WO2016017751A1 - 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, metal-clad laminate, printed wiring board, semiconductor device

The present invention relates to an epoxy resin composition that gives a cured product excellent in heat resistance and water resistance, a prepreg impregnated with a fiber base material, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device.

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

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Particularly in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), the required characteristics are becoming higher year by year. For example, there is a demand for higher Tg of peripheral materials due to an increase in semiconductor driving temperature. Yes.

Epoxy resins generally increase in water absorption when the Tg is increased (Non-patent Document 1). This is due to an increase in crosslink density. However, while high Tg is required for semiconductor peripheral materials that require low moisture absorption, there is an urgent need to develop a resin having these contradictory characteristics.
On the other hand, Patent Document 1 discloses a phenol novolac resin having a biphenyl skeleton and a phenol novolac type epoxy resin obtained by epoxidizing the phenol novolak resin, and describes its usefulness for use as a semiconductor encapsulant.
However, although this epoxy resin combines high heat resistance and flame retardancy in combination with a phenol resin, there is a problem in using it for electronic materials that have high water absorption and require extremely high reliability.
In addition, there is no description about the characteristics of the composition containing these epoxy resins and amine-based curing agents, and there is no description on the usefulness of the printed wiring board.

Japanese Unexamined Patent Publication No. 2013-43958

Ichiro Ogura, “Relationship between Chemical Structure and Properties of Epoxy Resin”, DIC Technical Review No. 7, Japan, 2001, page 7

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

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides (1) the following general formula (1)

(Wherein the ratio of (a) and (b) is (a) / (b) = 1 to 3. G represents a glycidyl group, n is the number of repetitions and is 0 to 5.) An epoxy resin composition comprising an epoxy resin and an amine curing agent as essential components,
(2)
A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to item (1),
(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 includes 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 in which a metal foil is laminated on at least one surface of the prepreg described in the preceding paragraphs (2) to (4),
(6)
A resin sheet formed by forming an insulating layer made of the epoxy resin composition according to item (1) on a film or a metal foil;
(7)
A printed wiring board using the metal-clad laminate as described in (5) above for an inner circuit board;
(8)
A printed wiring board obtained by curing the prepreg according to any one of (2) to (4) or the resin sheet according to (6);
(9)
A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to (7) or (8),
Is to provide.

Since the epoxy resin composition of the present invention provides a cured product that can simultaneously achieve high heat resistance and water resistance in the cured product, it is extremely useful for producing laminated boards such as printed wiring boards and build-up boards. Material.
According to the present invention, an epoxy resin composition whose cured product has high heat resistance, water absorption and low dielectric constant, and a prepreg, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor device using the epoxy resin composition. Can be provided.

It is a graph showing the relationship between the heat resistance of the hardened | cured material of an epoxy resin composition, and a water absorption characteristic.

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention comprises, as an essential component, a compound represented by the following formula (1) (hereinafter referred to as “epoxy resin of formula (1)”) and an amine curing agent as an epoxy resin.

(In the formula, the ratio of (a) and (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 the formula (1) used in the present invention is disclosed in Japanese Unexamined Patent Publication No. 2011-252037, Japanese Unexamined Patent Publication No. 2008-156553, Japanese Unexamined Patent Publication No. 2013-043958, International Publication WO2012 / 053522, WO2007 / Although it can be synthesized by the method described in 007827, any method may be used as long as it has the structure of the formula (1).
However, in the present invention, those in which the ratio (polyfunctionalization ratio) of the formula (a) to the formula (b) is (a) / (b) = 1 to 3 are used. When the structure (a) is large, the heat resistance is improved, but the water absorption characteristics are deteriorated, and the structure becomes brittle and hard. Therefore, the polyfunctionalization rate within the above range is used.

The softening point (ring and ball method) of the epoxy resin used is preferably 50 to 150 ° C., more preferably 52 to 100 ° C., and particularly preferably 52 to 95 ° C. Below 50 ° C., stickiness is severe, handling is difficult, and problems may arise in productivity. Moreover, when it is 150 degreeC or more, since it is a temperature near molding temperature and the fluidity | liquidity at the time of shaping | molding may not be ensured, it is unpreferable.

