CN106661200B - Epoxy resin compositions, resin sheets, prepregs, metal-clad laminates, printed wiring boards, semiconductor devices - Google Patents

Abstract

The present invention aims to provide an epoxy resin composition, and resin sheets, metal-clad laminates, printed wiring substrates, and semiconductor devices using the epoxy resin composition, wherein the cured epoxy resin composition has high heat resistance, low water absorption, and low dielectric constant. The epoxy resin composition of the present invention uses epoxy resin and amine curing agent as essential components as shown in the following general formula (1), (wherein, the ratio of (a) to (b) is (a)/(b) = 1 to 3, G represents glycidyl group; n is the repetition number and is 0 to 5).

Description

Epoxy resin composition, resin sheet, prepreg and metal-clad laminate, printed wiring Substrates, semiconductor devices

technical field

The present invention relates to an epoxy resin composition providing a cured product excellent in heat resistance and water resistance, a prepreg obtained by impregnating a fiber base material with the epoxy resin composition, a resin sheet, and a metal-clad laminate boards, printed wiring boards, and semiconductor devices.

Background technique

Epoxy resin compositions are widely used in the fields of electrical/electronic parts, structural materials, adhesives, coatings, etc. due to their excellent workability and their excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance), etc. widely used.

However, in recent years, in the electrical/electronic field, along with its development, including the high purity of the resin composition, moisture resistance, adhesion, dielectric properties, and fillers (inorganic or organic fillers) are required to be highly Further improvement of various properties such as lowering of the viscosity of filling and improvement of reactivity for shortening the molding cycle. In addition, as structural materials, materials that are lightweight and excellent in mechanical properties are required for aerospace materials, recreational and sports equipment applications, and the like. In the field of semiconductor encapsulation in particular, in the substrate (the substrate itself or its surrounding material), the required characteristics are increasing year by year, for example, the high Tg of the surrounding material due to the increase in the driving temperature of the semiconductor is required.

In general, when the Tg of the epoxy resin is increased, the water absorption rate increases (Non-Patent Document 1). This is due to the increase in crosslink density. However, in order to increase the Tg of semiconductor peripheral materials that require low moisture absorption, it is imperative to develop resins having the opposite properties.

On the other hand, Patent Document 1 discloses a phenol novolak resin having a biphenyl skeleton and a phenol novolak-type epoxy resin obtained by epoxidizing the same, and describes its usefulness for semiconductor encapsulant applications.

However, this epoxy resin has both high heat resistance and flame retardancy in combination with a phenol resin, but has a high water absorption rate and has a problem when used for electronic materials requiring very high reliability.

In addition, there is no description of the properties of the compositions containing these epoxy resins and amine-based curing agents, and no description of their usefulness for printed wiring board applications.

prior art literature

Patent Literature

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

Non-patent literature

Non-Patent Document 1: Ichiro Oguru, "Relationship between chemical structure and properties of epoxy resins", DIC Technical Review No. 7, Japan, 2001, p.7

SUMMARY OF THE INVENTION

The problem to be solved by the invention

The present invention is a result of studies in order to solve such a problem, and an object of the present invention is to provide an epoxy resin composition, and a prepreg, resin sheet, metal-clad laminate, printing using the epoxy resin composition In a wiring board and a semiconductor device, the cured product of the epoxy resin composition has high heat resistance, water absorption, and low dielectric constant.

means to solve the problem

The present inventors have completed the present invention as a result of intensive studies in order to solve the above-mentioned problems.

That is, the present invention provides:

(1)

An epoxy resin composition, wherein the epoxy resin composition is an epoxy resin represented by the following general formula (1) and an amine curing agent as essential components,

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

(2)

A prepreg obtained by impregnating a fiber base material with the epoxy resin composition described in (1) above;

(3)

The prepreg according to (2) above, wherein the fiber base material is a glass fiber base material;

(4)

The prepreg according to (3) above, 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;

(5)

A metal-clad laminate obtained by laminating metal foil on at least one surface of the prepreg described in (2) to (4) above;

(6)

A resin sheet obtained by forming an insulating layer comprising the epoxy resin composition described in (1) above on a film or on a metal foil;

(7)

A printed wiring board obtained by using the metal-clad laminate described in (5) above for an inner-layer circuit board;

(8)

A printed wiring board obtained by curing the prepreg described in any one of (2) to (4) above or the resin sheet described in (6) above;

(9)

A semiconductor device obtained by mounting a semiconductor element on the printed wiring board according to the above (7) or (8).

Invention effect

The epoxy resin composition of the present invention provides a cured product that can achieve both high heat resistance and water resistance in the cured product, and is therefore an extremely useful material for producing laminates such as printed wiring boards and build-up boards.

