CN106661200A - Epoxy resin composition, resin sheet, and prepreg, and metal-clad laminate board, printed circuit board, and semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide an epoxy resin composition that, when cured, is highly heat-resistant, is water-absorbent, and has a low dielectric constant. The purpose of the present invention is also to provide a resin sheet, a metal-clad laminate board, and a printed circuit board that use the epoxy resin composition and to provide a semiconductor device. This epoxy resin composition contains as essential components an epoxy resin that is represented by general formula (1) and an amine curing agent. (In the formula, the ratio ((a)/(b)) of (a) and (b) is 1-3, G represents a glycidyl group, and n represents the number of repetitions and is 0-5.)

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 the epoxy resin composition into a fiber substrate, a resin sheet, and a metal-clad laminate boards, printed wiring substrates, and semiconductor devices.

Background technique

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

However, in recent years, with the development of the electric/electronic field, moisture resistance, adhesion, and dielectric properties are required, including high purity of the resin composition. In order to make the filler (inorganic or organic filler) highly Further improvement of various characteristics such as low viscosity of filling, improvement of reactivity for shortening molding cycle, etc. In addition, as structural materials, materials that are lightweight and have excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. Especially in the field of semiconductor sealing, the required characteristics of the substrate (substrate itself or its peripheral materials) are increasing year by year, for example, higher Tg of peripheral materials due to the increase in driving temperature of semiconductors is required.

Generally, when the epoxy resin has a higher Tg, the water absorption rate increases (Non-Patent Document 1). This is the effect of increased crosslink density. However, there is an urgent need to develop a resin having the opposite characteristics due to the high Tg demand for semiconductor peripheral materials requiring low moisture absorption.

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

However, although this epoxy resin has both high heat resistance and flame retardancy when combined with a phenolic resin, it has a high water absorption rate and has a problem when it is used for electronic materials requiring very high reliability.

In addition, there is no description on the characteristics of the composition containing these epoxy resins and amine curing agents, and there is no description on the usefulness for printed wiring board applications.

prior art literature

patent documents

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

non-patent literature

Non-Patent Document 1: Ichiro Ogura, "Relationship between Chemical Structure and Properties of Epoxy Resins", DIC Technical Review No.7, Japan, 2001, p.7

Contents of the invention

The problem to be solved by the invention

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

means of solving problems

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, completed the present invention.

That is, the present invention provides:

(1)

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

(wherein, the ratio of (a)(b) is (a)/(b)=1～3, G represents glycidyl, n is the number of repetitions and is 0～5);

(2)

A prepreg obtained by impregnating the epoxy resin composition described in the above (1) into a fiber substrate;

(3)

The prepreg as described in (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 a metal foil on at least one surface of the prepreg described in (2) to (4);

(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 as 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 described in (7) or (8) above.

Invention effect

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

According to the present invention, it is possible to provide an epoxy resin composition, a prepreg using the epoxy resin composition, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device. The curing of the above-mentioned epoxy resin composition The material is high heat resistance and water absorption, low dielectric constant.

Description of drawings

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

detailed description

Hereinafter, the epoxy resin composition of this invention is demonstrated.

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

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

The epoxy resin of formula (1) used in the present invention can be disclosed by Japanese Patent Application Publication No. 2011-252037, Japanese Patent Application Publication No. The method described in /007827 is synthesized, and the epoxy resin synthesized by any method can be used as long as it has the structure of the above-mentioned formula (1).

Among them, in the present invention, the ratio (polyfunctionalization rate) of the above-mentioned formula (a) to the above-mentioned formula (b) is particularly an epoxy resin of (a)/(b)=1-3. When the structure of (a) is large, the heat resistance is improved, but accordingly, not only the water absorption property is deteriorated, but also it becomes brittle and hard. Therefore, an epoxy resin having a polyfunctionalization rate within the above range is used.