The epoxy equivalent of the epoxy resin used is 180 to 350 g / eq. It is preferable that In particular, 190 to 300 g / eq. It is preferable that Epoxy equivalent is 180 g / eq. When the ratio is less than 1, since the functional group is too many, the cured product after curing tends to have a high water absorption rate and may become brittle. Epoxy equivalent is 350 g / eq. If it exceeds 1, the softening point becomes very large or epoxidation has not progressed cleanly, which is not preferable because the amount of chlorine may become very large.

The chlorine content of the epoxy resin used in the present invention is preferably 200 to 1500 ppm, particularly preferably 200 to 900 ppm in terms of total chlorine (hydrolysis method). From the JPCA standard, it is desired that epoxy alone does not exceed 900 ppm. Furthermore, a large amount of chlorine is not preferable because it may affect the electrical reliability. When it is less than 200 ppm, an excessive purification step is required, which may cause problems in productivity, which is not preferable.

The melt viscosity at 150 ° C. of the epoxy resin used in the present invention is preferably 0.05 to 5 Pa · s, particularly preferably 0.05 to 2.0 Pa · s. When the melt viscosity is higher than 5 Pa · s, there is a problem in fluidity, and there may be a problem in flow property and embedding property during pressing. When it is less than 0.05 Pa · s, the molecular weight is too small, and the heat resistance may be insufficient.

In the above formula, the ratio of (a) to (b) is (a) / (b) = 1-3. That is, more than half are glycidyl ethers having a resorcin structure. This ratio is important for the precipitation of crystals and the improvement of heat resistance, and (a) / (b) preferably exceeds 1. Moreover, water absorption and toughness can be improved by restrict | limiting the quantity of the glycidyl ether body of a resorcinol structure because (a) / (b) is 3 or less.
In the above formula, n is a repeating unit and is 0-5. When n does not exceed 5, the flowability and fluidity of the prepreg or resin sheet are controlled. When this exceeds 5, a problem arises not only in fluidity but also in solubility in a solvent.
In the epoxy resin used in the present invention, solubility in a solvent is important. For example, when a biphenyl aralkyl type epoxy resin having the same skeleton is used in combination, these resins also need to be soluble in solvents such as methyl ethyl ketone, toluene, propylene glycol monomethyl ether and the like.
In the present invention, solubility in methyl ethyl ketone is particularly important, and it is required that crystals do not precipitate for 2 months or more at 5 ° C., room temperature or the like. Although it is also related to the ratio of (a) / (b) described above, it is important that (a) / (b) is 1 or more because crystals are likely to appear when the value of (a) is large. Become.

The epoxy resin composition of the present invention contains an amine curing agent as an essential component. Examples of amine 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 substituted phenyls (1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and An aniline resin obtained by polycondensation with 1,4-bis (hydroxymethyl) benzene or the like, but is not limited thereto.

Particularly preferred amine-based curing agents are bifunctional or higher amine compounds, and resins having a structure represented by the following formula are preferred.

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

Each of the amine curing agents used in the present invention exhibits a crystal or resin shape.
In the case of crystals, the melting point is preferably 35 to 200 ° C., particularly preferably 40 to 185 ° C. In the case of the melting point, unlike the softening point, the solubility in other resins is also involved, and therefore it is not always necessary that the temperature be lower than the molding temperature like a resin.
In the case of a resin, a softening point (ring and ball method) of 50 to 150 ° C. is preferable, and 50 to 100 ° C. is particularly preferable. In the case of resin, those with a softening point of 50 ° C. or lower are not preferable because stickiness may occur, and when the softening point exceeds 150 ° C., fluidity problems occur at the time of molding, and it cannot be molded cleanly. In addition, there may be a problem that the solvent cannot be removed.

The functional group equivalent of the amine compound is 60 to 600 g / eq. (Measurement by potentiometric titration) is preferred. When the active hydrogen equivalent is 60 or less, the cured product may have problems with water absorption and toughness. If it exceeds 600, it may be difficult to maintain heat resistance.

