TW201609853A - Epoxy-resin-containing varnish, epoxy-resin-composition-containing varnish, prepreg, resin sheet, laminate board, printed circuit board, semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide an epoxy-resin-containing varnish that is highly stable in a solvent and that is manageable in a varnish state. The purpose of the present invention is also to provide an epoxy-resin-composition-containing varnish that uses the epoxy-resin-containing varnish, a prepreg and a resin sheet that comprise an impregnated substrate, and a laminate board, a printed substrate, and a semiconductor device that are produced from the prepreg and the resin sheet and that have high heat resistance and advanced dielectric characteristics. This epoxy-resin-containing varnish contains as essential components an epoxy resin that is represented by general formula (1) and an organic solvent. (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 1-5.).

Description

Epoxy-containing varnish, varnish containing epoxy resin composition, prepreg, resin sheet, laminated board, printed wiring board, semiconductor device

The present invention relates to an epoxy resin-containing varnish excellent in stability in a solution, a varnish containing the epoxy resin composition using the varnish, and a molded body thereof, and a cured product excellent in dielectric properties. Epoxy resin.

Further, the present invention relates to a varnish, a prepreg, a resin sheet, a laminated board, a printed wiring board, which is an epoxy resin-containing composition suitable for use as a high-performance electronic material, particularly a semiconductor sealing agent or a film substrate material. , semiconductor devices.

The epoxy resin composition is widely used in electrical, electronic parts, structural materials, adhesives, paints, and the like due to workability and excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance) of the cured product. in.

However, in recent years, in the field of electric/electronics, with the development of the resin composition, it is required to have high purity of the resin composition, moisture resistance, adhesion, dielectric properties, and a filler (inorganic or organic filler). Further improvement in various properties such as low filling with high filling and improved reactivity for shortening the molding cycle. Further, as a structural material, materials which are lightweight and excellent in mechanical properties are required for aerospace materials, entertainment/sports applications, and the like.

Especially in recent years, the communication between machines has increased significantly, and the traffic of people has increased significantly. In the obvious increase of the above traffic, the amount of information has been greatly increased.

At present, the communication frequency of smart phones or Wifis is increased, and smart phones use communication bands with frequencies from 700 MHz to 3.4 GHz. If wifi or the like, communication bands such as 2 to 5 GHz are used, so that dielectrics in a wide range of bands are used. Characteristics, especially dielectric loss tangent, become important (Non-Patent Document 1)

Moreover, the amount of information communication becomes very large, and how to transmit more information faster becomes important, and high-speed communication becomes an important factor for the substrate.

In addition, in order to keep the size of the battery, the size of the battery has been greatly reduced (Non-Patent Document 2). In turn, the function must be dramatically improved year by year. In such an environment, it is necessary to reduce the thickness and thickness of the substrate to be used, and it is necessary to have heat resistance and rigidity of the substrate which is a step resistance in the production.

As a material for high-speed communication, special resins such as polyphenylene ether or BT resin are mainly used depending on their characteristics. However, if used alone, it is difficult to operate and has insufficient characteristics to improve adhesion or strength. And used in combination with epoxy resin. In addition, in the case of the above-mentioned special resin, the combination of the above-mentioned special resin is increased in order to improve the dielectric properties (Non-Patent Document 3 and Non-Patent Document 4). ). In the combination with the above-mentioned special resin, if it is not used as a varnish, it cannot be blended, and if it is produced at the time of production, or if it is used for dispersion, the productivity is very poor. Furthermore, if the compatibility of the varnish is poor, or the crystals are precipitated and separated immediately after the production, the production cannot be stably performed, and it is difficult to establish it as a production business. Therefore, there is a demand for a highly functional epoxy resin which can be stably produced in the form of a varnish.

An epoxy resin of a bisphenylene aralkyl type may be cited as an epoxy resin having good dielectric properties. Although the epoxy resin has very good electrical properties, it has poor solubility in a solvent when it is formed into a substrate, and even if it is dissolved, crystals tend to precipitate, and heat resistance is difficult to be improved (Patent Document 1 and Patent) Document 20).

