkyl group having 1 to 3 carbon atoms, or an unsubstituted double malayan Ampicillin or phenolic novolac type maleic imine resin.

The maleimide resin is not reacted with the cyanate resin in an equivalent amount, but is polymerized separately or in a random introduction manner, and thus the blending ratio is not particularly limited, in order to further enhance the epoxy resin composition of the present invention. The characteristics are preferably from 10 to 45% by weight, particularly preferably from 10 to 40% by weight, based on the total of the epoxy resin, cyanate ester and maleimide resin.

The epoxy resin composition of the present invention may also contain a hardening accelerator. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl) a tertiary amine such as phenol or 1,8-diazabicyclo[5,4,0]undecene-7; a phosphine such as triphenylphosphine; a metal compound such as stannous octoate or the like. The hardening accelerator may be used in an amount of 0.1 to 5.0 parts by weight, based on 100 parts by weight of the epoxy resin.

In the epoxy resin composition of the present invention, an additive such as a flame retardant or a filler may be blended in a range in which the properties such as dielectric properties or heat resistance of the cured product are not deteriorated.

The flame retardant to be blended as needed is not particularly limited, and is preferably a flame retardant which is not reactive with a cyanooxy group. Here, the term "non-reactive with cyanooxy group" means that when a flame retardant is added to a printed wiring board resin composition, the flame retardant is not mixed with cyanate even if it is mixed in a range of 300 ° C or less. The cyanooxy group of the compound is reacted, but is directly contained in the printed wiring substrate resin composition in a form of dispersion or dissolution. This reaction does not include the reaction of the flame retardant in the case where the resin composition is heated and burned. Usually, the resin composition for a printed wiring board, and a varnish, a prepreg, a metal-clad laminate, a printed wiring board, or the like using the same, are used and used. It is carried out in the range of 300 ° C or less.

The filler to be blended as needed is not particularly limited, and examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, calcium carbonate, calcium silicate, barium sulfate, talc, clay, and magnesium oxide. , alumina, cerium oxide, iron oxide, titanium oxide, aluminum nitride, tantalum nitride, boron nitride, mica, glass, quartz, mica, and the like. Further, in order to impart a flame retardant effect, a metal hydroxide such as magnesium hydroxide or aluminum hydroxide is preferably used. However, it is not limited to these. Further, two or more kinds may be used in combination. Among these inorganic fillers, cerium oxide such as molten cerium oxide or crystalline cerium oxide is preferred because it is low in cost and excellent in electrical reliability. In the epoxy resin composition of the present invention, the inorganic filler is used in an amount of usually 5% by weight to 70% by weight, preferably 10% by weight to 60% by weight, more preferably 15% by weight to 60% by weight. The range of %. If the amount of the inorganic filler used is too small, the effect of flame retardancy may not be obtained, and the modulus of elasticity may be lowered. If the amount of the inorganic filler used is too large, it may be formed into a varnish dissolved in a sealed solution. The filler precipitates and a homogeneous molded body cannot be obtained.

Further, the shape, particle diameter, and the like of the inorganic filler are not particularly limited, but are usually 0.01 to 50 μm, preferably 0.1 to 15 μm.

In the epoxy resin composition of the present invention, a coupling agent may be blended in order to improve the adhesion of the glass cloth or the inorganic filler to the resin component. As the coupling agent, any of the previously known ones can be used, and examples thereof include vinyl alkoxy decane, alkyl alkoxy decane, styryl alkoxy decane, and methacryl oxiran alkoxy decane. Various alkoxydecane compounds such as propylene methoxy alkoxy decane, amino alkoxy decane, mercapto alkoxy decane, isocyanoxy alkoxy decane, alkoxy titanium compounds, aluminum chelates Wait. These may be used alone or in combination of two or more. Regarding the method of adding the coupling agent, the surface of the inorganic filler can be previously prepared by using a coupling agent. After the treatment, the resin is kneaded, and the coupling agent may be mixed in the resin, and then the inorganic filler may be kneaded.

An organic solvent may be added to the epoxy resin composition of the present invention to prepare a varnish-like composition (hereinafter, simply referred to as varnish). Examples of the solvent to be used include γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N. - a guanamine solvent such as dimethylimidazolidone; an anthracene such as tetramethylene hydrazine; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether single ethyl An ether solvent such as an acid ester or propylene glycol monobutyl ether; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone; or an aromatic solvent such as toluene or xylene. The solvent is used in the range of 10 to 80% by weight, preferably 20 to 70% by weight, based on the solid content of the obtained varnish.

