JP6735097B2 - Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin mixture, an epoxy resin composition, a cured product thereof, and a semiconductor device suitable for use in electric and electronic materials that require heat resistance.

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

However, in recent years, along with the development thereof in the electric and electronic fields, high-purity resin compositions, moisture resistance, adhesiveness, dielectric properties, and low viscosity for highly filling fillers (inorganic or organic fillers), Further improvements in various characteristics such as increased reactivity for shortening the molding cycle are required. Further, as a structural material, a lightweight material having excellent mechanical properties is required for aerospace materials, leisure/sports equipment applications and the like. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), with the transition of the semiconductor, thinning, stacking, systemization, and three-dimensionalization have become complicated, resulting in extremely high levels. Required properties such as heat resistance and high fluidity are required. In addition, especially with the expansion of plastic packages for in-vehicle use, the demand for improvement in heat resistance is becoming more severe. Specifically, as the driving temperature of the semiconductor rises, heat resistance of 150° C. or higher is required. Generally, an epoxy resin having a high softening point tends to have high heat resistance, but on the other hand, it tends to increase in viscosity, making it difficult to use as an encapsulating material. Further, lowering of the thermal decomposition temperature and lowering of flame retardancy become problems.

"2008 STRJ Report Semiconductor Roadmap Expert Committee 2008 Report", Chapter 8, p1-1, [online], March 2009, JEITA (Japan) Electronics and Information Technology Industries Association Semiconductor Technology Roadmap Expert Committee Meeting, [Search May 30, 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Nobuyuki Takakura et al., Matsushita Electric Industrial Co., Ltd. Vehicle-related device technology High temperature operation IC for vehicle, No. 74, Japan, May 31, 2001, pp. 35-40

Generally, when the Tg of the epoxy resin is increased, the flame retardancy decreases. This is due to the increase in crosslink density. However, with the demand for higher Tg in semiconductor peripheral materials that are required to have flame retardancy, there has been an urgent need to develop a resin having these contradictory properties.
In addition, Japanese Patent Laid-Open No. 2013-43958 and International Publication No. 2007/007827 introduce a biphenylene aralkyl type resin using dihydroxybenzenes as a method for solving this problem.
However, although the above epoxy resin achieves both high heat resistance and flame retardancy, the mechanical properties are deteriorated. Moreover, since the viscosity of the epoxy resin itself is too high, it is difficult to actually use it as a sealing material.
That is, the present invention, while having excellent heat resistance of the cured product, is a property contradictory to the heat resistance, mechanical strength of the cured product, flame retardancy, excellent elastic modulus at high temperature, viscosity before curing It is an object of the present invention to provide an epoxy resin mixture capable of simultaneously satisfying the characteristics such as low viscosity, and further to provide an epoxy resin composition, a cured product and a semiconductor device using the epoxy resin mixture.

The present inventors have completed the present invention as a result of earnest studies in view of the above-mentioned actual conditions.

That is, the present invention is
(1)
An epoxy resin mixture obtained by simultaneously reacting a phenol resin (A) represented by the following formula (1) and a biphenol with an epihalohydrin (B),

(In the formula, the ratio (molar ratio) of (a) and (b) is (a)/(b)=1 to 3, and n represents the number of repetitions),
(2) The ratio of the phenol resin (A) to the biphenol (B) is such that the hydroxyl group of (B) is 0.08 to 0.33 times the molar amount of 1 molar equivalent of the hydroxyl group of (A). The epoxy resin mixture described in
(3)
The epoxy resin mixture as described in (1) or (2) above, which has a softening point of 80 to 100° C.
(4)
The epoxy resin mixture as described in any one of the above items (1) to (3), which has an ICI melt viscosity (corn plate method) at 150° C. of 0.05 to 0.30 Pa·s,
(5)
A curable resin composition comprising the epoxy resin mixture according to any one of the above items (1) to (4) and a curing agent as essential components,
(6)
An epoxy resin composition comprising the epoxy resin mixture according to any one of the above items (1) to (4) and a curing catalyst as essential components,
(7)
A cured product obtained by curing the curable resin composition according to the above (5) or (6),
(8)
A semiconductor device obtained by encapsulating a semiconductor chip with the curable resin composition according to the above (5) or (6),
Regarding

Since the cured product of the epoxy resin mixture of the present invention has excellent heat resistance, water absorption properties, and mechanical properties, it can be used as an insulating material for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.) and CFRP. It is useful for various composite materials, adhesives, paints, etc.