According to the present invention, an epoxy resin composition and a prepreg, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device using the epoxy resin composition, and the curing of the epoxy resin composition can be provided. It has high heat resistance, water absorption and low dielectric constant.

Description of drawings

FIG. 1 is a graph showing the relationship between heat resistance and water absorption characteristics of a cured product of an epoxy resin composition.

Detailed ways

Hereinafter, the epoxy resin composition of the present invention will be described.

The epoxy resin composition of the present invention includes, as an epoxy resin, a compound represented by the following formula (1) (hereinafter, referred to as "epoxy resin of formula (1)") and an amine-based curing agent as essential components.

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

The epoxy resin of formula (1) used in the present invention can be obtained from Japanese Patent Laid-Open No. 2011-252037, Japanese Patent Laid-Open No. 2008-156553, Japanese Patent Laid-Open No. 2013-043958, International Publication WO2012/053522, and WO2007 The epoxy resin synthesized by the method described in /007827 can be synthesized by any method as long as it has the structure of the above formula (1).

Especially, in this invention, the ratio (polyfunctionalization rate) of the said formula (a) and the said formula (b) is (a)/(b)=1-3 epoxy resins are used. When the structure of (a) is long, the heat resistance is improved, but the water absorption property is not only deteriorated, but also becomes brittle and hard. Therefore, the epoxy resin of the polyfunctionalization rate in the said range is used.

The softening point (ring and ball method) of the epoxy resin to be used is preferably 50°C to 150°C, more preferably 52°C to 100°C, and particularly preferably 52°C to 95°C. When the softening point is 50° C. or lower, stickiness may be severe, handling may be difficult, and a problem may arise in productivity. In addition, when the softening point is 150° C. or higher, it is a temperature close to the molding temperature, and fluidity at the time of molding may not be ensured, which is not preferable.

The epoxy equivalent of the epoxy resin used is preferably 180 g/eq. to 350 g/eq. Particularly preferably, it is 190 g/eq. to 300 g/eq. When the epoxy equivalent is less than 180 g/eq., since there are too many functional groups, the cured product after curing may have a high water absorption rate and become brittle. When the epoxy equivalent exceeds 350 g/eq., it is considered that the softening point becomes very large, or the epoxidation does not proceed completely, and the amount of chlorine becomes very large, which is not preferable.

In addition, 200 ppm - 1500 ppm are preferable as total chlorine (hydrolysis method), and, as for the chlorine content of the epoxy resin used by this invention, it is especially preferable that it is 200 ppm - 900 ppm. According to the standards of JPCA, it is expected that the chlorine content of the epoxy monomer also does not exceed 900 ppm. In addition, when there is a large amount of chlorine, electrical reliability may be affected accordingly, which is not preferable. When the amount of chlorine is less than 200 ppm, an excessive purification step may be required, which may cause problems in productivity, which is not preferable.

In addition, the melt viscosity at 150 degreeC of the epoxy resin used by this invention becomes like this. Preferably it is 0.05 Pa.s - 5 Pa.s, Especially preferably, it is 0.05 Pa.s - 2.0 Pa.s. When the melt viscosity is higher than 5 Pa·s, a problem may arise in fluidity, and a problem may arise in flowability or embedment during pressurization. When it is less than 0.05 Pa·s, since the molecular weight is too small, the heat resistance may be insufficient.

The ratio of (a) to (b) in the above formula is (a)/(b)=1-3. That is, it is characterized in that more than half is in the form of a glycidyl ether of a resorcinol structure. This ratio is important for precipitation of crystals and improvement of heat resistance, and it is preferable that (a)/(b) exceed 1. In addition, by setting (a)/(b) to be 3 or less, the amount of the glycidyl ether form of the resorcinol structure is limited, whereby the water absorption rate and the toughness can be improved.

In the above formula, n is a repeating unit and is 0-5. The flowability or fluidity when made into a prepreg or a resin sheet is controlled by making n not more than 5. When it exceeds 5, a problem arises not only in fluidity, but also in solubility in a solvent.

The solubility of the epoxy resin used in the present invention in a solvent is important. For example, when biphenyl aralkyl type epoxy resins having the same skeleton are used together, these resins also require solubility in solvents such as methyl ethyl ketone, toluene, and propylene glycol monomethyl ether.

In the present invention, especially the solubility in methyl ethyl ketone is important, and it is required that crystals do not precipitate for 2 months or more under conditions such as 5°C and room temperature. Also related to the ratio of (a)/(b), when the value of (a) is large, crystals are likely to be precipitated, so it is important that (a)/(b) be 1 or more.