Further, a known additive may be blended into the epoxy resin composition of the present invention as needed. Specific examples of the additives which can be used include polybutadiene and modified substances thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimine, fluororesin, and Malay. A quinone imine compound, a cyanate ester compound, a polyoxyxanthene gel, a polyoxygenated oil, and a coloring agent such as carbon black, phthalocyanine blue, or phthalocyanine green.

The resin sheet of the present invention will be described.

The resin sheet using the epoxy resin composition of the present invention has a thickness of the varnish after drying by various coating methods such as a gravure coating method, a screen printing method, a metal mask method, and a spin coating method known per se. It is obtained by applying it to a planar support at a specific thickness, for example, 5 to 100 μm, and then drying it. However, the coating method used depends on the type, shape, size, thickness of the coating, and thickness of the support. The heat resistance of the body is appropriately selected. Examples of the planar support include polyamine, polyamidiamine, polyarylate, polyethylene terephthalate, and poly Various polymers such as butylene terephthalate, polyether ketone, polyether oxime, polyether ether ketone, polyketone, polyethylene, polypropylene, Teflon (registered trademark), and/or copolymers thereof The produced film or metal foil such as copper foil.

After coating, it is dried to obtain a sheet-like composition (resin sheet of the present invention), but the sheet may be cured by further heating the sheet. Further, it is also possible to perform the solvent drying and hardening step in one heating.

In the epoxy resin composition of the present invention, both sides or one side of the support may be coated and heated by the above method to form a layer of a cured product on both sides or a single side of the support. Moreover, the laminated body can also be produced by bonding the adherend before bonding and hardening it.

Further, the resin sheet of the present invention may be used as a back sheet by peeling off from the support, or may be brought into contact with the object to be bonded, and pressure and heat may be applied as needed to cause hardening and subsequent bonding.

The prepreg of the present invention will be described.

The prepreg system of the present invention is obtained by impregnating the above resin composition with a fibrous substrate. Thereby, a prepreg excellent in heat resistance, low expansion property, and flame retardancy can be obtained. Examples of the fiber base material include glass fiber substrates such as glass woven fabrics, glass nonwoven fabrics, and cellophane; and woven fabrics composed of synthetic fibers such as paper, polyarsenamide, polyester, aromatic polyester, and fluororesin. Or non-woven fabric; woven fabric, non-woven fabric, mat (mat) composed of metal fiber, carbon fiber, mineral fiber, and the like. These substrates may be used singly or in combination. Among these, a glass fiber substrate is preferred. Thereby, the rigidity and dimensional stability of the prepreg can be improved.

The glass fiber substrate preferably contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.

A method of impregnating the above resin composition with the above fibrous substrate, for example, The method of immersing a base material in a resin varnish, the method of apply|coating by various coating machines, the method of carrying out by the sprayer, etc. are mentioned. Among these, a method of immersing the substrate in a resin varnish is preferred. Thereby, the impregnation property of a resin composition with respect to a base material can be improved. Further, in the case where the substrate is immersed in a resin varnish, a usual impregnation coating apparatus can be used.

For example, the epoxy resin composition of the present invention is impregnated into a substrate such as a glass cloth either directly or in the form of a varnish dissolved or dispersed in a solvent, and is usually dried at 80 to 200 ° C (in which, In the case of using a solvent, it is dried at a temperature at which the solvent is volatilized at a temperature of 2 to 30 minutes, preferably 2 to 15 minutes, thereby obtaining a prepreg.

The metal clad laminate of the present invention will be described.

The laminated board used in the present invention is obtained by subjecting the above-mentioned prepreg to heat and pressure molding. Thereby, a metal-clad laminate excellent in heat resistance, low expansion property, and flame retardancy can be obtained. When it is a prepreg, the metal foil is superposed on the upper or lower sides or on one side. Further, two or more prepregs may be laminated. When two or more prepregs are laminated, a metal foil or a film is superposed on the lowermost side or the single side of the outermost layer of the prepreg of the laminate. Next, a metal-clad laminate can be obtained by heat-press molding the prepreg and the metal foil. The temperature at which the heating is carried out is not particularly limited, but is preferably 120 to 220 ° C, and particularly preferably 150 to 200 ° C. The pressure for pressurization described above is not particularly limited, but is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa. Further, post-hardening may be performed at a temperature of 150 to 300 ° C in a high temperature bath or the like as needed.

The printed wiring board of the present invention will be described.

