JP2010084019A - Resin composition and cured product - Google Patents

Abstract

A resin composition capable of easily reducing the roughness of the surface of a cured product by a roughening treatment so as to have excellent detachability of silica on the surface of the cured product and excellent adhesion, and heating the resin composition Provision of a cured product obtained by curing.
One or more curing agents selected from the group consisting of a biphenyl skeleton-containing phenolic curing agent, a dicyclopentadiene skeleton-containing phenolic curing agent, a triazine skeleton-containing phenolic resin, and a limonene skeleton-containing phenolic resin, and a bisphenol-type epoxy A resin composition in which a resin, a curing accelerator, and silica are blended, wherein the bisphenol-type epoxy resin is a compound in which two epoxy groups are introduced into one molecule of bisphenol or a derivative thereof, and the ratio of the number of molecules. 79-84% of a resin composition characterized by containing; Hardened | cured material characterized by heat-curing this resin composition.
[Selection figure] None

Description

  The present invention is a resin composition in which the surface of a cured product can be easily roughened so that the surface of the cured product has good silica detachability and the roughness is reduced, and the resin composition is heated and cured. It relates to a cured product.

  Conventionally, a resin used for a semiconductor device or the like is required to have high adhesiveness. For this purpose, various resin compositions containing an epoxy resin or the like have been developed. For example, attempts have been made to improve adhesiveness by containing a filler treated with imidazole silane (for example, Patent Document 1).

On the other hand, in the case of a circuit board or the like, after the resin composition is cured, the surface of the cured product is generally roughened in order to further improve the adhesion of the cured product. In the roughening treatment, the surface of the cured product is dissolved or deteriorated by the roughening treatment liquid to form a concavo-convex shape, thereby not only enhancing the adhesion of the surface but also providing an anchor effect.
Japanese Patent Laid-Open No. 2002-128772

  In recent years, the L / S of copper wiring has become even smaller. Along with this, it is required to reduce the roughness of the surface after the roughening treatment in a circuit board or the like that requires a thin insulating layer. However, if the surface roughness is too small, the adhesion may be inferior when a metal layer such as copper plating is formed on the surface of the cured product of the resin composition serving as the insulating layer. On the other hand, in order to improve the adhesion, the surface roughness after the roughening treatment has to be increased, and it has been difficult to design a resin that can cope with finer wiring. In addition, even if the hardened product itself is difficult to be etched even if it is attempted to detach silica during the roughening treatment, there is a problem that silica is not detached. In this case, it is necessary to use a resin that is easily etched. However, the resin that is easily etched has a problem that the roughness of the surface becomes large and the variation in roughness becomes large. In the case of using a resin that is difficult to be etched during the roughening treatment, there is a problem that it is difficult to desorb silica. As described above, a practical resin composition is proposed as a resin composition that can easily reduce the surface roughness by roughening treatment and give a cured product with good silica detachment so as to exhibit good adhesion. The fact was not.

  The present invention has been made in view of the above circumstances, and it is possible to easily reduce the roughness of the surface of the cured product by roughening treatment so that the detachability of silica on the surface of the cured product is good and exhibits excellent adhesion. It is an object to provide a resin composition and a cured product obtained by heating and curing the resin composition.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by adjusting the number of repeating units of the bisphenol type epoxy resin in the resin composition containing the bisphenol type epoxy resin. It came to be completed.

That is, to solve the above problem,
The invention according to claim 1 includes one or more curing agents selected from the group consisting of a biphenyl skeleton-containing phenolic curing agent, a dicyclopentadiene skeleton-containing phenolic curing agent, a triazine skeleton-containing phenol resin, and a limonene skeleton-containing phenol resin. A resin composition in which a bisphenol type epoxy resin, a curing accelerator, and silica are blended, wherein the bisphenol type epoxy resin is a compound in which two epoxy groups are introduced into one molecule of bisphenol or a derivative thereof, It is a resin composition characterized by containing 79 to 84% in terms of the number of molecules.
The invention according to claim 2 is that the bisphenol type epoxy resin is a bisphenol A type epoxy resin represented by the following general formula (1), wherein n = 0, The resin composition according to claim 1, which contains ˜84%.

  (In the formula, n is an integer of 0 or more.)