On the other hand, an epoxy resin having high heat resistance is an epoxy resin having a high crosslinking density.

The epoxy resin having a high crosslinking density is very poor in dielectric properties because of its high crosslinking density. Moreover, it becomes brittle and the thermal decomposition property deteriorates. When the crosslinking density is lowered, these characteristics are improved, but the heat resistance is lowered, and the glass transition point (Tg) is lowered.

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

Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-229436

Non-patent literature

Non-Patent Document 1: References SIG-1-3-2 The use of radio waves in China, such as the Ministry of Internal Affairs and Communications, [online], [Search on July 29, 2014], Internet <http://www.soumu .go.jp/main_sosiki/joho_tsusin/policyreports/chousa/wire/pdf/050915_2_san2.pdf>

Non-Patent Document 2: "76% increase in capacity, new battery decomposition of secondary batteries, both in area and thickness (3)" 2012/3/23 12:35 information source Japan Economic News electronic version, [online], 2012 March 23, 2014 [Search July 29, 2014], Internet <http://www.nikkei.com/article/DGXNASFK2103C_R20C12A3000000/>

Non-Patent Document 3: Hitachi-chem Technical Report No. 56 (2013. December), [online], December 2013, [Search for July 29, 2014], Internet <URL: http://www.hitachi -chem.co.jp/ japanese/report/056/56_tr02.pdf>

Non-Patent Document 4: Lichang Industrial RISHO NEWS Technical Report No91, [online], [Search July 29, 2014], Internet <URL: http://www.risho.co.jp/rishonews/technical_report/tr91 /r180_tr91.pdf>

An object of the present invention is to provide an epoxy resin-containing varnish which can be used in a varnish form having high stability in a solvent, a varnish containing the epoxy resin composition using the same, and a prepreg which is impregnated on the substrate. And a resin sheet, and a laminate, a printed wiring board, and a semiconductor device which are manufactured by these and have high heat resistance and high dielectric properties.

The present inventors conducted intensive studies in view of the above-described actual circumstances, and as a result, completed the present invention.

That is, the present invention provides: (1) an epoxy resin-containing varnish which is an essential component of an epoxy resin and an organic solvent represented by the following general formula (1).

(wherein the ratio of (a)(b) is (a)/(b)=1~3; G is a glycidyl group; n is a repeating number, 0 to 5); (2) an epoxy group a varnish of a resin composition using the epoxy resin-containing varnish described in the above (1), and (3) a prepreg using the epoxy resin-containing varnish described in the above (1) or the above (2) (4) A resin sheet using the epoxy resin-containing varnish described in (1) above or the varnish containing the epoxy resin composition described in (2) above (5) A laminated board obtained by molding the prepreg according to (3) or the resin sheet described in (4) above; (6) a printed wiring board which is made of the above (3) The prepreg according to the above description or the resin sheet according to the above (4) is cured; (7) a printed wiring board comprising the laminated board according to the above (5); (8) a semiconductor device The printed wiring board according to the above (6) or (7).

Since the epoxy resin-containing varnish of the present invention has high heat resistance and high dielectric properties, it can be used for laminated boards and printed wiring boards.

According to the present invention, it is possible to provide an epoxy resin-containing varnish which can be used in a varnish form having high stability in a solvent, a varnish containing the epoxy resin composition using the same, and a prepreg which is impregnated on the substrate. And a resin sheet, and a laminate, a printed wiring board, and a semiconductor device which are manufactured by these and have high heat resistance and high dielectric properties.

Fig. 1 is a graph showing the relationship between the heat resistance (TMA Tg) and the dielectric loss tangent of the laminate obtained in the examples and the comparative examples.

Fig. 2 is a graph showing the relationship between the heat resistance (DMA Tg) and the dielectric loss tangent of the laminate obtained in the examples and the comparative examples.

The epoxy resin-containing varnish of the present invention contains an epoxy resin and an organic solvent.

The epoxy resin used in the epoxy resin-containing varnish of the present invention is an epoxy resin represented by the following formula (1) as an essential component.