In the printed wiring board, the above-mentioned metal-clad laminate is used as the inner layer circuit board. The circuit is formed on one or both sides of the metal-clad laminate. The through holes may be formed by drilling processing or laser processing as the case may be, and electrical connection between the two sides may be achieved by plating or the like.

The commercially available or resin sheet of the present invention or the prepreg of the present invention may be superposed on the inner layer circuit board and subjected to heat and pressure molding to obtain a multilayer printed wiring board.

Specifically, the insulating layer side of the resin sheet is overlapped with the inner layer circuit board, and vacuum heat press molding is performed using a vacuum pressure type bonding apparatus or the like, and thereafter, the insulating layer is formed by a hot air drying device or the like. Obtained by heat hardening.

Here, the conditions for performing the heat and pressure molding are not particularly limited, and may be carried out at a temperature of 60 to 160 ° C and a pressure of 0.2 to 3 MPa as an example. Further, the conditions for the heat curing are not particularly limited, and as an example, the temperature can be carried out at a temperature of 140 to 240 ° C for 30 to 120 minutes.

Alternatively, the prepreg of the present invention may be obtained by superposing the prepreg of the present invention on an inner layer circuit board, and performing heat and pressure molding using a flat plate press or the like. Here, the conditions for performing the heat and pressure molding are not particularly limited, and examples thereof can be carried out at a temperature of 140 to 240 ° C and a pressure of 1 to 4 MPa. In such heat and pressure molding by a flat plate press or the like, heat-press molding is performed while heat-hardening the insulating layer.

Moreover, the method for producing a multilayer printed wiring board according to the present invention includes the steps of superimposing the resin sheet or the prepreg of the present invention on a surface of an inner layer circuit substrate on which an inner layer circuit pattern is formed and continuously laminating, and borrowing The step of forming a conductor circuit layer by a semi-additive method.

In the hardening of the insulating layer formed of the resin sheet or the prepreg of the present invention, in order to facilitate the subsequent removal of the laser irradiation and the resin residue, the desmear property is improved, and it is set in advance. The case of a semi-hardened state. Moreover, the insulating layer of the first layer is heated at a temperature lower than a normal heating temperature, thereby partially hardening (semi-hardening) on the insulating layer, thereby forming a layer or even a plurality of insulating layers to insulate the semi-hardened layer. The layer is again heat-hardened to the extent that it is practically problem-free, whereby the adhesion between the insulating layers and between the insulating layer and the circuit can be improved. The The temperature of the semi-hardening in the case is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 180 ° C. Further, in the subsequent step, the laser is irradiated to form an opening in the insulating layer, but the substrate must be peeled off before. Regarding the peeling of the substrate, there is no particular problem even if it is carried out at any time after the formation of the insulating layer, before the heat curing, or after the heat curing.

In the inner layer circuit board used for obtaining the multilayer printed wiring board, for example, a specific conductor circuit can be formed on both surfaces of the copper clad laminate by etching or the like, and the conductor circuit portion can be blackened. By.

The resin residue or the like after the laser irradiation is preferably removed by using an oxidizing agent such as permanganate or dichromate.

Further, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by metal plating can be improved.

Second, an outer circuit is formed. The method of forming the outer layer circuit is to form a connection between the insulating resin layers by metal plating, and to form an outer layer circuit pattern by etching. The multilayer printed wiring board can be obtained in the same manner as in the case of using a resin sheet or a prepreg.

Further, in the case of using a resin sheet or a prepreg having a metal foil, a circuit is formed by etching in order to use it as a conductor circuit without peeling off the metal foil. In this case, when the insulating resin sheet with the base material of the thick copper foil is used, it becomes difficult to form a fine pitch in the subsequent circuit pattern formation. Therefore, an extremely thin copper foil of 1 to 5 μm is used, or A case where a copper foil of 12 to 18 μm is thinned by etching to a half etching of 1 to 5 μm is performed.

Further, an insulating layer may be laminated and formed in the same manner as described above. In the design of the multilayer printed wiring board, after the circuit is formed on the outermost layer, a solder resist layer is formed. The method for forming the solder resist layer is not particularly limited, and is formed, for example, by the following method: A method in which a dry film type solder resist layer is laminated (laminated), exposed and developed, or formed by exposing and developing a liquid resist. In the case where the obtained multilayer printed wiring board is used for a semiconductor device, a connection electrode portion is provided in order to mount the semiconductor element. The electrode portion for connection can be appropriately covered with a metal film such as gold plating, nickel plating, or solder plating. A multilayer printed wiring board can be produced by the above method.