The invention according to claim 3 is the resin composition according to claim 1 or 2, wherein the compounding amount of the silica is 15 to 40% by mass in the total amount of the compounding components excluding the solvent component.
The invention according to claim 4 is characterized in that a phenoxy resin is further blended, and the blending amount of the phenoxy resin is 5 to 30% by mass in the total blending component excluding the solvent component. It is a resin composition as described in any one.
The invention concerning Claim 5 is a hardened | cured material formed by heat-curing the resin composition as described in any one of Claims 1-4.

  According to the present invention, there is provided a resin composition that has excellent silica detachability on the surface of a cured product obtained by heat curing, exhibits excellent adhesion, and can easily reduce the roughness of the surface of the cured product by roughening treatment. can get.

The present invention will be described in detail below.
<Resin composition>
The resin composition of the present invention comprises one or more curing agents selected from the group consisting of a biphenyl skeleton-containing phenolic curing agent, a dicyclopentadiene skeleton-containing phenolic curing agent, a triazine skeleton-containing phenolic resin, and a limonene skeleton-containing phenolic resin. , A resin composition containing a bisphenol-type epoxy resin, a curing accelerator, and silica, wherein the bisphenol-type epoxy resin is a molecule in which two epoxy groups are introduced into one molecule of bisphenol or a derivative thereof. It is characterized by containing 79 to 84% by number.
Here, the “ratio of the number of molecules” can be determined from the measurement value of a known molecular weight distribution measurement method. The molecular weight distribution measurement may be performed, for example, by detecting UV absorption.

[Bisphenol type epoxy resin]
The bisphenol-type epoxy resin is obtained by reacting bisphenol or a derivative thereof with an epoxide derivative, and can be obtained by reacting bisphenol or a derivative thereof with epichlorohydrin. Of these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and the like can be exemplified, and bisphenol A type epoxy resin is particularly preferable.

  In the present invention, a bisphenol-type epoxy resin containing 79 to 84% of a compound in which two epoxy groups are introduced into one molecule of bisphenol or a derivative thereof in terms of the number of molecules is used. Here, the “derivative of bisphenol” refers to one having only one bisphenol skeleton.

  The bisphenol A type epoxy resin is most preferably one containing 79 to 84% in terms of the number of molecules represented by the following general formula (1), where n = 0.

  (In the formula, n is an integer of 0 or more.)

In the formula, when the ratio of n = 0 is 65% or more and less than 79% and the ratio of the total amount of n = 0 and n = 1 is 95 to 100%, the cured product has a glass transition. Although the point (hereinafter abbreviated as Tg) becomes very high, it becomes difficult to roughen and the silica detachability deteriorates. Further, when the ratio of n = 0 is less than 79% and the ratio of n = 1 is as small as less than 10%, the Tg of the cured product does not appear, and the curing becomes uneven, As a result, it is very easy to etch during the roughening treatment, the surface roughness becomes large, and the curing characteristics also deteriorate.
On the other hand, when the ratio of n = 0 exceeds 84%, the cured product is very uniform and dense. However, since the cured product is dense, it is difficult to etch during the roughening treatment, and the detachment property of silica deteriorates. End up. Furthermore, even if the conditions for the swelling treatment and the roughening treatment are changed, the roughening property is hardly changed, and the detachability of silica cannot be improved.

As a hardened | cured material formed by hardening | curing the resin composition of this invention, the following can be illustrated. That is, the surface roughness when a film having a thickness of 40 μm cured under conditions of 150 ° C./30 minutes is subjected to roughening treatment under conditions of swelling: 60 ° C./20 minutes and roughening: 80 ° C./20 minutes ( Ra) is preferably 30 nm ≦ Ra ≦ 250 nm.
When the surface roughness (Ra) exceeds 250 nm, the roughened surface becomes too rough and various problems are likely to occur. For example, electroless and electrolytic plating is performed after the roughening treatment to form a copper pattern, and then copper is removed for unnecessary portions. However, when the roughened surface is rough, a metal such as copper and palladium is used. Removal is likely to be incomplete. Furthermore, regarding fine pattern formability that is expected to develop in the future, pattern formation tends to be difficult when the roughened surface is rough.
On the other hand, when the surface roughness is less than 30 nm, when the metal layer is formed by subjecting the cured product of the present invention to a roughening treatment, for example, by plating with metal such as copper, the metal layer and the cured body The adhesiveness (peel strength) may be weakened. In addition, after performing pattern formation on the metal layer, using a film-like insulating resin or the like and laminating the cured body and the pattern so as to seal, the film-like insulating resin or the like and the cured body The adhesiveness of the film becomes insufficient, and the dry film may be easily peeled off.