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

Further, the organic solvent is preferably a ketone selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, acetone, and isophorone; and aromatic hydrocarbons such as toluene and xylene; One or more kinds of esters such as propylene glycol monomethyl ether acetate, ethyl lactate, and γ-butyrolactone.

In order to improve the surface of the solvent during drying, it is effective to add a high boiling point solvent such as dimethylacetamide or N-methylpyrrolidone, dimethyl hydrazine or carbitol acetate as needed. The state at the time of drying can be changed by adding methanol, ethanol, propanol, butanol or the like.

The use of a halogen-based solvent is not good in terms of environmental problems, and diethyl ether or the like is not preferable in terms of its risk.

Further, the epoxy resin-containing varnish of the present invention is in the range of a uniform solution (having a haze of 200 or less when measured at any temperature of 0 ° C to 50 ° C to a quartz cell of 1 cm square), in addition to the above In addition to the epoxy resin and the solvent, the following coupling agent, rubber component, or polymer component may be added.

The resin concentration is preferably from 10 to 80% by weight. Especially good is 15~75%. When the concentration is high, it can be diluted in the subsequent steps, so it does not become a big problem. However, if the fluidity cannot be ensured, it is not only difficult to operate, but also the amount of waste to the can or the drum is increased, and the amount of waste is increased. Big, and the load on the environment becomes bigger.

The resin viscosity is preferably between 10 ° C and 50 ° C at any temperature of 10 mPa. s~100Pa. The range of s, especially 100mPa. s~80Pa. s. Regarding the viscosity, there is a suitably preferred viscosity depending on the coating step. For example, when applying a tens of micrometers to several hundreds of micrometers to the surface support by using an applicator or the like, the film thickness of the resin sheet formed by the shrinkage or the formed resin sheet may be 5 to 80 Pa. The viscosity around s.

In the method for producing an epoxy resin-containing varnish of the present invention, for example, when the solvent is stirred, the epoxy resin used in the present invention is added in portions, and the epoxy resin is gradually dissolved while being uniformly formed.

The time for dissolution in batch mode is usually 30 to 10 hours. About dissolution The temperature is preferably dissolved at a temperature lower than the softening point of the resin by 20 ° C or higher or a temperature higher than the softening point of the resin. In the temperature range of the softening point of the resin to the softening point of -20 ° C (specifically, if the softening point is 80 ° C, 80 to 60 ° C), the resin adheres to each other, the pot is broken, and the pot is damaged. However, the possibility that the metal or the glass piece in the pot is mixed as a foreign matter is not preferable.

The epoxy resin-containing varnish obtained in the above manner is preferably stored by filtration using a filter having a mesh fineness of 100 μm or less. Especially preferred is 1~78μm. In the case of a filter having a mesh of more than 100 μm, in the case where foreign matter is mixed, there is a possibility that the support becomes uneven after coating and the support is damaged, which is not preferable. When a filter having a mesh fineness of less than 1 μm is used, there is a tendency that the filtration speed becomes very slow and the productivity is poor.

The filtration temperature is usually 10 to 100 ° C, and particularly preferably 20 to 90 ° C.

It is easy to filter by increasing the fluidity by heating, but if it exceeds 100 ° C, it depends on the boiling point of the solvent, but the odor from the filtrate becomes strong and the person is injured. Poor. Further, if it is less than 10 ° C, the fluidity is liable to be deteriorated, and the production is time-consuming and therefore unsatisfactory.

With respect to the epoxy resin-containing varnish of the present invention obtained as described above, precipitation of crystals or precipitation of a resin was not observed at 5 ° C for 2 months or more at 0 ° C for 1 month or longer.

In the present invention, the prepreg or the resin sheet can be molded by using the epoxy resin-containing varnish of the present invention.

The varnish containing the epoxy resin composition of the present invention uses the epoxy resin-containing varnish of the present invention.