The epoxy resin mixture of the present invention is a mixture of an epoxidized product of a phenol resin (A) represented by the following formula (1) and a glycidylated product of a biphenol (B).

(In the formula, the ratio (molar ratio) of (a) and (b) is (a)/(b)=1 to 3, and n represents the number of repetitions.)

Here, in the epoxy resin mixture of the present invention, in the epoxy compound of the phenol resin represented by the above formula (1), in the area% of gel permeation chromatography (GPC) measurement, the epoxy compound of n=0 is 5 Is preferably 59 to 59 area %, more preferably 10 to 49 area %, and the epoxy compound with n=1 is preferably 5 to 35 area %, and is 5 to 29 area %. Is more preferable.
On the other hand, the epoxidized product of biphenol is preferably 5 to 25 area %, and more preferably 5 to 19 area% in the area% measured by GPC in the epoxy resin mixture of the present invention.
The epoxy resin mixture of the present invention preferably has a melt viscosity of 0.05 to 0.30 Pa·s (ICI melt viscosity 150° C. cone plate method).

The phenol resin used in the present invention is a phenol resin represented by the following formula (1).

(In the formula, the ratio (molar ratio) of (a) and (b) is (a)/(b)=1 to 3, and n represents the number of repetitions.)

55-100 degreeC is preferable, as for the softening point of the phenol resin represented by the said Formula (1), 55 degreeC-80 degreeC is more preferable, and 60-80 degreeC is preferable.
Moreover, as n which is the number of repetitions, 1.05 to 3.0 are preferable, and 1.05 to 2.0 are more preferable.

Furthermore, the ratio (molar ratio) of (a) and (b) is usually (a)/(b)=1 to 3, and more preferably 1 to 2.5. This is because if the ratio of (a) is too large, gelation may occur. This ratio can be calculated by gel permeation chromatography (GPC) based on the area ratio of the peaks derived from (a) and (b) at n=1.
Here, the compound of n=1 in the phenol resin is an RR structure in which (i) (resorcin)-(biphenyllen)-(resorcin) structure, (ii) (resorcin)-(biphenylene)-(phenol) structure It is preferable that the ratio of the RP structure is (iii) and the PP structure is (phenol)-(biphenylene)-(phenol) structure is 4>(RP structure)/(RR structure)>0.5. This is because if it is within this range, high heat resistance can be secured. Further, it is preferable that 4>(RP structure)/(PP structure)>0.5. This is because if it is within this range, high flame retardancy can be secured.

The biphenol used in the present invention has the following structure.

(In the above formula, a plurality of R _1's each independently exist and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4.)

The biphenol having the above structure includes, for example, 2,2′-form, 2,4′-form, 4,4′-form and the like, and among them, 4,4′-form biphenol is preferable.
Further, those having a purity of 95% or more can be preferably used.

In the present invention, the desired epoxy resin mixture is obtained by simultaneously epoxidizing the mixture of the phenol resin represented by the above formula (1) and the biphenol with epihalohydrin.
Here, the ratio of the phenol resin (A) and the biphenol (B) represented by the formula (1) is 0.08 to 0.08 for the hydroxyl group of the biphenol (B) with respect to 1 molar equivalent of the hydroxyl group of the phenol resin (A). The molar amount is preferably 0.43 times, and more preferably 0.08 to 0.33 times.
If it is 0.08 times mol or more, the viscosity is lowered and the mechanical properties are further improved, and if it is 0.43 times mol or less, the precipitation of crystals during production is further reduced, the yield is further improved, and the heat resistance Sex is also improved.