The epoxy resin composition of the present invention contains an amine-based curing agent as an essential component. Examples of amine-based curing agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, Aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) , or the polycondensation of substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), etc. The obtained aniline resin etc. are not limited to these.

A particularly preferable amine-based curing agent is a bifunctional or higher amine compound, and is preferably a resin having a structure represented by the following formula.

(In the formula, n is the number of repetitions and is 1 to 10).

The amine-based curing agents used in the present invention each take the form of crystals or resins.

In the case of a crystal, the melting point is preferably 35°C to 200°C, and particularly preferably 40°C to 185°C. Unlike the softening point, the melting point is also related to solubility in other resins, so it does not necessarily have to be a temperature lower than the molding temperature like a resin.

In the case of resin, the softening point (ring and ball method) of 50°C to 150°C is preferable, and 50°C to 100°C is particularly preferable. In the case of resins, amine-based curing agents with a softening point of 50°C or lower may cause problems of stickiness, so it is not preferable. It cannot be completely formed, and the solvent cannot be completely removed.

The functional group equivalent of the amine compound is preferably 60 g/eq. to 600 g/eq. (measurement by potentiometric titration). When the active hydrogen equivalent is 60 or less, problems may arise in the water absorption rate and toughness of the cured product. When it exceeds 600, it may become difficult to maintain heat resistance.

In the epoxy resin composition of this invention, it is preferable that the usage-amount of an amine type hardening|curing agent is 0.2 equivalent - 0.6 equivalent in the amine equivalent of an amine compound with respect to 1 equivalent of epoxy groups of an epoxy resin. It is especially preferable that it is 0.3 equivalent - 0.55 equivalent. When it is less than 0.2 equivalent and when it exceeds 0.6 equivalent with respect to 1 equivalent of an epoxy group, since there exists a possibility that hardening may become incomplete and favorable hardening property cannot be acquired, it is unpreferable.

The epoxy resin composition of the present invention may contain a curing accelerator. Specific examples of curing accelerators that can be used include formic acid, acetic acid, lactic acid, glycolic acid, n-butyric acid, isobutyric acid, propionic acid, caproic acid, caprylic acid, n-heptanoic acid, monochloroacetic acid, and dichloroacetic acid , trichloroacetic acid, thioglycolic acid, phenol, m-cresol, p-chlorophenol, p-nitrophenol, 2,4-dinitrophenol, o-aminophenol, p-aminophenol, 2,4,5-trichlorophenol, Resorcinol, hydroquinone, catechol, phloroglucinol, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid, salicylic acid, Phthalic acid, isophthalic acid, terephthalic acid, malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid, citric acid and other acids; monoethanolamine, diethanolamine, triethanolamine amines such as thiophenol, 2-mercaptoethanol, sulfur-containing species; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl) tertiary amines such as phenol and 1,8-diazabicyclo[5.4.0]undec-7ene; phosphines such as triphenylphosphine; metal compounds such as tin octoate, etc. 0.1 weight part - 5.0 weight part of hardening accelerators can be used as needed with respect to 100 weight part of epoxy resins.

In the epoxy resin composition of the present invention, other epoxy resins may be used in combination. Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the formula (1) 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, etc.) , alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthalene formaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) polycondensate; the above phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl , butadiene, isoprene, etc.) polymers; polycondensates of the above-mentioned phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ; The condensation polymer of above-mentioned phenols and aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.); Above-mentioned phenols and aromatic dichloromethyls (a, a'-dichloroxylene, dichloromethane, etc.) base biphenyl, etc.) polycondensates; the above-mentioned phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins obtained by glycidylation of the polycondensates of the above bisphenols and various aldehydes or alcohols, etc. , glycidyl ester epoxy resin, etc., however, as long as it is a commonly used epoxy resin, it is not limited to these. These epoxy resins may be used alone, or two or more of them may be used.