In the varnish containing the epoxy resin composition of the present invention, as a further added material, it is a special resin, another epoxy resin used together, a hardener for an epoxy resin, a hardening accelerator, a coupling agent, The inorganic filler preferably contains at least two of these types (that is, three or more kinds in combination with an epoxy resin-containing varnish).

As a special resin, those which are described above include polyphenylene ether resin and benzo. A resin such as a resin, a soluble polyimine, a soluble polyamine, a BT resin, a cyanate resin, a maleimide resin, a styrene/maleic anhydride copolymer or a modified body thereof.

The amount of the resin used is preferably from 10 to 90% by weight, particularly preferably from 20 to 80% by weight, based on the total amount of the resin.

Specific examples of the other epoxy resin which can be used in combination with the epoxy resin composition represented by the formula (1) used in the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, and Biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) Polycondensate of various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); And various diene compounds (dicyclopentadiene, terpenes, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, two a polymer of isopropenylbiphenyl, butadiene, isoprene, etc.; a phenol and a ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone) a polycondensate of the above; a polycondensate of the above phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.); the above phenols and aromatic dichloro a polycondensate of the class (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); the above phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxy) a polycondensate of methyl biphenyl, bisphenoxymethylbiphenyl, or the like; a glycidyl ether ring obtained by subjecting the bisphenol to a polycondensate or an alcohol of various aldehydes to be epoxy-propylated Oxygen resin, alicyclic epoxy resin, epoxypropylamine epoxy resin, ring The oxypropyl ester epoxy resin or the like is not limited to these as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.

In the case of blending the epoxy resin composition used in the present invention, a hardener may be used. Specific examples of the curing agent that can be used include an amine compound (including an aniline resin), or phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, and tetrahydrophthalic acid. An acid anhydride compound such as an acid anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride; bisphenols, phenols (phenol, alkane) Substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxy naphthalene) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkane) Polycondensates of substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.; phenols and various diene compounds (dicyclopentadiene, terpenes, Vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polymers; phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) The polycondensate or the like is not limited thereto. These may be used alone or in combination of two or more.

In the epoxy resin composition used in the present invention, the amount of the curing agent used in the case of using the curing agent is preferably from 0.6 to 1.1 equivalents per equivalent of the epoxy group of the epoxy resin. When the epoxy group exceeds 1.1 equivalents and is less than 0.6 equivalents, the hardener remains and the hardening becomes incomplete, and good hardened physical properties cannot be obtained. In the case where the epoxy resin and the hardenable special resin are contained, it is not in the above range, and it is necessary to use the amount of the hardener which is relative to the residual epoxy group minus the amount of the epoxy group consumed by the specific resin. Adjust as appropriate.

The epoxy resin composition used in the present invention may further contain a curing accelerator. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl) a tertiary amine such as phenol or 1,8-diazabicyclo[5,4,0]undecene-7; a phosphine such as triphenylphosphine; or a metal compound such as stannous octoate. The hardening accelerator may be used in an amount of 0.1 to 10.0 parts by weight, based on 100 parts by weight of the epoxy resin.

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

The filler to be blended as needed is not particularly limited, and examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, calcium carbonate, calcium silicate, barium sulfate, talc, clay, and magnesium oxide. , alumina, cerium oxide, iron oxide, titanium oxide, aluminum nitride, tantalum nitride, boron nitride, mica, glass, quartz, mica, and the like. Further, in order to impart a flame retardant effect, a metal hydroxide such as magnesium hydroxide or aluminum hydroxide is preferably used. However, it is not limited to these. Further, two or more kinds may be used in combination. Among these inorganic fillers, cerium oxide such as molten cerium oxide or crystalline cerium oxide is preferred because it is low in cost and excellent in electrical reliability.

In the epoxy resin composition used in the present invention, the inorganic filler is used in an amount of usually 10% by weight to 95% by weight, preferably 10% by weight to 80% by weight, more preferably 10% by weight. A range of 75 wt%. If the amount of the inorganic filler used is too small, the effect of flame retardancy may not be obtained, and the modulus of elasticity may be lowered. Further, if the amount of the inorganic filler used is too large, it may be made into a varnish dissolved in the sealed solution. When the filler precipitates, a homogeneous molded body cannot be obtained.