  As a cured product obtained by curing the resin composition of the present invention, Tg in DMA measurement is 120 ° C. or more, tensile strength at room temperature is 50 MPa or more, and at room temperature. A Young's modulus is 1.5 GPa or more and less than 7 GPa.

  A bisphenol type epoxy resin may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.

  The blending amount of the bisphenol-type epoxy resin in the blending component excluding the solvent component is preferably 15 to 40% by weight, and more preferably 20 to 35% by weight.

[Curing agent]
One or more curing agents selected from the group consisting of the biphenyl skeleton-containing phenolic curing agent, dicyclopentadiene skeleton-containing phenolic curing agent, triazine skeleton-containing phenolic resin, and limonene skeleton-containing phenolic resin (hereinafter abbreviated as curing agent). ) Can be appropriately selected from known ones. Among these, a biphenyl skeleton-containing phenolic curing agent or a dicyclopentadiene skeleton-containing phenolic curing agent is preferable, and a biphenyl skeleton-containing phenolic curing agent is more preferable.

  Biphenyl skeleton-containing phenolic curing agent, dicyclopentadiene skeleton-containing phenolic curing agent, triazine skeleton-containing phenolic resin and limonene skeleton-containing phenolic resin may be used alone or in combination of two or more. May be. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.

  It is preferable that the compounding quantity of the hardening | curing agent in the compounding component except a solvent component is 15-40 mass%, and it is more preferable that it is 20-35 mass%.

[Curing accelerator]
A well-known thing can be suitably selected as said hardening accelerator. Of these, an imidazole skeleton-containing curing accelerator, an imidazoline skeleton-containing curing accelerator, or a triazine skeleton-containing curing accelerator is preferable.
Examples of the imidazole skeleton-containing curing accelerator, imidazoline skeleton-containing curing accelerator or triazine skeleton-containing curing accelerator include imidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole. 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]- Ethyl-s-tria 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid addition Product, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazoline, 2,3-dihydro-1H- Pyrrolo [1,2-a] benzimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2,4-diamino-6-vinyl-s Triazine, 2,4-diamino-6-vinyl-s-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s- Examples include triazine isocyanuric acid adducts.
Moreover, you may use imidazole silane etc. which are normally used for the surface treatment of a silica as a hardening accelerator.

A hardening accelerator may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
Moreover, 1 mass% or less may be normally sufficient as the compounding quantity of the hardening accelerator in the compounding components except a solvent component, and it is preferable that it is 0.5-0.9 mass%.

[silica]
Silica includes crystalline silica obtained by pulverizing natural silica raw material, crushed fused silica obtained by flame melting and pulverizing, spherical fused silica obtained by flame melting, pulverizing and flame melting, fumed silica (Aerosil) Or synthetic silica such as sol-gel silica. Since synthetic silica often contains ionic impurities, fused silica is preferably used in terms of purity.

  Examples of the shape of silica include a true spherical shape and an indefinite shape. When the roughened resin is subjected to a roughening treatment, the silica is more easily detached, so that it is preferably spherical.

  In the present invention, it is preferable to use silica having an average particle diameter of 5 μm or less in order to obtain a fine rough surface. When the average particle diameter is larger than 5 μm, it becomes difficult for silica to be detached when a roughening treatment is performed on the cured resin, and the pores formed in the detached portion become larger, resulting in a rough surface roughness.

The average particle diameter of silica is preferably 1 μm or less. When the average particle diameter is 1 μm or less, the silica is more easily detached when the resin-cured product is subjected to a roughening treatment, and the pores formed on the surface of the detached cured product are further reduced.
A median diameter (d50) value of 50% can be adopted as the average particle diameter of silica, and it can be measured with a laser diffraction / scattering particle size distribution analyzer.

  The maximum particle diameter of silica is preferably 5 μm or less. When the maximum particle size is 5 μm or less, the silica is more easily detached when the resin composition is subjected to a roughening treatment, and further, relatively coarse irregularities are not formed on the surface of the cured product. Can be formed.