The softening point (ring and ball method) of the epoxy resin used is preferably 50°C to 150°C, more preferably 52°C to 100°C, 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 problems may arise in terms of productivity. In addition, when the softening point is 150° C. or higher, the temperature is 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., there are too many functional groups, so the cured product after curing may have a high water absorption rate and may become brittle. When the epoxy equivalent exceeds 350 g/eq., it is considered that the softening point becomes very large, or epoxidation does not proceed completely, and the amount of chlorine may become very large, so it is not preferable.

In addition, the amount of chlorine in the epoxy resin used for this invention is preferably 200 ppm-1500 ppm, especially preferably 200 ppm-900 ppm as total chlorine (hydrolysis method). According to the standard of JPCA, it is expected that the amount of chlorine in the epoxy monomer will not exceed 900 ppm. In addition, when the amount of chlorine is large, 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 a problem in productivity, so it is not preferable.

It should be noted that the melt viscosity at 150° C. of the epoxy resin used in the present invention is preferably 0.05 Pa·s to 5 Pa·s, particularly preferably 0.05 Pa·s to 2.0 Pa·s. When the melt viscosity is higher than 5 Pa·s, there may be problems in fluidity, flowability and embedding properties at the time of pressurization. When it is less than 0.05 Pa·s, since the molecular weight is too small, heat resistance may be insufficient.

The ratio of (a) and (b) in the above formula is (a)/(b)=1-3. That is, it is a glycidyl ether form characterized by more than half of the resorcinol structure. This ratio is important for precipitation of crystals and improvement of heat resistance, and it is preferable that (a)/(b) exceeds 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, thereby improving water absorption and toughness.

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

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 in combination, solubility in solvents such as methyl ethyl ketone, toluene, and propylene glycol monomethyl ether is also required for these resins.

In the present invention, solubility in methyl ethyl ketone is particularly important, and it is required that crystals should not be precipitated for 2 months or more under conditions such as 5° C. and room temperature. It is also related to the ratio of (a)/(b) above. When the value of (a) is large, crystals tend to precipitate, so it is important that (a)/(b) be 1 or more.

The epoxy resin composition of the present invention contains an amine curing agent as an essential component. Examples of usable amine curing agents 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 substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.) The obtained aniline resin, etc., are not limited to these.

A particularly preferable amine curing agent is a bifunctional or higher functional amine compound, 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 exhibit a crystal or resin shape.

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

In the case of a resin, it preferably has a softening point (ring and ball method) of 50°C to 150°C, particularly preferably 50°C to 100°C. In the case of a resin, an amine-based curing agent with a softening point of 50°C or lower may cause stickiness, so it is not preferable. In the case of a softening point exceeding 150°C, there may be a problem with fluidity during molding. Problems such as not being able to form completely, 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 cured product in terms of water absorption or toughness. When it exceeds 600, it may be difficult to maintain heat resistance.

In the epoxy resin composition of the present invention, the usage-amount of the amine curing agent is preferably 0.2 to 0.6 equivalents in terms of amine equivalents of the amine compound with respect to 1 equivalent of epoxy groups in the epoxy resin. Particularly preferably, it is 0.3 equivalent to 0.55 equivalent. When it is less than 0.2 equivalent or more than 0.6 equivalent with respect to 1 equivalent of epoxy groups, since hardening may become incomplete and favorable hardened|cured material property may not be acquired, it is unpreferable.

The epoxy resin composition of the present invention may also contain a curing accelerator. Specific examples of usable curing accelerators include formic acid, acetic acid, lactic acid, glycolic acid, n-butyric acid, isobutyric acid, propionic acid, caproic acid, octanoic 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, and sulfur-containing compounds; 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and other imidazoles; 2-(dimethylaminomethyl base) phenol, 1,8-diazabicyclo[5.4.0]undec-7ene and other tertiary amines; triphenylphosphine and other phosphines; metal compounds such as tin octoate, etc. 0.1-5.0 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 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 , alkyl aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthalene formaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); the above-mentioned phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl , butadiene, isoprene, etc.); polycondensates of the above phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ; Polycondensates of the above phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.); the above phenols and aromatic dichloromethyls (a, a'-dichloroxylene, dichloromethane polycondensate of the above phenols and aromatic bis-alkoxymethyl groups (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) Polycondensates of polycondensates; glycidyl ether epoxy resins, alicyclic epoxy resins, and glycidylamine epoxy resins obtained by glycidylating the polycondensates of the above-mentioned bisphenols and various aldehydes or alcohols , glycidyl ester epoxy resin, etc., but it is not limited to these as long as it is a commonly used epoxy resin. These epoxy resins may be used alone or in combination of two or more.