Further, the shape, particle diameter, and the like of the inorganic filler are not particularly limited, but are usually 0.01 to 50 μm in particle diameter, preferably 0.1 to 20 μm.

In the epoxy resin composition used in the present invention, a coupling agent may be blended in order to improve the adhesion of the glass cloth or the inorganic filler to the resin component. As the coupling agent, any of the previously known ones can be used, and examples thereof include vinyl alkoxy decane, alkyl alkoxy decane, styryl alkoxy decane, and methacryl oxiran alkoxy decane. Examples of various alkoxydecane compounds such as acryloxy alkoxydecane, amino alkoxy decane, mercapto alkoxy decane, and isocyanato alkoxy decane, alkoxide titanium compounds, aluminum chelate compounds, and the like. These may be used alone or in combination of two or more. As a method of adding the coupling agent, the surface of the inorganic filler may be treated with a coupling agent in advance, and then mixed with a resin, or the coupling agent may be mixed with the resin, and then the inorganic filler may be mixed.

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

Further, a known varnish may be blended into the varnish containing the epoxy resin composition of the present invention as needed. Specific examples of the additives that can be used include polybutadiene and modified substances thereof, modified products of acrylonitrile copolymer, polystyrene, polyethylene, fluororesin, polyoxyxide gel, polyoxygenated oil, and And colorants such as carbon black, phthalocyanine blue, and phthalocyanine.

The prepreg of the present invention will be described.

In the prepreg system of the present invention, the above-mentioned epoxy resin-containing varnish or the above-mentioned varnish containing the epoxy resin composition is used, for example, such that the varnish is impregnated into the fiber substrate. Thereby, a prepreg excellent in heat resistance, low expansion property, and flame retardancy can be obtained.

Examples of the fiber base material include glass fiber substrates such as glass woven fabrics, glass nonwoven fabrics, and cellophane; and woven fabrics composed of synthetic fibers such as paper, aromatic polyamide, polyester, aromatic polyester, and fluororesin. Cloth or non-woven fabric; woven fabric, non-woven fabric, fiber mat (mat) composed of metal fiber, carbon fiber, mineral fiber, and the like. These substrates may be used singly or in combination. Among these, a glass fiber substrate is preferred. Thereby, the rigidity and dimensional stability of the prepreg can be improved.

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

The method of impregnating the above-mentioned resin composition with the above-mentioned fiber base material, for example, a method of immersing a base material in a resin-containing varnish, a method of coating by various coaters, a method of blowing by a sprayer, etc. . Among these, a method of immersing the substrate in a resin-containing varnish is preferred. Thereby, the impregnation property of a resin composition with respect to a base material can be improved. Further, in the case where the substrate is immersed in a resin-containing varnish, a usual impregnation coating apparatus can be used.

For example, the epoxy resin composition is impregnated into a substrate such as a glass cloth directly or in the form of a varnish dissolved or dispersed in a solvent, and is usually dried at a temperature of 80 to 200 ° C (wherein the solvent is used). In this case, it is preferably at a temperature at which the solvent is volatilized, and is preferably dried at a temperature of 150 to 200 ° C for 1 to 30 minutes, preferably 1 to 15 minutes, thereby obtaining a prepreg.

Further, a method in which a resin sheet described below is pressed against a glass cloth and transferred to obtain a prepreg may be applied.

The resin sheet of the present invention will be described.

The resin sheet using the epoxy resin-containing varnish or the varnish containing the epoxy resin composition of the present invention is coated by various methods such as a gravure coating method, a screen printing method, a metal mask method, a spin coating method, and the like which are known per se. In the method, the varnish is applied to a planar support after drying to a specific thickness, for example, 5 to 100 μm, and is dried, but the coating method is based on the type and shape of the support. The size, the film thickness of the coating, the heat resistance of the support, and the like are appropriately selected. Examples of the planar support include polyamine, polyamidiamine, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ketone, and polyether oxime. A film made of various polymers such as imine, polyetheretherketone, polyketone, polyethylene, polypropylene, Teflon (registered trademark), and/or a copolymer thereof, or a metal foil such as a copper foil.