The specific surface area of silica is preferably 3 m ² / g or more. When the specific surface area is less than 3 m ² / g, for example, when a metal plating layer such as copper is formed on the surface of the cured product, the adhesion between the cured product and the metal plating may not be sufficient. There is a risk that the characteristics will deteriorate. The specific surface area can be determined by the BET method.

  Silica may be used as a silica slurry in a state dispersed in a solvent. By using the silica slurry, workability and productivity can be improved during the production of the resin composition.

Silica may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
Moreover, it is preferable that the compounding quantity of the silica in a compounding component except a solvent component is 15-40 mass%, and it is more preferable that it is 20-35 mass%.

In the present invention, as the silica, a silica component whose surface is treated with a silane coupling agent may be blended.
The silica component is preferably one in which 100 parts by mass of the silica is surface-treated with 0.5 to 20 parts by mass of a silane coupling agent, and is surface-treated with 1 to 4.0 parts by mass of a silane coupling agent. Is more preferable. By making the sila coupling agent 0.5 parts by mass or more, the dispersibility of the silica component can be further enhanced. Furthermore, by increasing the dispersibility of the silica component, it is possible to reduce variations in the surface roughness of the roughened cured body surface. Furthermore, the Tg of the cured product can be increased.
Silica surface-treated with a silane coupling agent can be used as a silica slurry in a state of being dispersed in a solvent, like untreated silica. By using such a silica slurry, workability and productivity can be improved during the production of the resin composition.

  A general silane compound can be used as the silane coupling agent. Among these, one or more selected from the group consisting of epoxy silane, amino silane, isocyanate silane, acryloxy silane, methacryloxy silane, vinyl silane, styryl silane, ureido silane, sulfide silane and imidazole silane are preferable. Further, the silica may be surface-treated with an alkoxysilane such as silazane.

  A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.

Examples of the method for surface-treating the silica with a silane coupling agent include a dry method and a wet method.
Examples of the dry method include a method of obtaining the silica component by directly attaching a silane coupling agent to silica and dehydrating and condensing the silane coupling agent and silica.
As a wet method, a silica slurry containing silica is stirred, a silane coupling agent is added, stirred, filtered, dried, and the silane compound and silica are dehydrated and condensed by heating to obtain the silica component. A method can be exemplified.

[Optional ingredients]
In the resin composition of the present invention, other optional components may be blended as necessary in addition to the above essential components within a range not impeding the effects of the present invention. Preferred examples of optional components include resins copolymerizable with the bisphenol-type epoxy resin, other curing agents other than the curing agent, and organic layered silicates.

(Resin copolymerizable with bisphenol type epoxy resin)
In the present invention, in addition to the bisphenol type epoxy resin, a resin copolymerizable with the epoxy resin (hereinafter abbreviated as other resin) may be used in combination. Such a resin can be arbitrarily selected according to the purpose, but preferred examples include polyfunctional biphenyl skeleton-containing epoxy resins and phenoxy resins.

When using the said other resin, 1 type may be used independently and 2 or more types may be used together. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
Moreover, it is preferable that the compounding quantity of the other resin in the compounding component except a solvent component is 5-30 mass%, and it is more preferable that it is 10-20 mass%.

(Other curing agents)
In the present invention, other curing agents other than the biphenyl skeleton-containing phenol-based curing agent, dicyclopentadiene skeleton-containing phenol-based curing agent, triazine skeleton-containing phenol resin, and limonene skeleton-containing phenol resin may be used in combination. Examples of other curing agents include amine compounds.

Examples of the amine compound include a chain aliphatic amine, a cyclic aliphatic amine, and an aromatic amine.
Examples of the chain aliphatic amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine.
Examples of the cycloaliphatic amine include mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9- Examples thereof include bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane.
Examples of the aromatic amine include m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-. Examples include diisopropylbenzene.

When an amine compound is used as the other curing agent, one kind may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
Moreover, the compounding quantity of the amine compound in the compounding components excluding the solvent component is usually 1% by mass or less, and preferably 0.2 to 0.8% by mass.

(Organized layered silicate)
The resin composition of the present invention may contain an organically modified layered silicate.
The organic layered silicate refers to a layered silicate that has been subjected to a known organic treatment for the purpose of improving dispersibility and cleavage in a resin. Here, the layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product. And the mechanical characteristic of a resin composition can be improved by using layered silicate with a large aspect ratio.