When mix|blending the epoxy resin composition of this invention, a conventionally well-known hardening|curing agent can be used together. As another curing agent which can be used together, an acid anhydride type compound, an amide type compound, a phenol type compound, a carboxylic acid type compound, etc. are mentioned, for example. Specific examples of the curing agent that can be used include amide compounds such as dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic tetrakis Acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other acid anhydrides Compounds; Bisphenol A, Bisphenol F, Bisphenol S, Bisphenol Fluorene, Terpene Diphenol, 4,4'-Biphenol, 2,2'-Biphenol, 3,3',5,5 '-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)methane, 1, 1,2,2-Tetrakis(4-hydroxyphenyl)ethane; as phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, ethyl Novolak resins of condensation polymers of aldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, furfural; as phenol or cresol with bis(hydroxymethyl)benzene, Reaction products of bis(methoxymethyl)benzene or bis(halomethyl)benzene, or phenol or cresol with bischloromethylbiphenyl, dimethoxymethylbiphenyl or dihydroxymethylbiphenyl The reaction product of phenol, or the phenol aralkyl resin of the reaction product of phenol and benzene diisopropanol, benzene diisopropanol dimethyl ether or benzene bis (chloroisopropane), and their modified products; tetrabromobisphenol Halogenated bisphenols such as A; phenolic compounds such as condensates of terpenes and phenols, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, etc., but not limited to these. These curing agents may be used alone, or two or more of them may be used.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive phosphorus-containing compound or an additive-type phosphorus-containing compound. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, cresyl diphenyl phosphate, and cresyl phosphate-2,6- bis(xylyl) ester, 1,3-phenylene bis(bis(xylyl) phosphate), 1,4-phenylene bis(bis(xylyl) phosphate), 4,4' - Phosphate compounds such as biphenyl (bis(xylyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-di Hydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphines; phosphorus-containing epoxy compounds obtained by reacting epoxy resins with the active hydrogen of the phosphines, red phosphorus etc., preferably phosphoric acid esters, phosphines or phosphorus-containing epoxy compounds, particularly preferably 1,3-phenylene bis(bis(xylyl) phosphate), 1,4-phenylene bis(bis(bis(dimethyl) phosphate) tolyl) ester), 4,4'-biphenyl (bis(xylyl) phosphate), or a phosphorus-containing epoxy compound.

However, due to environmental problems and concerns about electrical properties, the usage-amount of the phosphate-based compound as described above is preferably phosphate-based compound/epoxy resin≤0.1 (weight ratio). More preferably, it is 0.05 or less. Particularly preferably, the phosphorus-containing compound may not be added except as a curing accelerator.

The epoxy resin composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, and titanium oxide. , Aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, mica, etc. In addition, in order to impart a flame retardant effect, metal hydroxides such as magnesium hydroxide and aluminum hydroxide are also preferably used. But not limited to these. Moreover, you may mix and use 2 or more types. Among these inorganic fillers, silicas such as fused silica and crystalline silica are preferred because of their low cost and good electrical reliability.

In the epoxy resin composition of the present invention, the use amount of the inorganic filler is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 15 to 60% by weight in terms of internal ratio . When the amount is too small, the linear expansion may increase, and warpage may become a problem, or rigidity may not be generated due to the progress of thinning of the substrate, which may cause a problem in the process. In addition, if too much, the homogeneity may be lost due to sedimentation of the filler, or the embeddability of the substrate may be deteriorated, and the adhesion to the metal may be deteriorated. Therefore, when forming as a substrate, peeling or breakdown occurs There is a high possibility of adverse effects on electrical characteristics such as voltage.

In addition, the shape, particle diameter, etc. of the inorganic filler are not particularly limited, but are usually inorganic fillers with particle diameters of 0.01 μm to 50 μm, preferably 0.1 μm to 15 μm.

In order to improve mold release from a mold during molding, a mold release agent may be blended in the epoxy resin composition of the present invention. As the release agent, any of conventionally known release agents can be used, and examples thereof include ester waxes such as carnauba wax and montan wax; fatty acids such as stearic acid and palmitic acid, and their metal salts; oxidized Polyolefin waxes such as polyethylene and non-oxidized polyethylene, etc. These release agents may be used alone or in combination of two or more. The blending amount of these release agents is preferably 0.5% by weight to 3% by weight with respect to all organic components. When the content is too small, the mold release from the mold may be poor, and when it is too large, the adhesion to the base material or the like may be poor.

In order to improve the adhesiveness of an inorganic filler and a resin component, a coupling agent may be mix|blended with the epoxy resin composition of this invention. As the coupling agent, any conventionally known coupling agent can be used, and examples thereof include vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, and methacryloxy Various alkoxysilane compounds such as alkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxysilane, alkoxytitanium compounds, aluminum Chelates, etc. These coupling agents may be used alone or in combination of two or more. As for the method of adding the coupling agent, the surface of the inorganic filler may be treated with the coupling agent in advance and then kneaded with the resin, or the coupling agent may be mixed with the resin and then the inorganic filler may be kneaded.

An organic solvent can be added to the epoxy resin composition of this invention, and it can be set as a varnish-like composition (henceforth abbreviated as varnish). As a solvent to be used, for example, γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylacetamide can be mentioned. Amide solvents such as imidazolidinone; sulfones such as sulfolane; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, etc. ketone solvents; methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and other ketone solvents; toluene, xylene and other aromatic solvents. The solvent is used within the range of usually 10% by weight to 80% by weight, preferably 20% by weight to 70% by weight, of the solid content concentration other than the solvent in the obtained varnish.