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

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

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

The laminated board of the present invention will be described.

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

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

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

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

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

Here, the conditions for performing the heat and pressure molding are not particularly limited, and examples thereof can be carried out at a temperature of 60 to 160 ° C and a pressure of 0.2 to 3 MPa. Moreover, the conditions for performing heat curing are not particularly limited, and if an example is given, it can be carried out at a temperature of 140 to 240 ° C for 30 to 120 minutes.

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

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

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

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

The resin residue or the like after the laser irradiation is preferably removed by using an oxidizing agent such as permanganate or dichromate. Further, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by metal plating can be improved.

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

Further, in the case of using a resin sheet having a metal foil or a prepreg, the circuit is formed by etching in order to prevent the metal foil from being used as a conductor circuit. In this case, when the insulating resin sheet with the base material of the thick copper foil is used, it becomes difficult to form a fine pitch in the subsequent circuit pattern formation. Therefore, an extremely thin copper foil of 1 to 5 μm is used. Alternatively, a case where a copper foil of 12 to 18 μm is thinned by etching to a half etching of 1 to 5 μm is performed.

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

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

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

Regarding the connection method of the semiconductor element and the multilayer printed wiring board, the flip chip bonding is used. After the electrode or the connection electrode portion on the substrate is aligned with the solder bump of the semiconductor element, the solder bump is heated to a melting point or higher by using an IR reflow soldering apparatus, a hot plate, or another heating device to laminate the multilayer printed wiring substrate. Bonding is performed by fusion bonding with the solder bumps. In addition, in order to improve the connection reliability, a metal layer having a relatively low melting point such as solder paste may be formed in advance on the connection electrode portion on the multilayer printed wiring board. The flux may be applied to the surface of the solder bump and the connection electrode portion on the multilayer printed wiring board before the bonding step, thereby improving connection reliability.

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

Example

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

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

‧Epoxy equivalent

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

‧Softening Point

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

Synthesis Example 1

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

Example 1 and Comparative Example 1

The epoxy resin (EP1) obtained in Synthesis Example 1 and the epoxy resin for comparison (manufactured by Nippon Chemical Co., Ltd.) were dissolved in methyl ethyl ketone as a solvent so that the resin concentration became 60% by weight. A varnish containing epoxy resin is obtained.

Regarding the obtained epoxy resin-containing varnish of the present invention, precipitation of crystals or precipitation of a resin was not observed at 5 ° C for 2 months or more at 0 ° C for 1 month or longer. On the other hand, regarding the comparative epoxy resin-containing varnish, the molecular weight of the epoxy resin contained was substantially equal, but precipitation of crystals was confirmed at the second week.

Example 2

As a varnish containing an epoxy resin composition, 21 parts of (EP1) obtained in Synthesis Example 1 and 20 parts of a curing agent (manufactured by a Japanese chemical manufacturer, biphenyl aralkyl resin KAYAHARD GPH-65) and a hardening accelerator are prepared. 0.2 parts, 40 parts of methyl ethyl ketone and uniformly dissolved were prepared. The obtained varnish was applied to Polyimide using a 100-micrometer applicator, and then dried at 120 ° C for one minute by a nitrogen air dryer using a hot air dryer to obtain a resin sheet of the present invention. The DSC of the obtained resin sheet was measured, and it was confirmed that there was a heat generation peak at 82 ° C, which was a hardenable sheet.

Example 3

With respect to the epoxy resin (EP1) obtained in Synthesis Example 1, the hardener was blended in an equivalent amount with respect to the epoxy equivalent of 1 molar equivalent, and was blended in an amount of 1 part by weight based on 100 parts by weight of the epoxy resin. The catalyst was mixed with methyl ethyl ketone to adjust the resin concentration to 80%, and a varnish containing the epoxy resin composition was prepared in the composition shown in Table 1. Using a 100 micron applicator, the separately obtained varnish was applied to Polyilex, and the hot air was passed through the nitrogen gas at 120 ° C. The desiccator was dried for 10 minutes to obtain a resin sheet of the present invention.