When blending the epoxy resin composition of the present invention, a conventionally known curing agent can be used in combination. Examples of other curing agents that can be used in combination include acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of curing agents that can be used include: amide compounds such as dicyandiamide and polyamide resins synthesized from linolenic acid dimers and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Anhydrides such as acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. 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.) Novolac resins of polycondensates of aldehydes, 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 and benzene diisopropanol, benzene diisopropanol dimethyl ether or benzene bis (chloroisopropane) reaction product of phenol aralkyl resin 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 are not limited to these. These curing agents may be used alone or in combination of two or more.

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-type phosphorus-containing compound or an additive-type phosphorus-containing compound. Specific examples of phosphorus-containing compounds include: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, cresyl diphenyl phosphate, 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 (di(xylyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-di Phosphines such as hydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxides; 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(di(xylyl)phosphate) cresyl) ester), 4,4'-biphenyl (bis(xylyl) phosphate), or phosphorus-containing epoxy compounds.

However, due to environmental issues and concerns about electrical properties, the amount of the phosphoric acid ester compound used above is preferably phosphoric acid ester compound/epoxy resin ≤ 0.1 (weight ratio). More preferably, it is 0.05 or less. It is particularly preferable not to add a phosphorus-containing compound other than 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, alumina, beryllium oxide, iron oxide, and titanium oxide. , aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, mica, etc. In addition, metal hydroxides such as magnesium hydroxide and aluminum hydroxide are also preferably used in order to impart a flame-retardant effect. 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 preferable because they are inexpensive and have good electrical reliability.

In the epoxy resin composition of the present invention, the amount of the inorganic filler used is usually in the range of 5% by weight to 70% by weight, preferably 10% by weight to 60% by weight, more preferably 15% by weight to 60% by weight, as an internal ratio. . When the amount is too small, the linear expansion increases, and warpage may become a problem, or rigidity may not be generated due to progress in thickness reduction of the substrate, and problems may arise in the process. In addition, if there is too much, there is a possibility that the homogeneity will be lost due to the sedimentation of the filler, or the embedding property of the substrate will be deteriorated, and the adhesion to the metal will be deteriorated. There is a high possibility of adverse effects on electrical characteristics such as voltage.

In addition, the shape, particle size, etc. of the inorganic filler are not particularly limited, and are usually an inorganic filler with a particle size of 0.01 μm to 50 μm, preferably 0.1 μm to 15 μm.

In order to improve release from a mold during molding, a release agent may be blended in the epoxy resin composition of the present invention. As the release agent, any of the existing known release agents can be used, for example: ester waxes such as carnauba wax and montan wax; fatty acids such as stearic acid and palmitic acid and their metal salts; Polyolefin waxes such as polyethylene and non-oxidized polyethylene. These release agents may be used alone or in combination of two or more. It is preferable that the compounding quantity of these release agents is 0.5 weight% - 3 weight% with respect to the whole organic component. When too much less than the said range, release from a mold may worsen, and when too much, adhesion with a base material etc. may worsen.

In order to improve the adhesiveness of an inorganic filler and a resin component, the epoxy resin composition of this invention can mix|blend a coupling agent. As the coupling agent, any conventionally known coupling agent can be used, for example: vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryloxy Various alkoxysilane compounds such as alkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxysilane, alkoxytitanium compound, 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 a 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 may be added to the epoxy resin composition of the present invention to obtain a varnish-like composition (hereinafter, simply referred to as a varnish). Examples of the solvent used include: γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl 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. solvents; methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and other ketone solvents; toluene, xylene and other aromatic solvents. The solid content concentration other than the solvent in the obtained varnish is usually 10% by weight to 80% by weight, preferably 20% by weight to 70% by weight.