Moreover, a well-known additive can be mix|blended with the epoxy resin composition of this invention as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, and fluorine-containing resins. , maleimide compounds, cyanate ester compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, phthalocyanine green, etc.

The resin sheet of this invention is demonstrated.

The resin sheet using the epoxy resin composition of the present invention is obtained by applying the above-mentioned varnish by various coating methods such as gravure coating, screen printing, metal mask method, and spin coating methods known per se. It is clothed on a planar support so that the thickness after drying is a predetermined thickness, for example, 5 μm to 100 μm, and then dried to obtain; which coating method is used depends on the type, shape, size of the support The heat resistance of the support and the like are appropriately selected.

Examples of the planar support include polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ketone, polyether acyl Films made of various polymers such as imine, polyetheretherketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark) and/or copolymers thereof, or metal foils such as copper foil, etc.

A sheet-like composition (resin sheet of the present invention) may be obtained by drying after application, but a sheet-like cured product may be obtained by further heating the sheet. In addition, a single heating may serve as both solvent drying and curing steps.

The epoxy resin composition of the present invention can be applied to both sides or one side of the above-mentioned support by the method described above and heated to form a layer of a cured product on both sides or one side of the support. In addition, a laminated body may be produced by bonding an adherend and curing it before curing.

Moreover, the resin sheet of this invention can also be used as an adhesive sheet by peeling from a support body, and it can make it come into contact with a to-be-adhered body, pressure and heat can be applied as needed, and it can be hardened and adhered.

The prepreg of the present invention will be described.

The prepreg of the present invention is a prepreg obtained by impregnating a fiber base material with the epoxy resin composition of the present invention described above. Thereby, the prepreg excellent in heat resistance, low expansion property, and flame retardance can be obtained. Examples of the above-mentioned fiber base material include glass fiber base materials such as glass woven fabric, glass nonwoven fabric, and cellophane; Woven or non-woven fabrics; woven fabrics, non-woven fabrics, mats, etc. containing metal fibers, carbon fibers, mineral fibers, etc. These substrates can be used alone or in combination. Among them, glass fiber substrates are preferred. Thereby, the rigidity and dimensional stability of the prepreg can be further 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.

The method of impregnating the above-mentioned fiber base material with the epoxy resin composition of the present invention includes, for example, a method of dipping a base material into a resin varnish, a method of coating with various coaters, and spraying with a spray device. method etc. Among these methods, the method of immersing the base material in a resin varnish is preferable. Thereby, the impregnability of the resin composition to the base material can be improved. In addition, when immersing a base material in a resin varnish, a normal dip coating equipment can be used.

For example, the epoxy resin composition of the present invention is impregnated on a substrate such as glass cloth as it is or in the form of a varnish obtained by dissolving or dispersing in a solvent, and then in a drying oven, etc., at a temperature of usually 80°C to 200°C ( Here, in the case of using a solvent, the prepreg is obtained by drying for 2 minutes to 30 minutes, preferably 2 minutes to 15 minutes, at a temperature at which the solvent can volatilize or higher).

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

The laminate used in the present invention is a laminate obtained by heat-press molding the above-mentioned prepreg of the present invention. Thereby, a metal-clad laminate excellent in heat resistance, low expansion, and flame retardancy can be obtained. In the case of one prepreg, metal foils are overlapped on the upper and lower sides or on one side. In addition, two or more prepregs may be laminated. When two or more prepregs are stacked, metal foils or films are stacked on both upper and lower surfaces or on one surface of the outermost prepregs after the stacking. Next, a metal-clad laminate can be obtained by subjecting a material obtained by overlapping a prepreg and a metal foil to heat and pressure molding. The temperature of the above heating is not particularly limited, but is preferably 120°C to 220°C, particularly preferably 150°C to 200°C. The pressure of the above pressurization is not particularly limited, but is preferably 1.5 MPa to 5 MPa, particularly preferably 2 MPa to 4 MPa. Moreover, you may post-curing at the temperature of 150 degreeC - 300 degreeC in a high temperature tank etc. as needed.

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

The printed wiring board of the present invention uses the above-described metal-clad laminate of the present invention as an inner-layer circuit board. Circuits are formed on one or both sides of the metal clad laminate. Depending on the case, through holes may be formed by drilling processing or laser processing, and electrical connection on both sides may be obtained by plating or the like.