Comparative example 2

In the third embodiment, the epoxy resin (EP1) was changed to the other epoxy resin shown in Table 1, and the comparative resin sheet was obtained by the same blending method.

Example 4~6

Ten pieces of the resin sheet obtained in Example 3 were peeled off from the polyimide, and placed on a hot plate press, and then formed by heating and pressurizing at 10 kg/cm ² and a temperature of 180 ° C for 10 minutes. Make a laminate. The characteristics of the laminated sheets produced were measured by the following items and methods. The measurement results are shown in Table 1.

‧Elastic Modulus (DMA)

Dynamic viscoelasticity tester: TA-instRuments, DMA-2980

Measuring temperature range: -30~280°C

Heating rate: 2 ° C / min

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

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

‧ glass transition temperature (Tg)

Thermomechanical measuring device (TMA): Thermomechanical measuring device manufactured by TA-instRuments TMA Q400EM

Heating rate: 2 ° C / min

‧ dielectric constant, dielectric loss tangent

Measurement using a cavity resonator and a fixture of 1 GHz manufactured by Kanto Electronics Applied Chemicals (using a cut of 0.5 mm × 70 mm)

Comparative Example 3~9

In the examples 4 to 6, the resin sheet of the present invention was changed to the comparative resin sheet obtained in Comparative Example 2, and a laminate for comparison was produced by the same method. The measurement results are shown in Table 1.

Further, the hardened physical properties obtained in Table 1 are shown in Fig. 1 with the heat resistance (TMA Tg) as the horizontal axis and the dielectric loss tangent as the vertical axis, which will be hardened for Table 1. The physical properties are shown in Fig. 2 with the heat resistance (DMA Tg) as the horizontal axis and the dielectric loss tangent as the vertical axis.

1 and 2, when other epoxies containing an epoxy resin are used, the dielectric properties are increased in proportion to the improvement in heat resistance (deterioration) and the slope thereof is substantially constant. On the other hand, in the case of using the epoxy resin-containing varnish of the present invention, it is understood that the slope of the deterioration of the dielectric properties as the heat resistance is improved is gentle.

That is, it is understood that the resin composition using the epoxy resin-containing varnish of the present invention tends to have a low dielectric loss tangent with respect to heat resistance, and has a high heat resistance and dielectric properties.

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

In addition, the present application is based on a Japanese patent application filed on Aug. 1, 2014 (Japanese Patent Application No. 2014-157632), the entire contents of which is incorporated by reference. Again, all references cited herein are hereby incorporated by reference in their entirety.

Industrial availability

The epoxy resin-containing varnish of the present invention has high heat resistance and high dielectric properties, and thus can be used for laminated boards and printed wiring boards, and can be preferably used as a sealing material for high-performance electronic materials, particularly semiconductors. Agent, film substrate material.

Claims (8)

An epoxy resin-containing varnish having an epoxy resin and an organic solvent represented by the following general formula (1) as essential components. (In the formula, the ratio of (a) to (b) is (a)/(b) = 1 to 3; G represents a glycidyl group; and n is a repeating number of 0 to 5). A varnish containing an epoxy resin composition using the epoxy resin-containing varnish of the first application of the patent scope. A prepreg comprising the epoxy resin-containing varnish of claim 1 or the varnish containing the epoxy resin composition of claim 2 of the patent application. A resin sheet which uses the epoxy resin-containing varnish of the first application of the patent application or the varnish of the epoxy resin composition of claim 2 of the patent application. A laminate comprising a prepreg of claim 3 or a resin sheet of claim 4 of the patent application. A printed wiring board obtained by hardening a prepreg of claim 3 or a resin sheet of claim 4 of the patent application. A printed wiring board comprising the laminated board of the fifth aspect of the patent application. A semiconductor device comprising the printed wiring board of claim 6 or 7.