In the epoxy resin composition of the present invention, the amount of the amine curing agent used is preferably 0.2 to 0.6 equivalent in terms of amine equivalent of the amine compound with respect to 1 equivalent of epoxy group of the epoxy resin. Particularly preferred is 0.3 to 0.55 equivalent. When less than 0.2 equivalent or more than 0.6 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

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, iso-butyric acid, propionic acid, caproic acid, octanoic acid, n-heptylic acid, monochloroacetic acid, 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, phloroglicinol, 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, que Acids, acids such as monoethanolamine, diethanolamine, triethanolamine, thiophenol, 2-mercaptoethanol, sulfur-containing compounds, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole Imidazoles such as 2-amine, 2- (dimethylaminomethyl) phenol, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, phosphines such as triphenylphosphine, octyl Examples thereof include metal compounds such as tin oxide. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

In the epoxy resin composition of the present invention, other epoxy resins can 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 Group-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde) , Crotonaldehyde, cinnamaldehyde, etc.); the above phenols and various dieneization A polymer of the above-mentioned phenols and ketones (acetone, acetone, Polycondensates of methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc .; polycondensates of the phenols with aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.); the phenols and aromatic dichloromethyl Polycondensates (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.); phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl) Glycidyl ether epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin obtained by glycidylation of polycondensates of the above bisphenols and various aldehydes or alcohols, etc., Examples thereof include glycidyl ester-based epoxy resins, but are not limited thereto as long as they are usually used epoxy resins. These 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 polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, Acid anhydride compounds such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalenediol Tris- (4-hydroxyph Nyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde , P-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, novolak resin which is a polycondensate of furfural, phenol or cresol and phenylenedimethylol, dimethoxymethyl or halogenated methyl Reaction product of or with phenol or cresol and bischloromethylbiphenyl, bismethoxymethylbiphenyl or bishydroxymethyl Phenol aralkyl resins that are a reaction product of biphenyl, a reaction product of phenol and benzene diisopropanol, benzene diisopropanol dimethyl ether, or benzene bis (chloroisopropane), and modified products thereof, and halogenated bisphenols such as tetrabromobisphenol A And phenolic compounds such as terpene and phenol condensates, imidazole, trifluoroborane-amine complexes, guanidine derivatives and the like, but are not limited thereto. These 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 or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid ester compounds such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9- Phosphanes such as oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; activity of epoxy resin and said phosphanes Phosphorus obtained by reacting with hydrogen -Containing epoxy compounds, red phosphorus, and the like. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylyl) is preferable. Renyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
However, the amount of the phosphoric acid ester compound as described above is preferably phosphoric acid ester compound / epoxy resin ≦ 0.1 (weight ratio) due to environmental problems and concerns about electrical characteristics. More preferably, it is 0.05 or less. It is particularly preferable not to add a phosphorus compound except that it is added as a curing accelerator.

The epoxy resin composition of the present invention may contain an inorganic filler. Inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, titanium oxide, aluminum nitride, silicon nitride, and nitride Examples thereof include boron, mica, glass, quartz, and mica. Further, it is also preferable to use a metal hydroxide such as magnesium hydroxide or aluminum hydroxide in order to impart a flame retardant effect. However, it is not limited to these. Two or more kinds may be mixed and used. Of these inorganic fillers, silicas such as fused silica and crystalline silica are preferred because of low cost and good electrical reliability.
In the epoxy resin composition of the present invention, the amount of the inorganic filler used is usually 5% to 70% by weight, preferably 10% to 60% by weight, more preferably 15% to 60% by weight. It is a range. If the amount is too small, the linear expansion increases, warping becomes a problem, and the substrate is becoming thinner, so that rigidity may not be achieved and a problem may occur during the process. In addition, if it is too much, there is a risk that the homogeneity may be lost due to sedimentation of the filler, the embedding property of the substrate may be deteriorated, and the adhesion with the metal may be deteriorated. In addition, there is a high possibility that electrical characteristics such as peeling and breakdown voltage will be adversely affected.
Further, the shape, particle size and the like of the inorganic filler are not particularly limited, but usually the particle size is 0.01 to 50 μm, preferably 0.1 to 15 μm.

In the epoxy resin composition of the present invention, a release agent can be blended to improve the release from the mold during molding. Any conventionally known release agent can be used, for example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, polyolefins such as polyethylene oxide and non-oxidized polyethylene And waxes. These may be used alone or in combination of two or more. The compounding amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If the amount is too small, release from the mold is poor, and if the amount is too large, adhesion to the substrate or the like may be deteriorated.