Next, a semiconductor device of the present invention will be described.

A semiconductor element having solder bumps is mounted on the multilayer printed wiring board obtained as described above, and is connected to the multilayer printed wiring board via solder bumps. Then, a liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device. The solder bump is preferably made of an alloy composed of tin, lead, silver, copper, tantalum or the like.

In the method of connecting a semiconductor element and a multilayer printed wiring board, an IR reflow device is used after the connection electrode portion on the substrate is aligned with the solder bump of the semiconductor element using a flip chip bonding machine or the like. The hot plate and other heating means heat the solder bumps to a temperature higher than the melting point, and the multilayer printed wiring board and the solder bumps are fusion-bonded to be connected. In addition, in order to improve the connection reliability, a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board. The flux may be applied to the surface of the solder bump and the connection electrode portion on the multilayer printed wiring board before the bonding step, thereby improving connection reliability.

The substrate is used for a mother board, a mesh substrate, a package substrate, or the like. In particular, it is useful as a package substrate as a thin layer substrate for a single-sided sealing material. Further, in the case of being used as a semiconductor sealing material, examples of the semiconductor device obtained by blending thereof include DIP (Dual inline package) and QFP (Quad Flat Package). BGA (Ball Grid Array), CSP (Chip Scale Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (TQFP) Thin Quad Flat Package, thin quad flat package).

Example

The characteristics of the present invention will be further specifically described below by way of Synthesis Examples and Examples. The materials, processing contents, processing procedures, and the like described below can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention should not be construed as being limited by the specific examples shown below.

Here, the measurement conditions of the respective physical property values are as follows.

. Epoxy equivalent

The measurement was carried out by the method described in JIS K-7236, and the unit was g/eq.

. Softening Point

The measurement was performed in accordance with the method of JIS K-7234, and the unit was °C.

. Elastic modulus (DMA)

Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980

Measuring temperature range: -30~280°C

Heating rate: 2 ° C / min

Test piece size: use a cut of 5mm × 50mm

Tg: The peak point of Tan-δ in the DMA measurement is set to Tg.

Synthesis Example 1

Nitrogen flushing was carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device. A phenol resin represented by the following formula manufactured according to WO2007/007827 ((a)/(b)=1.3n=0.5 (calculated from the molecular weight distribution of GPC and hydroxyl equivalent)) hydroxyl equivalent of 134 g/eq. softening point 93 was added. °C) 134 parts, 450 parts of epichlorohydrin, and 54 parts of methanol were dissolved under stirring, and the temperature was raised to 70 °C. Then, 42.5 parts of flaky sodium hydroxide was added in portions over 90 minutes, and further reacted at 70 ° C for 1 hour. After completion of the reaction, the mixture was washed with water and the salt was removed. Then, a solvent such as an excess of epichlorohydrin was distilled off under reduced pressure using a rotary evaporator with respect to the obtained organic layer. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and 17 parts of a 30% by weight aqueous sodium hydroxide solution was added thereto with stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and rotation was used. In the evaporator, methyl isobutyl ketone or the like was distilled off from the obtained solution under reduced pressure, whereby 195 parts of the epoxy resin (EP1) represented by the formula (1) was obtained. The obtained epoxy resin has an epoxy equivalent of 211 g/eq., a softening point of 71 ° C, and a melt viscosity of 150 ° C (ICI melt viscosity cone #1) of 0.34 Pa. s.

Example 1

211 parts of 2,2-bis(4-cyanooxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as BisA-OCN) was mixed with 211 parts of the epoxy resin (EP1) obtained in Synthesis Example 1. Further, 356 parts of methyl ethyl ketone was added, and the mixture was stirred at 40 ° C for 10 minutes to obtain an appropriate viscosity. Preparation. To the preparation liquid, 6 parts of an imidazole catalyst (manufactured by 2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was further added, and the mixture was further stirred at 40 ° C for 5 minutes to obtain a composition for a resin sheet and/or a prepreg as a preparation liquid (A). This preparation liquid was impregnated into a glass cloth 1037 (manufactured by Asahi Kasei) cut into an A4 size, and the excess resin liquid was removed, and then dried at 180 ° C for 5 minutes to obtain a prepreg. The appearance of the smoothness of the surface containing the obtained prepreg was not problematic. It becomes a sheet of light reddish brown in color. It was confirmed that the DSC-based heat generation peak was 129 ° C, which was a hardenable sheet.