The specific method for producing an epoxy resin mixture will be described below.
The epoxy resin mixture of the present invention can be obtained by reacting a mixture of the phenol resin (A) represented by the above formula (1) and the biphenol (B) with epihalohydrin. Hereafter, the mixture of the phenol resin (A) and the biphenol (B) is referred to as the phenol resin mixture of the present invention.
The epoxy equivalent of the epoxy resin mixture of the present invention is 1.02 times to 1.13 times the theoretical epoxy equivalent of the starting phenol resin mixture. It is more preferably 1.03 to 1.10 times. If it is less than 1.02 times, it may be costly to synthesize and purify the epoxy, and if it is more than 1.11 times, a problem due to the chlorine amount may occur as described above.
The total chlorine remaining in the epoxy resin mixture obtained by the reaction is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 1000 ppm or less. The adverse effect due to the amount of chlorine is the same as described above. The chlorine ion and sodium ion are preferably 5 ppm or less, and more preferably 3 ppm or less. Needless to say, chlorine ions are described above, but cations such as sodium ions also become a very important factor particularly in power device applications, and contribute to a failure mode when a high voltage is applied.
Here, the theoretical epoxy equivalent refers to an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol resin mixture of the present invention is glycidylated without excess or deficiency. When the epoxy equivalent is within the above range, an epoxy resin having excellent heat resistance and electrical reliability of the cured product can be obtained.

The epoxy resin mixture of the present invention has a resinous form with a softening point. Here, the softening point is preferably 70 to 110°C, more preferably 80 to 100°C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperature. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with another resin (for example, a curing agent). The melt viscosity is preferably 0.05 to 0.30 Pa·s (ICI melt viscosity 150° C. cone plate method), and more preferably 0.07 to 0.20 Pa·s. When an inorganic material (such as a filler) is mixed and used, problems such as poor fluidity occur.

As the epihalohydrin used in the method for synthesizing the epoxy resin mixture of the present invention, epichlorohydrin which is industrially easily available is preferable. The amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, and particularly preferably 1 mol of the hydroxyl group of the phenol resin mixture of the present invention. Is 4.5 to 8.5 mol.
If it is less than 3.0 mol, the epoxy equivalent of the obtained epoxy resin mixture may increase, and the handling workability of the obtained epoxy resin mixture may deteriorate. If it exceeds 15 moles, the amount of solvent becomes large.

An alkali metal hydroxide can be used in the above reaction. Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, a solid may be used, or an aqueous solution thereof may be used, but in the present invention, in particular, From the viewpoint of solubility and handling, it is preferable to use a solid material molded into flakes.
The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, and more preferably 1 mol to 1 mol of the hydroxyl group of the raw material phenol resin mixture of the present invention. It is 0.99 to 1.15 mol.

In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of the raw material phenol mixture.

In this reaction, in addition to the above epihalohydrin, it is preferable to use a non-polar protic solvent (dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.) and an alcohol having 1 to 5 carbon atoms in combination. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The amount of the non-polar protic solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of epihalohydrin used. The epoxidation may be carried out by controlling the water content in the system by a method such as azeotropic dehydration.
If the system contains a large amount of water, the cured product of the obtained epoxy resin mixture may have poor electrical reliability, and it is preferable to control the water content to 5% or less for synthesis. Further, when an epoxy resin is obtained using a non-polar protic solvent, a cured product of an epoxy resin mixture having excellent electrical reliability can be obtained, and therefore a non-polar protic solvent can be preferably used.

The reaction temperature is usually 30 to 90°C, preferably 35 to 80°C. Particularly in the present invention, 60° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. When the reaction time is short, the reaction does not proceed, and when the reaction time is long, by-products are formed, which is not preferable.
After washing the reaction products of these epoxidation reactions with or without washing with water, the epihalohydrin, solvent, etc. are removed under reduced pressure with heating. Further, in order to obtain an epoxy resin mixture containing less hydrolyzable halogen, the recovered epoxidized product is a ketone compound having 4 to 7 carbon atoms (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It is also possible to dissolve as a solvent and add an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to carry out the reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol resin mixture used for the epoxidation. The reaction temperature is usually 50 to 120° C., and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the formed salt is removed by filtration, washing with water and the like, and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of the present invention.