In the epoxy resin composition of the present invention, a coupling agent can be blended in order to enhance the adhesion between the inorganic filler and the resin component. Any conventionally known coupling agent can be used. For example, vinyl alkoxy silane, epoxy alkoxy silane, styryl alkoxy silane, methacryloxy alkoxy silane, acryloxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, isocyanate alkoxy Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. The coupling agent may be added by treating the surface of the inorganic filler with the coupling agent in advance and then kneading with the resin, or mixing the coupling agent with the resin and then kneading the inorganic filler. .

An organic solvent can be added to the epoxy resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents 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, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned. The solvent is used in the range where the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.

Furthermore, a known additive can be blended in the epoxy resin composition of the present invention as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, and silicone oil. And colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

The resin sheet of the present invention will be described.
The resin sheet using the epoxy resin composition of the present invention has a thickness after drying the above varnish on a planar support by various coating methods such as gravure coating, screen printing, metal mask, and spin coating. Can be obtained by drying after coating so that the thickness becomes a predetermined thickness, for example, 5 to 100 μm. Which coating method is used depends on the type, shape, size, thickness of coating, support It is appropriately selected depending on the heat resistance of the body.
Examples of the planar support include various types such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetherketone, polyetherimide, polyetheretherketone, polyketone, polyethylene, polypropylene, and Teflon (registered trademark). Examples thereof include films made from molecules and / or copolymers thereof, and metal foils such as copper foils.
After application, it can be dried to obtain a sheet-like composition (resin sheet of the present invention), but it can also be made into a sheet-like cured product by further heating the sheet. Moreover, you may serve as a solvent drying and hardening process by one heating.
The epoxy resin composition of the present invention can form a cured product layer on both sides or one side of the support by coating and heating on both sides or one side of the support by the above method. It is also possible to produce a laminate by bonding and adhering the adherend before curing.
Moreover, the resin sheet of this invention can also be used as an adhesive sheet by peeling off from a support body, and it can also be made to contact with a to-be-adhered body and to apply pressure and heat as needed, and to make it adhere | attach with hardening.

The prepreg of the present invention will be described.
The prepreg of the present invention is obtained by impregnating a fiber base material with the epoxy resin composition of the present invention. Thereby, the prepreg excellent in heat resistance, low expansibility, and a flame retardance can be obtained. Examples of the fiber base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, paper, aramid, polyester, aromatic polyester, and synthetic fibers such as fluororesin, etc. Examples thereof include woven fabrics, nonwoven fabrics, mats and the like made of fibers, carbon fibers, mineral fibers and the like. These substrates may be used alone or in combination. Among these, a glass fiber base material is preferable. Thereby, the rigidity and dimensional stability of the prepreg can be further improved.
As a glass fiber base material, what contains at least 1 type chosen from the group which consists of T glass, S glass, E glass, NE glass, and quartz glass is preferable.

Examples of the method of impregnating the fiber base material with the epoxy resin composition of the present invention include a method of immersing the base material in a resin varnish, a method of applying with various coaters, and a method of spraying. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.
For example, the epoxy resin composition of the present invention is used as it is or in the form of a varnish dissolved or dispersed in a solvent, after impregnating a substrate such as a glass cloth, usually in a drying furnace or the like, usually at 80 to 200 ° C. (however, When the solvent is used, the temperature is set to a temperature at which the solvent can be volatilized or higher), and the prepreg is obtained by drying for 2 to 30 minutes, preferably 2 to 15 minutes.

The metal-clad laminate of the present invention will be described.
The laminate used in the present invention is formed by heating and pressing the above-described prepreg of the present invention. Thereby, the metal-clad laminated board excellent in heat resistance, low expansibility, and a flame retardance can be obtained. When one prepreg is used, the metal foil is overlapped on both the upper and lower surfaces or one surface. Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg. Next, a metal-clad laminate can be obtained by heat-pressing a laminate of a prepreg and a metal foil. The heating temperature is not particularly limited, but is preferably 120 to 220 ° C, and particularly preferably 150 to 200 ° C. The pressure to be pressurized is not particularly limited, but is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. with a high-temperature iron or the like.