Example 2

Five sheets of the prepreg obtained in Example 1 were stacked, and formed by pressurization with a hot plate at a pressure of 15 minutes and 10 kg/cm ² to obtain a substrate sample. The obtained substrate sample was further cured at 175 ° C for 1 hour and then cured at 220 ° C for 1 hour, whereby a sufficiently hardened laminate was obtained. The hardened physical properties were measured on the obtained laminate. Regarding the obtained cured sheet, the peak of heat generation based on DSC was not confirmed at 200 ° C or lower, and it was judged that it was sufficiently hardened.

Example 3

The preparation liquid (A) was applied to a 35 μm copper foil (rough surface), and dried at 175 ° C for 5 minutes to obtain a copper-clad resin sheet.

Example 4

The obtained copper-clad resin sheet was formed by pressurization with a hot plate at a pressure of 15 minutes and 10 kg/cm ² to obtain a substrate sample. The obtained substrate sample was further cured at 175 ° C for 1 hour, and then cured at 220 ° C for 1 hour, whereby a copper clad laminate was obtained.

Example 5

The copper-clad resin sheet obtained in Example 3 was superposed on the two sheets of the prepreg obtained in Example 1, and was formed by a hot plate press at a pressure of 15 minutes and 10 kg/cm ² . Copper clad laminate. The obtained substrate sample was further cured at 175 ° C for 1 hour and then cured at 220 ° C for 1 hour, whereby a sufficiently hardened laminate was obtained.

Example 6

The prepreg obtained in Example 1 was directly formed by pressurization with a hot plate at a pressure of 15 minutes and 10 kg/cm ² to obtain a substrate sample. The obtained substrate sample was further cured at 175 ° C for 1 hour, and then cured at 220 ° C for 1 hour to obtain a sufficiently cured printed wiring board. The hardened physical properties were measured on the obtained substrate. The results are shown in Table 1.

In addition, as for the obtained cured sheet, the peak of heat generation based on DSC was not confirmed at 200 ° C or lower, and it was judged that it was sufficiently hardened.

Comparative example 1

In the first embodiment, in place of BisA-OCN, the phenol resin for comparison (KAYAHARD, GPH-103, hereinafter referred to as "PN1") was changed to 231 parts, and was set to 120 in the solvent drying step at the time of preparation of the prepreg. A prepreg was produced by the same operation except that the temperature was the same as in Example 6, and a printed wiring board sheet was produced. The results are shown in Table 1.

. PN1: a biphenyl aralkyl type phenol having a hydroxyl equivalent of 236 and a softening point of 102 ° C (manufactured by Nippon Kayaku Co., Ltd., KAYAHARD GPH-103)

. BisA-OCN: 2,2-bis(4-cyanooxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.)

It is confirmed from Table 1 that the printed wiring board composed of the epoxy resin composition of the present invention has higher heat resistance than that of Comparative Example 1, and has a very high modulus of elasticity at a high temperature.

The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications can be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on August 1, 2014 (Japanese Patent Application No. 2014-157630), the entire contents of which is incorporated by reference. Again, all references cited herein are hereby incorporated by reference in their entirety.

[Industrial availability]

The epoxy resin composition of the present invention is a material useful for producing a laminated board such as a printed wiring board or a build-up board because the cured product has high heat resistance and excellent high bending modulus in a high temperature region.

Claims (9)

An epoxy resin composition containing an epoxy resin represented by the following formula (1) and a cyanate compound having two or more cyanooxy groups in the molecule as an essential component. (In the formula, the ratio of (a) to (b) is (a)/(b) = 1 to 3; G represents a glycidyl group; and n is a repeating number of 0 to 5). A prepreg obtained by impregnating a fiber base material with the epoxy resin composition of claim 1 of the patent application. The prepreg of claim 2, wherein the fibrous substrate is a glass fiber substrate. The prepreg according to claim 3, wherein the glass fiber substrate contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass. A metal-clad laminate having a metal foil in at least one area layer of the prepreg according to any one of claims 2 to 4. A resin sheet obtained by forming an insulating layer composed of an epoxy resin composition of the first application of the patent application on a film or a metal foil. A printed wiring board obtained by using a metal-clad laminate of the fifth application of the patent application for an inner layer circuit board. A printed wiring board obtained by hardening a prepreg according to any one of claims 2 to 4 or a resin sheet of claim 6 of the patent application. A semiconductor device in which a semiconductor element is mounted on a printed wiring board of claim 7 or 8.