In addition, known additives can be blended in the epoxy resin composition of the present 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, fluororesins , maleimide compounds, cyanate compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

The resin sheet of this invention is demonstrated.

The resin sheet using the epoxy resin composition of the present invention is obtained by coating the above-mentioned varnish with various coating methods such as gravure coating, screen printing, metal masking, and spin coating. Spread on a planar support so that the thickness after drying is a predetermined thickness, such as 5 μm to 100 μm, and then dry; which coating method to use can be determined according to the type, shape, size, coating thickness, and thickness of the support. The heat resistance of the support and the like are appropriately selected.

As a planar support, for example: polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetheramide Films made of various polymers such as imine, polyether ether ketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark), and/or copolymers thereof, or metal foils such as copper foil.

A sheet-like composition (resin sheet of the present invention) may be obtained by drying after coating, but may also be made into a sheet-like cured product by further heating the sheet. In addition, it is also possible to perform both solvent drying and curing steps by heating once.

The epoxy resin composition of the present invention can be applied to both surfaces or one surface of the support by the method described above and heated to form a layer of a cured product on both surfaces or one surface of the support. In addition, before curing, an adherend may be bonded and cured to produce a laminate.

In addition, the resin sheet of the present invention may be used as an adhesive sheet by peeling from a support, or it may be brought into contact with an adherend, and pressure and heat may be applied as necessary to make it adhere while curing.

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 above-mentioned epoxy resin composition of the present invention. Thereby, a prepreg excellent in heat resistance, low expansion, and flame retardancy can be obtained. Examples of the above-mentioned fiber substrates include: glass fiber substrates such as glass woven fabrics, glass non-woven fabrics, and cellophane; synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluorine-containing resins; Woven or non-woven fabrics; woven fabrics, non-woven fabrics, mats, etc. containing metal fibers, carbon fibers, mineral fibers, etc. These base materials 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 epoxy resin composition of the present invention into the fiber base material includes, for example, a method of impregnating the base material with 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 substrate in the resin varnish is preferable. Thereby, the impregnation property of a resin composition to a base material can be improved. In addition, when dipping a base material in a resin varnish, a general dip coating equipment can be used.

For example, the epoxy resin composition of the present invention is impregnated into a base material 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. ( However, when a solvent is used, the prepreg is obtained by drying for 2 minutes to 30 minutes, preferably 2 minutes to 15 minutes, at a temperature above which the solvent can volatilize.

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

The laminate used in the present invention is 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 laminated on both upper and lower surfaces or one surface. In addition, two or more prepregs may be laminated. When laminating two or more prepregs, metal foils or films are laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs. Next, a metal-clad laminate can be obtained by heating and press-forming a material obtained by laminating a prepreg and a metal foil. The heating temperature is not particularly limited, but is preferably 120°C to 220°C, particularly preferably 150°C to 200°C. The pressurized pressure is not particularly limited, but is preferably 1.5 MPa to 5 MPa, particularly preferably 2 MPa to 4 MPa. In addition, post-curing may be performed at a temperature of 150° C. to 300° C. in a high-temperature bath or the like as needed.

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

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

A multilayer printed wiring board can be obtained by laminating a commercially available or the resin sheet of the present invention or the prepreg of the present invention on the above-mentioned inner layer circuit board, followed by heating and press molding.

Specifically, the insulating layer side of the above-mentioned resin sheet can be bonded to the inner layer circuit board, vacuum-heated and press-molded using a vacuum pressure lamination device, etc., and then the insulating layer can be heat-cured by using a hot-air drying device or the like. And get.

Here, the conditions of the heat press molding are not particularly limited, and one example is given, and it can be carried out under 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 a heat hardening condition, An example is given, It can implement on conditions of temperature 140 degreeC - 240 degreeC, time 30 minutes - 120 minutes.