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 circuit board. A circuit is formed on one or both sides of the metal-clad laminate. In some cases, through holes can be formed by drilling or laser processing, and electrical connection on both sides can be achieved by plating or the like.

A commercially available or resin sheet of the present invention, or the prepreg of the present invention is superposed on the inner layer circuit board and heated and pressed to obtain a multilayer printed wiring board.
Specifically, the insulating layer side of the resin sheet and the inner layer circuit board are combined, vacuum-pressed using a vacuum pressurizing laminator, etc., and then the insulating layer is heated and cured with a hot air dryer or the like. Can be obtained.
Here, the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3 MPa. The conditions for heat curing are not particularly limited, but for example, the temperature can be 140 to 240 ° C. and the time can be 30 to 120 minutes.
Alternatively, it can be obtained by overlaying the prepreg of the present invention on an inner circuit board and subjecting it to hot press molding using a flat plate press or the like. Here, the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa. In the heat and pressure forming by such a flat plate press apparatus or the like, the insulating layer is heat-cured simultaneously with the heat and pressure forming.

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

Curing of the resin sheet or the insulating layer formed from the prepreg of the present invention may be left in a semi-cured state in order to facilitate the subsequent laser irradiation and removal of the resin residue and improve desmearability. In addition, the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer. By heat-curing again to such an extent that there is no practical problem, the adhesion between the insulating layer and between the insulating layer and the circuit can be improved. In this case, the semi-curing temperature is preferably 80 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C. In the next step, laser is irradiated to form an opening in the insulating layer, but it is necessary to peel off the substrate before that. There is no particular problem with the peeling of the base material either after the insulating layer is formed, before heat curing, or after heat curing.
The inner layer circuit board used when obtaining the multilayer printed wiring board is preferably, for example, one in which a predetermined conductor circuit is formed by etching or the like on both surfaces of a copper clad laminate and the conductor circuit portion is blackened. Can be used.

Resin residues after laser irradiation are preferably removed with an oxidizing agent such as permanganate or dichromate. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by subsequent metal plating can be improved.

Next, an outer layer circuit is formed. The outer layer circuit is formed by connecting the insulating resin layers by metal plating and forming an outer layer circuit pattern by etching. A multilayer printed wiring board can be obtained in the same manner as when a resin sheet or prepreg is used.
When a resin sheet having a metal foil or a prepreg is used, a circuit may be formed by etching for use as a conductor circuit without peeling off the metal foil. In that case, if an insulating resin sheet with a base material using a thick copper foil is used, it becomes difficult to make a fine pitch in the subsequent circuit pattern formation, so use an ultrathin copper foil of 1 to 5 μm, or 12 to 18 μm. In some cases, the copper foil is half-etched to a thickness of 1 to 5 μm by etching.

Further, an insulating layer may be further laminated and a circuit may be formed in the same manner as described above. However, in the design of the multilayer printed wiring board, a solder resist is formed on the outermost layer after the circuit is formed. The method for forming the solder resist is not particularly limited. For example, a method of laminating (laminating) a dry film type solder resist, forming by exposure and development, or forming a printed liquid resist by exposure and development It is done by the method to do. 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 a connection is provided. The connecting electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, or solder plating. A multilayer printed wiring board can be manufactured 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 attempted through 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 made of an alloy made of tin, lead, silver, copper, bismuth or the like.
The semiconductor element and multilayer printed wiring board can be connected by aligning the connection electrode part on the substrate with the solder bump of the semiconductor element using a flip chip bonder, etc., and then using an IR reflow device, hot plate, etc. The solder bumps are heated to the melting point or higher by using a heating device, and the multilayer printed wiring board and the solder bumps are connected by fusion bonding. In order to improve connection reliability, a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this bonding step, the connection reliability can be improved by applying a flux to the solder bumps and / or the surface layer of the connection electrode portion on the multilayer printed wiring board.

As a substrate, it is used as a motherboard, a network substrate, a package substrate, etc., and used as a substrate. Especially 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 encapsulant, examples of semiconductor devices obtained from the blending include DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package). SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package), and the like.