A multilayer printed wiring board can be obtained by stacking a commercially available resin sheet or the resin sheet of the present invention, or the prepreg of the present invention described above on the inner layer circuit board, followed by heat and pressure molding.

Specifically, the insulating layer side of the above-mentioned resin sheet is bonded to the inner layer circuit board, and vacuum heating and pressure molding is performed using a vacuum pressurizing lamination apparatus or the like, and then the insulating layer can be heated and cured by a hot air drying apparatus or the like. and get.

Here, there are no particular limitations on the conditions of the heat-press molding, but as an example, it can be carried out under the conditions of a temperature of 60° C. to 160° C. and a pressure of 0.2 MPa to 3 MPa. Moreover, although it does not specifically limit as conditions of heat-hardening, It can implement on the conditions of temperature 140 degreeC - 240 degreeC, and time 30 minutes - 120 minutes as an example.

Alternatively, it can be obtained by stacking the prepreg of the present invention described above on an inner-layer circuit board and subjecting it to heat and pressure molding using a flat plate pressing apparatus or the like. Here, the conditions of the heat-press molding are not particularly limited, but as an example, it can be performed under the conditions of a temperature of 140° C. to 240° C. and a pressure of 1 MPa to 4 MPa. In such hot and press molding by a flat plate press or the like, heating and curing of the insulating layer is performed simultaneously with the hot and press molding.

Further, the method for producing a multilayer printed wiring board according to the present invention includes the steps of laminating the above-mentioned resin sheet or the prepreg of the present invention on the surface of the inner-layer circuit board on which the inner-layer circuit pattern is formed and continuously laminating, and a process of forming a conductor circuit layer by a semi-additive method.

The curing of the insulating layer formed of the resin sheet or the prepreg of the present invention may be preliminarily adjusted to a semi-cured state in order to facilitate subsequent laser irradiation and removal of resin residues and to improve desmearability. In addition, the first insulating layer is partially cured (semi-cured) by being heated at a temperature lower than the usual heating temperature, and one or more insulating layers are further formed on the insulating layer, so that the semi-cured insulating layer is further formed. The layer is reheated and hardened to such an extent that there is no practical problem, whereby the adhesion between the insulating layers and the insulating layer and the circuit can be improved. The temperature of the semi-curing in this case is preferably 80°C to 200°C, and more preferably 100°C to 180°C. In addition, in a subsequent process, although an opening part is formed in an insulating layer by irradiating a laser beam, it is necessary to peel off a base material before this. There is no particular problem in the peeling of the base material after forming the insulating layer, before heat curing, or at any time after heat curing.

It should be noted that, as the inner layer circuit board used in obtaining the above-mentioned multilayer printed wiring board, for example, a predetermined conductor circuit can be formed on both sides of the copper-clad laminate by etching or the like, and the conductor circuit portion can be preferably subjected to blackening treatment. The obtained inner layer circuit board.

Resin residues and the like after laser irradiation are preferably removed with an oxidizing agent such as permanganate and dichromate. In addition, the surface of the smooth insulating layer can be roughened at the same time, so that the adhesion of the conductive wiring circuit formed by the subsequent metal plating can be improved.

Next, the outer layer circuit is formed. The formation method of the outer layer circuit is as follows: the connection between insulating resin layers is achieved by metal plating, and the outer layer circuit pattern is formed by etching. A multilayer printed wiring board can be obtained in the same manner as when a resin sheet or a prepreg is used.

In addition, when using the resin sheet or prepreg which has a metal foil, in order to use as a conductor circuit without peeling a metal foil, a circuit formation can be performed by etching. In this case, when an insulating resin sheet with a base material using a thick copper foil is used, it is difficult to form a fine pitch in the subsequent circuit pattern formation, so an ultra-thin copper foil of 1 μm to 5 μm is used, or sometimes The copper foil of 12 μm to 18 μm is thinned to half etching of 1 μm to 5 μm by etching.

An insulating layer may be further laminated, and the same circuit formation as described above may be performed, and in the design of the multilayer printed wiring board, the solder resist layer may be formed after the circuit formation is performed on the outermost layer. The formation method of the solder resist layer is not particularly limited, and is accomplished by, for example, a method of laminating (laminating), exposing and developing a dry film type solder resist layer; or by applying a liquid resist after printing. A method of forming a solder resist layer by exposure and development. In addition, when using the obtained multilayer printed wiring board for a semiconductor device, in order to mount a semiconductor element, the electrode part for connection is provided. The electrode portion for connection can be appropriately covered with a metal coating such as gold plating, nickel plating, and solder plating. A multilayer printed wiring board can be produced by such a method.