  Examples of the layered silicate having a large aspect ratio include smectite clay minerals, swellable mica, vermiculite, and halloysite. Examples of smectite clay minerals include montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite. Among these, one or more selected from the group consisting of montmorillonite, hectorite and swellable mica are preferable.

  When the organic layered silicate and silica are contained in the resin composition, the organic layered silicate exists around the silica. In this case, the silica present on the surface of the cured product can be more easily desorbed by heating and curing the resin composition and further performing, for example, swelling and roughening treatment.

The organic layered silicate may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
Moreover, the compounding amount of the organically modified layered silicate in the compounding component excluding the solvent component may be appropriately set according to the use of the resin composition, but it may be usually 1% by mass or less, and 0.2 to 0.8. It is preferable that it is mass%.
The blending ratio (mass ratio) of silica and organic layered silicate is preferably 1: 0.05 to 1: 0.5. When the ratio of the organic layered silicate is low, it is difficult to obtain an effect of improving the separation of the silica, and when the ratio of the organic layered silicate is large, it becomes difficult to form a fine rough surface.

As optional components, in addition to the above components, thermoplastic resins, thermoplastic elastomers, crosslinked rubbers, oligomers, inorganic compounds, nucleating agents, antioxidants, anti-aging agents, thermal stabilizers that do not fall under these components Various additives such as a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant aid, an antistatic agent, an antifogging agent, a filler, a softener, a plasticizer, and a colorant may be used.
The blending amount of the additive may be appropriately adjusted according to the purpose, and is not particularly limited.
Moreover, the said additive may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.

The resin composition of the present invention can be produced by adding each of the above-mentioned blending components to a solvent and mixing them.
The solvent may be removed or may be used for curing the resin composition without being removed.
More specifically, it is preferable to manufacture by the following procedure. That is, a bisphenol type epoxy resin and other resin as an optional component are mixed in a solvent to make it uniform as required. Next, after mixing the curing agent to make it uniform, silica and optional components are mixed to make it even more uniform. Next, a blending liquid is obtained by mixing and homogenizing the curing accelerator. The obtained compounded liquid may be used as it is as a resin composition, or the solvent may be removed to form a resin composition.

  The solvent may be appropriately selected from known ones in consideration of the type of compounding components and the like, and those that can be easily removed by heating and drying are preferred. Moreover, the usage-amount of a solvent is not specifically limited, What is necessary is just a quantity suitable for mixing a mixing | blending component uniformly.

<Hardened product>
The resin composition of the present invention can be cured by heating. Specifically, the liquid resin composition is preferably degassed, and then heated in a desired form, for example, applied in a film shape so as to have a predetermined thickness. When using the resin composition containing a solvent, you may perform solvent removal simultaneously at the time of heat-hardening.

  The temperature at the time of heat curing is preferably 110 to 240 ° C, more preferably 130 to 200 ° C. In addition, although the heat curing time depends on the curing temperature, it is preferably 10 minutes to 5 hours, and more preferably 15 minutes to 3 hours when the curing temperature is within the above range.

  A hardened | cured material can form a fine uneven surface, for example by giving the surface the roughening process, or a swelling process and a roughening process.

Examples of the roughening treatment include manganese compounds such as potassium permanganate and sodium permanganate; chromium compounds such as potassium dichromate and anhydrous potassium chromate; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate. An oxidizing agent mainly composed of a compound can be used. These oxidizing agents are preferably used, for example, as an aqueous solution or an organic solvent dispersion solution. Especially, it is preferable to use together 30-90 g / L permanganic acid solution or permanganate solution with 30-90 g / L sodium hydroxide solution.
It is preferable that the temperature at the time of a roughening process is 30-85 degreeC. Although the roughening treatment time depends on the treatment temperature, it is preferably 1 to 10 minutes when the treatment temperature is within the above range.
The number of roughening treatments may be adjusted as appropriate, but usually 1 to 2 is sufficient. If the number of treatments is too large, the surface of the cured product will be scraped as much, and the improvement of the roughening effect due to the increase in the number of treatments may not be seen substantially, and the uneven surface may not be clearly distinguishable. .