Hereinafter, the features of the present invention will be described more specifically with reference to synthesis examples and examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited 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, the unit is g / eq. It is.
-Softening point Measured by a method according to JIS K-7234, the unit is ° C.
-Elastic modulus (DMA)
Dynamic viscoelasticity measuring instrument: TA-insRents, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature increase rate: 2 ° C./min. Test piece size: 5 mm × 50 mm cut out was used. Tg: Tan-δ peak point in DMA measurement was Tg. Water absorption: disk shape with diameter 5 cm × thickness 4 mm % Increase after boiling the test piece in 100 ° C water for 24 hours

Synthesis example 1
A phenol resin represented by the following formula ((a) / (b) = 1.3 n manufactured according to WO2007 / 007827 while applying nitrogen purge to a flask equipped with a stirrer, a reflux condenser, and a stirrer. = 1.5 Hydroxyl equivalent weight 134 g / eq. Softening point 93 ° C.) 134 parts, epichlorohydrin 450 parts and methanol 54 parts were added, dissolved under stirring, and heated to 70 ° C. Next, 42.5 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, the mixture was washed with water to remove the salt, and then the resulting organic layer was distilled off excess solvent such as epichlorohydrin under reduced pressure using a rotary evaporator. Add 500 parts of methyl isobutyl ketone to the residue, dissolve, add 17 parts of 30% by weight aqueous sodium hydroxide solution under stirring, react for 1 hour, and then wash with water until the washing water of the oil layer becomes neutral. From the obtained solution, 195 parts of an epoxy resin (EP1) of the formula (1) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 211 g / eq. The melt viscosity (ICI melt viscosity cone # 1) at a softening point of 71 ° C. and 150 ° C. was 0.34 Pa · s.

Example 1
The epoxy resin (EP1) obtained in Synthesis Example 1 was treated with A-1 (amine equivalent 198 g / eq, active hydrogen equivalent 97.5 g / eq, softening point 55 ° C.) as a curing agent with respect to 1 molar equivalent of epoxy equivalent. The epoxy resin composition is blended at 0.5 equivalent, and salicylic acid is blended at a ratio (parts by weight) of 1 part by weight with respect to 100 parts by weight of the epoxy resin, and mixed and kneaded uniformly using a mixing roll. Got. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. The evaluation results are shown in Table 1.
Details of the epoxy resin used for the evaluation are shown in Table 2 below.

Comparative Examples 1-7
In Example 1, the epoxy resin (EP1) obtained in Synthesis Example 1 and various epoxy resins were equivalent to A-1 or HA-1 (phenol novolak resin manufactured by Meiwa Kasei Kogyo Co., Ltd.) as a curing agent. A test piece for evaluation for comparison was obtained by the same composition and method as in Example 1 using triphenylphosphine (TPP) or salicylic acid as a catalyst. The evaluation results are shown in Table 1.

From Table 1, when Example 1 and Comparative Example 3 are compared, by using an amine curing agent as compared with using a phenol resin as a curing agent, a cured product having excellent heat resistance and water absorption characteristics can be obtained. It was confirmed that

Further, FIG. 1 is a graph in which the cured physical properties obtained in Table 1 are plotted with heat resistance (Tg) on the horizontal axis and water absorption characteristics (%) on the vertical axis.
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 correlation such that the water absorption increases as Tg increases. On the other hand, the cured product using the epoxy resin of formula (1) and the amine curing agent has high heat resistance, but has a low water absorption rate, which is different from the above correlation. It can be confirmed that it is a combination.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on August 1, 2014 (Japanese Patent Application No. 2014-157629), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The epoxy resin composition of the present invention provides a cured product that can simultaneously achieve high heat resistance and water resistance in the cured product, and thus is extremely useful for producing laminated boards such as printed wiring boards and build-up substrates. Material.

Claims (9)

An epoxy resin composition comprising 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. N is the number of repetitions and is 0 to 5.) A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to claim 1. The prepreg according to claim 2, wherein the fiber base material is a glass fiber base material. The prepreg according to claim 3, wherein the glass fiber substrate includes at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass. A metal-clad laminate in which a metal foil is laminated on at least one surface of the prepreg according to any one of claims 2 to 4. A resin sheet formed by forming an insulating layer made of the epoxy resin composition according to claim 1 on a film or a metal foil. A printed wiring board using the metal-clad laminate according to claim 5 as an inner layer circuit board. 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. A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to claim 7 or 8.

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