Alternatively, it can be obtained by laminating the above-mentioned prepreg of the present invention on an inner-layer circuit board and subjecting it to heat-press molding using a flat-plate pressing device or the like. Here, the conditions of the heat press molding are not particularly limited, and one example is given, and it can be carried out under conditions of a temperature of 140° C. to 240° C. and a pressure of 1 MPa to 4 MPa. In such heat-press forming using a flat-plate press device or the like, heat-curing of the insulating layer is performed simultaneously with heat-press forming.

In addition, the method for manufacturing a multilayer printed wiring board according to the present invention includes the steps of successively 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 a process of forming a conductor circuit layer by a semi-additive method.

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 resin residue removal and improve desmearability. In addition, the first insulating layer is heated at a temperature lower than the usual heating temperature, thereby partially curing (semi-curing), and one or more insulating layers are further formed on the insulating layer, so that the semi-cured insulating layer The layers are cured by heating again to a level where there is no practical problem, thereby improving the adhesion between the insulating layers and between the insulating layers and the circuit. The temperature of semi-curing in this case is preferably 80°C to 200°C, more preferably 100°C to 180°C. It should be noted that, in the subsequent process, the opening is formed in the insulating layer by irradiating laser light, but the base material needs to be peeled off before that. There is no particular problem in performing the peeling of the base material at any time after the insulating layer is formed, before heat curing, or after heat curing.

It should be noted that the inner layer circuit board used to obtain the above-mentioned multilayer printed wiring board can be preferably used, for example, by forming predetermined conductive circuits on both sides of the copper-clad laminate by etching or the like, and blackening the conductive circuit parts. The obtained inner layer circuit substrate.

Resin residues and the like after laser irradiation are preferably removed by an oxidizing agent such as permanganate or 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, outer layer circuits are formed. The forming method of the outer layer circuit is as follows: the connection between insulating resin layers is realized 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 prepreg is used.

In addition, when using the resin sheet or prepreg which has metal foil, in order to use it as a conductor circuit without peeling metal foil, you may perform circuit formation by etching. In this case, when using an insulating resin sheet with a base material using a thick copper foil, 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 it may be carried out. Half etching is used to reduce the thickness of copper foil from 12 μm to 18 μm to 1 μm to 5 μm by etching.

An insulating layer may be further laminated, and the same circuit formation as above may be performed, and in the design of the multilayer printed wiring board, a solder resist layer may be formed after circuit formation is performed on the outermost layer. The formation method of the solder resist layer is not particularly limited, for example, it is completed by the following method: by laminating (laminating), exposing and developing a dry film type solder resist layer; A method of exposing and developing to form a solder resist layer. 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 coated with a metal coating such as gold plating, nickel plating, or 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 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 bump is preferably composed of an alloy containing tin, lead, silver, copper, bismuth, or the like.

The method of connecting a semiconductor element to a multilayer printed wiring board is a method of aligning the connection electrode portion on the substrate with the solder bump of the semiconductor element using a flip-chip bonding machine, etc., and then using an infrared reflow device (IR reflow device ), a hot plate, or other heating devices to heat the solder bumps to a temperature above the melting point, and fuse and bond the multilayer printed wiring board and the solder bumps to thereby perform connection. 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. Before this bonding step, a flux may be applied to the surface layer of the solder bump and/or the connection electrode portion on the multilayer printed wiring board to improve connection reliability.

The substrate is used for a motherboard, a network substrate, a packaging 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 combining it, for example: DIP (Dual in-line package, dual in-line package), QFP (Quad Flat Package, quadrilateral flat package) , 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 Package), etc.

Example

Hereinafter, the characteristics of the present invention will be described more concretely with reference to synthesis examples and examples. Materials, processing contents, processing procedures, and the like described below can be appropriately changed without departing from the spirit 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

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

·Softening Point

It measures by the method based on JISK-7234, and the unit is degreeC.