For the swelling treatment, for example, an aqueous solution or an organic solvent dispersion solution of a treatment agent mainly composed of ethylene glycol or the like can be used. Especially, 40 mass% ethylene glycol aqueous solution is preferable.
The temperature during the swelling treatment is preferably 30 to 85 ° C. The wet treatment time depends on the treatment temperature, but when the treatment temperature is within the above range, it is preferably 1 to 20 minutes.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
After blending each component with the composition shown in Tables 1 and 2 and synthesizing an epoxy resin, it was cast into a film, dried and cured, and a cured film having a thickness of 40 μm was obtained (Example) 1-7, Comparative Examples 1-3). Further, the surface roughness (Ra) when the obtained cured product was subjected to a roughening treatment under conditions of swelling: 60 ° C./20 minutes and roughening: 80 ° C./20 minutes was measured. Details are as follows.

[Example 1]
18.32 g of bisphenol A type epoxy resin (828-US, manufactured by Japan Epoxy Resin Co., Ltd.), 2.58 g of polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin (YX6954BH30, Japan) 14.26 g of epoxy resin (solid content 35 wt%) and 10.13 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were mixed to obtain a uniform solution, and then a biphenyl skeleton-containing phenol type curing was made. 17.30 g of an agent (MEH7851-4H, manufactured by Meiwa Kasei Co., Ltd.) and 0.25 g of an amine curing agent (DICY, manufactured by Adeka Resin Co., Ltd.) were mixed and stirred until they were completely uniform. Thereto, 36.67 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Subsequently, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.37 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 2]
18.32 g of bisphenol A type epoxy resin (828, manufactured by Japan Epoxy Resin Co., Ltd.), 2.58 g of polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin (YX6954BH30, Japan Epoxy Resin) Co., Ltd., solid content 35 wt%) 14.26 g and dimethylformamide (Wako Pure Chemical Industries, Ltd.) 10.13 g as a solvent were mixed to make a uniform solution, and then a biphenyl skeleton-containing phenol type curing agent ( 17.30 g of MEH7851-4H (manufactured by Meiwa Kasei Co., Ltd.) and 0.25 g of an amine curing agent (DICY, manufactured by Adeka Resin Co., Ltd.) were mixed and stirred until they were completely uniform. Thereto, 36.67 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Subsequently, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.37 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 3]
Bisphenol A type epoxy resin (850A, manufactured by DIC Corporation) 18.32 g, polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 2.58 g, phenoxy resin (YX6954BH30, Japan Epoxy Resin Corporation) Manufactured, solid content 35 wt%) 14.26 g and dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) 10.13 g as a solvent were mixed to obtain a uniform solution, and then a biphenyl skeleton-containing phenol type curing agent (MEH7851- 4H, manufactured by Meiwa Kasei Co., Ltd.) 17.30 g and amine curing agent (DICY, manufactured by Adeka Resin Co., Ltd.) 0.25 g were mixed and stirred until they were completely uniform. Thereto, 36.67 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Subsequently, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.37 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 4]
18.32 g of bisphenol A type epoxy resin (828-US, manufactured by Japan Epoxy Resin Co., Ltd.), 12.65 g of phenoxy resin (YX6954BH30, manufactured by Japan Epoxy Resin Co., Ltd., solid content 35 wt%), and dimethylformamide (Japanese) After mixing with 8.85 g (manufactured by Kojun Pharmaceutical Co., Ltd.) to make a uniform solution, 15.57 g of a biphenyl skeleton-containing phenol type curing agent (MEH7851-4H, manufactured by Meiwa Kasei Co., Ltd.) and an amine curing agent ( DICY (manufactured by Adeka Resin Co., Ltd.) 0.23 g was mixed and stirred until it was completely uniform. Thereto, 32.53 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Next, an imidazole skeleton-containing accelerator (2MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.04 g and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.33 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 5]