The epoxy resin mixture of the present invention exhibits a semi-crystalline resinous state.
A normal epoxy resin mixture is a resin in a transparent amorphous state without being oriented. In the present invention, the resin mixture has crystallinity and becomes cloudy and not transparent. The semi-crystalline state indicates this state, and the hardness of the resin formed by becoming the semi-crystalline state becomes hard, and the resin is easy to pulverize at the time of kneading and pulverizing, and the resin has high productivity. Here, the semi-crystalline form indicates not only a resin in a cloudy state as described above, but even a transparent resin in an amorphous state is left in a range of 100° C.±30° C. for 10 minutes or more after reaction, Including those that become cloudy when gradually cooled. Crystallization of such a resin is also promoted by kneading during the preparation of the resin composition, which contributes to productivity.

In the epoxy resin mixture of the present invention, the epoxidized phenol resin represented by the above formula (1) and bisglycidyloxybiphenyl (provided that the aromatic ring has a substituent, the number of substituents is 4 or less, the number of carbon atoms is 4 or less). Is 4 or less at the same time. However, in the reaction under the above preferable conditions, the structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin is also present. Exists. Therefore, by simultaneously epoxidizing the phenol resin mixture of the present invention, the structure is generated and the viscosity tends to be relatively low, which is preferable in improving the fluidity which is the object of the present invention. Also, mechanical properties such as toughness are improved.
Further, as compared with the case of epoxidizing only biphenol, the epoxy resin mixture obtained by such a method has low crystallinity, so that purification can be easily performed, so that an epoxy resin mixture having a small residual chlorine content can be obtained. Will be easier.
In the present invention, the epoxy resin having a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin is preferably 0.01 to 10 area% in terms of area% measured by GPC. , 0.1 to 10 area% is particularly preferable.

The epoxy resin composition of the present invention contains the epoxy resin mixture of the present invention, a curing catalyst and/or a curing agent. Further, it is preferable to contain another epoxy resin as an optional component.

The epoxy resin composition of the present invention may contain another type of epoxy resin other than the epoxy resin mixture of the present invention. The proportion of the epoxy resin mixture of the present invention in all epoxy resins is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include novolac type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[ 1,1′-biphenyl]-4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclo Pentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene or Polycondensates with 1,4-bis(methoxymethyl)benzene and the like and modified products thereof, glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A and alcohols, alicyclic epoxy resins, glycidyl Amine-based epoxy resin, glycidyl ester-based epoxy resin, silsesquioxane-based epoxy resin (chain-like, cyclic, ladder-like, or a siloxane structure of at least two or more thereof mixed with a glycidyl group and/or an epoxycyclohexane structure However, the present invention is not limited to these.

Specific examples of the curing catalyst (curing accelerator) that can be used in the present invention include amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca. 7-ene, imidazole, triazole, tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazole (1′))Ethyl-s-triazine, 2,4-diamino-6(2′-undecylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-ethyl,4 -Methylimidazole (1'))ethyl-s-triazine, 2,4-diamino-6(2'-methylimidazole (1'))ethyl-s-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2:3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3. ,5-dicyanoethoxymethylimidazole and other various heterocyclic compounds, and these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, Salts with polycarboxylic acids such as oxalic acid, amides such as dicyandiamide, diaza compounds such as 1,8-diaza-bicyclo(5.4.0)undecene-7 and salts thereof such as tetraphenylborate and phenol novolac. , The above-mentioned polyvalent carboxylic acids, or salts with phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethyl Butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, trio Ammonium salts such as octylmethyl ammonium hydroxide, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetramethyl ammonium acetate, trioctyl methyl ammonium acetate, triphenylphosphine, tri(toluyl)phosphine, tetraphenylphosphonium Phosphines and phosphonium compounds such as bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid) , Zinc salt of mistyric acid, tin salt, zirconium salt), phosphate ester metal (zinc salt of octyl phosphoric acid, stearyl phosphoric acid), alkoxy metal salt (tributyl aluminum, tetrapropyl zirconium, etc.), acetylacetone salt (acetylacetone) Zirconium chelate, acetylacetone titanium chelate, etc.) and the like. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring during curing and changes thereof. When a quaternary salt is used, the salt with halogen may leave halogen in the cured product.
The curing accelerator may be used in an amount of 0.01 to 5.0 parts by weight based on 100 parts of the epoxy resin.