·Elastic modulus (DMA)

Dynamic viscoelasticity tester: TA-instruments, DMA-2980

Measuring temperature range: -30℃～280℃

Heating rate: 2°C/min

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

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

·Water absorption

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

Synthesis Example 1

In a flask equipped with a stirrer, a reflux condenser, and a stirring device, a phenolic resin produced in accordance with WO2007/007827 and represented by the following formula ((a)/(b)=1.3, n= 1.5, hydroxyl equivalent 134g/eq., softening point 93°C), 134 parts, 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 were added stepwise over 90 minutes, and then reacted at 70°C for 1 hour. After completion of the reaction, water was washed to remove the salt, and excess solvents such as epichlorohydrin were distilled off from the obtained organic layer under reduced pressure using a rotary evaporator. 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 with stirring to react for 1 hour, and then washed with water until the washing water of the oil layer became neutral. Using a rotary evaporator, 195 parts of epoxy resins (EP1) of the formula (1) were obtained by distilling off methyl isobutyl ketone and the like from the obtained solution under reduced pressure. The obtained epoxy resin had an epoxy equivalent of 211 g/eq., a softening point of 71° C., and a melt viscosity (ICI melt viscosity, cone #1) at 150° C. of 0.34 Pa·s.

Example 1

For the epoxy resin (EP1) obtained in Synthesis Example 1, A-1 (amine equivalent 198g/eq, active hydrogen equivalent 97.5g/eq, softening point 55° C. ) as a curing agent, salicylic acid was blended as a catalyst in a ratio (parts by weight) of 1 part by weight relative to 100 parts by weight of epoxy resin, and mixed/kneaded uniformly using a mixer to obtain an epoxy resin combination things. This epoxy resin composition was pulverized with a mixer, and then tableted with a tablet machine. Transfer molding (175°C × 60 seconds) of the epoxy resin composition after the tableting was carried out, and then cured under the conditions of 160°C × 2 hours + 180°C × 6 hours after demoulding, thereby obtaining the Audition. Table 1 shows the evaluation results.

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

Comparative Examples 1-7

Using the epoxy resin (EP1) and various epoxy resins obtained by Synthesis Example 1 in Example 1, use equivalent A-1 or HA-1 (manufactured by Meiwa Chemical Industry (KK), phenol novolac

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

A test piece for evaluation for comparison was obtained by the same compounding and method as in Example 1. conclude the evaluation

The results are shown in Table 1.

Table 1

epoxy resin Epoxide Equivalent Hardener Active hydrogen equivalent catalyst Tg(°C) 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.) Trishydroxyphenylmethane type epoxy resin EPPN-501H Nippon Kayaku (Co., Ltd.) Trishydroxyphenylmethane type epoxy resin NC-3000 Nippon Kayaku (Co., Ltd.) Biphenyl type phenol aralkyl resin RE-310S Nippon Kayaku (Co., Ltd.) Bisphenol A type epoxy resin EOCN-1020-55 Nippon Kayaku (Co., Ltd.) Cresol Novolac Epoxy Resin FAE-2500 Nippon Kayaku (Co., Ltd.) Trishydroxyphenylmethane type epoxy resin

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

In addition, the cured product 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 can be confirmed that the cured products of Comparative Examples 1 to 3 and Comparative Examples 4 to 7 have a relationship in which the water absorption rate increases as Tg increases. On the other hand, it was confirmed that the cured product using the epoxy resin of formula (1) and the amine curing agent had high heat resistance but low water absorption and was a specific combination different from the above 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 JP Patent application (Japanese Patent Application No. 2014-157629) of an application on August 1, 2014, The whole is used by reference. In addition, all the references cited here are taken in as a whole.

Industrial applicability

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

Claims (9)

1. An epoxy resin composition, wherein, the epoxy resin composition is an essential component with an epoxy resin represented by the following general formula (1) and an amine curing agent, In the formula, the ratio of (a)(b) is (a)/(b)=1-3, G represents a glycidyl group, and n is 0-5 as the number of repetitions. 2. A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to claim 1. 3. The prepreg of claim 2, wherein the fibrous substrate is a glass fiber substrate. 4. The prepreg according to claim 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. 5. A metal-clad laminate obtained by laminating a metal foil on at least one surface of the prepreg according to any one of claims 2 to 4. 6. A resin sheet obtained by forming an insulating layer containing the epoxy resin composition according to claim 1 on a film or on 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 claim 2 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.