Next, the 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 the connection to the multilayer printed wiring board is realized via the 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 bumps are preferably composed of an alloy containing tin, lead, silver, copper, bismuth, or the like.

A method of connecting a semiconductor element to a multilayer printed wiring board is as follows: use a flip-chip bonding machine or the like to align the connection electrode portion on the board with the solder bumps of the semiconductor element, and then use an infrared reflow soldering apparatus (IR reflow soldering apparatus). ), a hot plate, or other heating means to heat the solder bumps to a temperature higher than the melting point, and to fuse the multilayer printed wiring board and the solder bumps to connect them. In addition, in order to improve connection reliability, a metal layer with a low melting point, such as solder paste, may be formed in advance on the connection electrode portion on the multilayer printed wiring board. The connection reliability may be improved by applying a flux to the surface layer of the solder bump and/or the electrode portion for connection on the multilayer printed wiring board before the bonding step.

The substrate is used for a motherboard, a network substrate, a package substrate, and the like, and is used as a substrate. In particular, as a package substrate, it is useful as a thin-layer substrate for a single-sided sealing material. In addition, when used as a semiconductor sealing material, as a semiconductor device obtained by blending it, for example, DIP (Dual in-line package, dual in-line package), QFP (Quad Flat Package, quad flat package) can be mentioned, for example. , BGA (Ball GridArray, ball array package), CSP (Chip Scale Package, chip size package), SOP (Small Outline Package, small size package), TSOP (Thin Small Outline Package, thin small size package), TQFP (ThinQuad Flat Package) , thin quad flat pack) and so on.

Example

The characteristics of the present invention will be described in more detail below with reference to Synthesis Examples and Examples. The materials, processing contents, processing procedures, and the like shown below can be appropriately changed within the scope of not departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific examples shown below.

Here, the measurement conditions of each physical property value are as follows.

·Epoxy equivalent

Measured by the method described in JIS K-7236, and the unit is g/eq.

·Softening Point

It measured by the method based on JIS K-7234, and the unit is °C.

·Modulus of elasticity (DMA)

Dynamic Viscoelasticity Tester: TA-instruments, DMA-2980

Measurement temperature range: -30℃～280℃

Heating rate: 2°C/min

Test piece size: A test piece cut into 5mm x 50mm was used

Tg: The peak point of Tan-δ in the DMA measurement was taken as Tg.

·Water absorption

Weight increase rate (%) after boiling a disc-shaped test piece with a diameter of 5 cm x thickness of 4 mm in water at 100° C. for 24 hours

Synthesis Example 1

A phenolic resin ((a)/(b)=1.3, n=produced in accordance with WO2007/007827 and represented by the following formula was added to a flask equipped with a stirrer, a reflux condenser, and a stirring device while purging with nitrogen. 1.5, 134 parts of hydroxyl equivalents (134 g/eq., softening point 93°C), 450 parts of epichlorohydrin, and 54 parts of methanol were dissolved under stirring, and the temperature was raised to 70°C. Next, 42.5 parts of flaky sodium hydroxide was added stepwise over 90 minutes, and the reaction was further performed at 70°C for 1 hour. After completion of the reaction, washing with water was performed to remove salts, and then, solvents such as excess epichlorohydrin were distilled off from the obtained organic layer under reduced pressure using a rotary evaporator. 500 parts of methyl isobutyl ketone was added to the residue and dissolved, and 17 parts of a 30% by weight aqueous sodium hydroxide solution was added 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, 195 parts of epoxy resins (EP1) of Formula (1) were obtained by distilling methyl isobutyl ketone etc. from the obtained solution under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin was 211 g/eq., the softening point was 71°C, and the melt viscosity at 150°C (ICI melt viscosity, cone #1) was 0.34 Pa·s.

Example 1

The epoxy resin (EP1) obtained in Synthesis Example 1 was compounded with A-1 (amine equivalent 198 g/eq, active hydrogen equivalent 97.5 g/eq, softening point 55° C.) in an amount of 0.5 equivalent per 1 molar equivalent of epoxy equivalent. ) as a curing agent, salicylic acid was mixed as a catalyst at a ratio of 1 part by weight relative to 100 parts by weight of the epoxy resin (parts by weight), and was uniformly mixed/kneaded using a kneader to obtain an epoxy resin combination thing. The epoxy resin composition was pulverized by a stirrer, and then tableted by a tableting machine. The tableted epoxy resin composition was transfer-molded (175°C x 60 seconds), and then cured under the conditions of 160°C x 2 hours + 180°C x 6 hours after demolding to obtain an evaluation tool. Audition. The evaluation results are shown in Table 1.

In addition, the detail of the epoxy resin used for evaluation is shown in Table 2 below.