Bisphenol A type epoxy resin (850A, manufactured by DIC Corporation) 18.32 g, polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 2.58 g, phenoxy resin (YX6954BH30, Japan Epoxy Resin Corporation) Manufactured, 35 wt% solid content) 13.59 g and 8.50 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were mixed to obtain a uniform solution, and then a biphenyl skeleton-containing phenol type curing agent (MEH7851- H, Meiwa Kasei Co., Ltd.) 15.50 g and an amine curing agent (DICY, Adeka Resin Co., Ltd.) 0.25 g were mixed and stirred until they were completely uniform. Thereto, 34.95 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in the solvent was mixed and stirred until it was completely uniform. Next, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.35 g) is added and stirred until completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 6]
Bisphenol A type epoxy resin (828-US, manufactured by Japan Epoxy Resin Co., Ltd.) 18.32 g, polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 2.58 g, and phenoxy resin (YX6954BH30, Japan) 14.26 g of epoxy resin (solid content 35 wt%) and 10.13 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were mixed to obtain a uniform solution, and then a biphenyl skeleton-containing phenol type curing was made. 17.30 g of an agent (MEH7851-4H, manufactured by Meiwa Kasei Co., Ltd.) and 0.25 g of an amine curing agent (DICY, manufactured by Adeka Resin Co., Ltd.) were mixed and stirred until they were completely uniform. Thereto, 36.67 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Subsequently, an imidazole skeleton containing accelerator (2P4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.13 g and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.37 g) was added and stirred until it was completely uniform. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Example 7]
Bisphenol A type epoxy resin (828-US, manufactured by Japan Epoxy Resin Co., Ltd.) 18.32 g, polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.) 2.58 g, and phenoxy resin (YX6954BH30, Japan) Epoxy Resin Co., Ltd. (solid content 35 wt%) 15.80 g and dimethylformamide (Wako Pure Chemical Industries, Ltd.) 15.13 g as a solvent were mixed to make a uniform solution, and then the biphenyl skeleton-containing phenol type curing 21.62 g of an agent (MEH7851-4H, manufactured by Meiwa Kasei Co., Ltd.) was mixed and stirred until it was completely uniform. Thereto, 40.62 g of silica slurry (SC1050-FJB, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in the solvent was mixed and stirred until it was completely uniform. Subsequently, an imidazole skeleton containing accelerator (2P4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.13 g, and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.41 g) was added and stirred until it was completely uniform. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Comparative Example 1]
17.25 g of bisphenol A type epoxy resin (RE410S, manufactured by Nippon Kayaku Co., Ltd.) that does not correspond to the bisphenol type epoxy resin in the present invention (n = 0 but the ratio of the number of molecules is not 79 to 84%), and many Functional biphenyl skeleton-containing epoxy resin (NC3000H, Nippon Kayaku Co., Ltd.) 2.58 g, phenoxy resin (YX6954BH30, Japan Epoxy Resin Co., Ltd., solid content 35 wt%) 13.87 g, and dimethylformamide (Wako Pure) 9.71 g (manufactured by Yaku Kogyo Co., Ltd.) was mixed to make a uniform solution, and then 17.30 g of a biphenyl skeleton-containing phenol type curing agent (MEH7851-4H, Meiwa Kasei Co., Ltd.) and an amine curing agent (DICY) , Made by Adeka Resin Co., Ltd.) Until the mixture was stirred. Thereto, 35.66 g of silica slurry (SC1050-FJB, manufactured by Admatex Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Next, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.36 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Comparative Example 2]
17.25 g of bisphenol A type epoxy resin (RE410S, manufactured by Japan Epoxy Resin Co., Ltd.) not corresponding to the bisphenol type epoxy resin in the present invention (n = 0 but the ratio of the number of molecules is not 79 to 84%), and many Functional biphenyl skeleton-containing epoxy resin (NC3000H, Nippon Kayaku Co., Ltd.) 2.58 g, phenoxy resin (YX8100H30, Japan Epoxy Resin Co., Ltd., solid content concentration 30 wt%) 16.19 g, and dimethylformamide (Wako Pure) 9.71 g (manufactured by Yakuhin Kogyo Co., Ltd.) was mixed to obtain a uniform solution, and then 15.57 g of a biphenyl skeleton-containing phenol type curing agent (MEH7851-H, Meiwa Kasei Co., Ltd.) and an amine curing agent ( DICY, manufactured by Adeka Resin Co., Ltd.) And the mixture was stirred until uniform. Thereto, 35.66 g of silica slurry (SC1050-FJB, manufactured by Admatex Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Next, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.36 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