Comparative Examples 1 to 7

The epoxy resin (EP1) and various epoxy resins obtained from Synthesis Example 1 in Example 1 were used, and an equivalent amount of A-1 or HA-1 (manufactured by Meiwa Chemical Industry (Co., Ltd.), phenol novolak) was used.

lacquer resin) as a curing agent, and use triphenylphosphine (TPP) or salicylic acid as a catalyst to combine with

The same compounding and method as Example 1 were used to obtain a test piece for evaluation for comparison. conclude the evaluation

The results are shown in Table 1.

Table 1

epoxy resin epoxide equivalent Hardener Active hydrogen equivalent catalyst Tg(℃) Water absorption (%) Comparative Example 1 EPPN-502H 170 HA-1 106 TPP 1phr 220 1.98 Comparative Example 2 EPPN-501H 166 HA-1 106 TPP lphr 220 1.91 Comparative Example 3 EP1 211 HA-1 106 TPP 1phr 209 1.58 Example 1 EP1 211 A-1 97.5 Salicylic acid 1phr 256 1.44 Comparative Example 4 NC-3000 277 A-1 97.5 Salicylic acid 1phr 172 1.06 Comparative Example 5 RE-310S 182 A-1 97.5 No catalyst 155 1.19 Comparative Example 6 EOCN-1020-55 195 HA-1 106 TPP 1phr 185 1.15 Comparative Example 7 FAE-2500 217 HA-1 106 TPP 1phr 215 1.73

Table 2

Product name manufacturer structure EPPN-502H Nippon Kayaku (Co., Ltd.) Trihydroxyphenylmethane type epoxy resin EPPN-501H Nippon Kayaku (Co., Ltd.) Trihydroxyphenylmethane type epoxy resin NC-3000 Nippon Kayaku (Co., Ltd.) Biphenyl type phenol aralkyl resin RE-310S Nippon Kayaku (Co., Ltd.) Bisphenol A epoxy resin EOCN-1020-55 Nippon Kayaku (Co., Ltd.) cresol novolac epoxy resin FAE-2500 Nippon Kayaku (Co., Ltd.) Trihydroxyphenylmethane type epoxy resin

From Table 1, when Example 1 was compared with Comparative Example 3, it was confirmed that a cured product with good heat resistance and water absorption characteristics was specifically formed by using an amine-based curing agent rather than using a phenol resin as a curing agent.

In addition, the cured physical properties obtained in Table 1 were plotted with the heat resistance (Tg) on the horizontal axis and the water absorption characteristics (%) on the vertical axis, and the obtained graph is shown in FIG. 1 .

From FIG. 1 , it was confirmed that the cured products of Comparative Examples 1 to 3 and Comparative Examples 4 to 7 had a correlation in which the water absorption rate increased as Tg increased. On the other hand, it was confirmed that the cured product using the epoxy resin of the formula (1) and the amine-based curing agent had high heat resistance, but the water absorption was low, and it was confirmed that it was a specific combination different from the above-mentioned correlation.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2014-157629) for which it applied on August 1, 2014, The whole is used by reference. Additionally, all references cited herein are incorporated herein in their entirety.

Industrial Applicability

The epoxy resin composition of the present invention provides a cured product that can achieve both high heat resistance and water resistance in the cured product, and is therefore an extremely useful material for producing laminates such as printed wiring boards and build-up boards.

Claims (9)

1. An epoxy resin composition comprising, as essential components, an epoxy resin represented by the following general formula (1) and an amine-based curing agent, wherein the amine-based curing agent is a bifunctional or higher aniline resin obtained by polycondensation of aniline and a substituted biphenyl or a substituted phenyl, and the amine-based curing agent has a functional group equivalent of 60g/eq to 600g/eq,

wherein 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.

2. A prepreg obtained by impregnating a fibrous base material with the epoxy resin composition according to claim 1.

3. A prepreg according to claim 2 wherein the fibrous substrate is a glass fibre substrate.

4. The prepreg according to claim 3, wherein the glass fiber substrate contains at least 1 selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.

5. A metal-clad laminate obtained by laminating a metal foil on at least one side of the prepreg according to any one of claims 2 to 4.

6. A resin sheet obtained by forming an insulating layer comprising the epoxy resin composition according to claim 1 on a film or a metal foil.

7. A printed wiring board obtained by using the metal-clad laminate according to claim 5 for an inner layer circuit board.

8. A printed wiring board obtained by curing the prepreg according to any one of claims 2 to 4 or the resin sheet according to claim 6.

9. A semiconductor device obtained by mounting a semiconductor element on the printed wiring board according to claim 7 or claim 8.