[Comparative Example 3]
21.70 g of a bisphenol A type epoxy resin (828XA, manufactured by Japan Epoxy Resin Co., Ltd.) that does not correspond to the bisphenol type epoxy resin in the present invention (the ratio of the number of molecules of n = 0 is not 79 to 84%), Polyfunctional biphenyl skeleton-containing epoxy resin (NC3000H, Nippon Kayaku Co., Ltd.) 2.58 g, phenoxy resin (YX6954BH30, Japan Epoxy Resin Co., Ltd., solid content 35 wt%) 15.92 g, and dimethylformamide (Japanese) 9.71 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was mixed to make a uniform solution, and then a biphenyl skeleton-containing phenol type curing agent (MEH7851-4H, Meiwa Kasei Co., Ltd.) 17.30 g and an amine curing agent ( DICY, manufactured by Adeka Resin Co., Ltd.) 0.25 g It was stirred until homogeneous in all. Thereto, 41.35 g of silica slurry (SC1050-FJC, manufactured by Admatechs Co., Ltd., silica content 50 wt%) dispersed in a solvent was mixed and stirred until it was completely uniform. Next, an imidazole skeleton containing accelerator (2 MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd., 0.05 g) and IM-1000 (manufactured by Nikko Metal Co., Ltd.) 0.36 g) is added and stirred until it is completely uniform. did. The resulting blended coating liquid is defoamed using a rotating / revolving mixer (Awatori Rentaro, manufactured by Shinky Co., Ltd.), then cast to a predetermined film thickness, and dried at 100 ° C. for 3 minutes. And then cured at 150 ° C. for 1 hour.
The obtained cured product was milky white with a yellowish color.

In addition, each abbreviation in a table | surface shows the following. Moreover, the numerical value in () shows a compounding quantity. “-” Indicates that it is not blended.
(1) Bisphenol A type epoxy resin A1; 828-US (made by Japan Epoxy Resin Co., Ltd.)
A2; 828 (made by Japan Epoxy Resin Co., Ltd.)
A3; 850A (manufactured by DIC Corporation)
A4; RE410S (manufactured by Nippon Kayaku Co., Ltd.)
A5; 828XA (manufactured by Japan Epoxy Resin Co., Ltd.)
(2) Polyfunctional biphenyl skeleton-containing epoxy resin B1; NC3000H (manufactured by Nippon Kayaku Co., Ltd.)
(C) Phenoxy resin C1; YX6954BH30 (manufactured by Japan Epoxy Resin Co., Ltd., solid content 35 wt%)
C2; YX8100H30 (Japan Epoxy Resin Co., Ltd., solid content 30 wt%)
(D) Biphenyl skeleton-containing phenol type curing agent D1; MEH7851-4H (Maywa Kasei Co., Ltd.)
D2; MEH7851-H (Maywa Kasei Co., Ltd.)
(E) Amine-based curing agent E1; DICY (manufactured by Adeka Resin Co., Ltd.)
(F) Silica F1; SC1050-FJB (manufactured by Admatex Co., Ltd., silica content 50 wt%), silica slurry dispersed in solvent (G) curing accelerator G1; 2MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.), Imidazole G2; 2P4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), imidazole skeleton containing accelerator G3; IM-1000 (manufactured by Nikko Metal Co., Ltd.), imidazole silane

  The present invention can be used for manufacturing a circuit board such as a semiconductor device.

Claims (5)

One or more curing agents selected from the group consisting of a biphenyl skeleton-containing phenolic curing agent, a dicyclopentadiene skeleton-containing phenolic curing agent, a triazine skeleton-containing phenolic resin, and a limonene skeleton-containing phenolic resin, a bisphenol-type epoxy resin, and curing A resin composition containing an accelerator and silica,
The resin composition, wherein the bisphenol-type epoxy resin contains 79 to 84% of a compound in which two epoxy groups are introduced into one molecule of bisphenol or a derivative thereof in terms of the number of molecules. The bisphenol-type epoxy resin is a bisphenol A-type epoxy resin represented by the following general formula (1), wherein n = 0 is contained by 79 to 84% in terms of the number of molecules. The resin composition according to claim 1.

(In the formula, n is an integer of 0 or more.)   3. The resin composition according to claim 1, wherein the amount of silica is 15 to 40% by mass based on the total amount of the components excluding the solvent component.   Furthermore, phenoxy resin is mix | blended and the compounding quantity of this phenoxy resin is 5-30 mass% in the compounding component total amount except a solvent component, The resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. object.   Hardened | cured material formed by heat-curing the resin composition as described in any one of Claims 1-4.