The epoxy resin composition of the present invention preferably contains a curing agent. Examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenolic resins, carboxylic acid compounds, and the like. Specific examples of the curing agent that can be used include nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a dimer of linolenic acid and a polyamide resin synthesized from ethylenediamine (amine, Amide compound); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydro Phthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic acid anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic acid anhydride, Acid anhydrides such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4. '-Bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene or 1,4'- Polycondensates with bis(methoxymethyl)benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, phenol resins such as condensates of terpenes and phenols; imidazole, trifluoroborane-amine complex, Examples include guanidine derivative compounds. It is not limited to. These may be used alone or in combination of two or more.
In the present invention, the above-mentioned phenol resin is preferable because it is used for electronic materials.

The amount of the curing agent used in the epoxy resin composition of the present invention (hereinafter, also referred to as curable resin composition) is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin. If the amount is less than 0.7 equivalent or more than 1.2 equivalent to 1 equivalent of epoxy group, the curing may be incomplete and good cured physical properties may not be obtained.

In addition, it is preferable to use a cyanate ester compound as another component. The cyanate ester compound can be made into a heat-resistant cured product having a higher crosslink density by a reaction with an epoxy resin in addition to a curing reaction by itself. Examples of the cyanate ester resin include 2,2-bis(4-cyanatephenyl)propane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2-bis(4-cyanatephenyl)ethane, These derivatives, aromatic cyanate ester compounds and the like can be mentioned. In addition, for example, it can be synthesized by reacting various phenolic resins with hydrocyanic acid or salts thereof as described in the above-mentioned curing material. In the present invention, those having a structure not having a methylene structure at the benzyl position in the molecule such as 2,2-bis(4-cyanatephenyl)propane and its derivatives (partial polymerization products) are particularly preferable. They may be used alone or in combination of two or more.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reaction type or an addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylene bis( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylene bis(dixylylenyl phosphate), and 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide, phosphanes such as 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Examples of the phosphorus-containing epoxy compound obtained by reacting with, red phosphorus and the like, phosphoric acid esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis(dixylylenyl phosphate), 1 , 4-phenylene bis(dixylylenyl phosphate), 4,4'-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably phosphorus-containing compound/total epoxy resin=0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Further, the epoxy resin composition of the present invention may contain a binder resin if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, and silicone resin. However, the present invention is not limited to these. The content of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight of the total of the epoxy resin and the curing agent. 0.05 to 20 parts by weight is used if necessary.

If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. As the inorganic filler, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc and the like powders or these Examples thereof include, but are not limited to, beads made by spheroidizing. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is generally 0 to 95% by weight in the epoxy resin composition of the present invention, although it depends on the intended use, and particularly when used in the encapsulating material application, preferably It is preferable to use properly in the range of 50 to 95% by weight, particularly preferably 65 to 95% by weight, depending on the shape of the package. Further, the epoxy resin composition of the present invention, antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, various compounding agents such as pigments, Various thermosetting resins can be added. Particularly, as the coupling material, it is preferable to add a coupling material having an epoxy group or a coupling material having a thiol.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, etc. are uniformly used by using an extruder, a kneader, a roll, a planetary mixer, etc., if necessary. Until sufficiently mixed to obtain an epoxy resin composition, and when the obtained epoxy resin composition is in a liquid state, the composition is impregnated into a base material by potting or casting or poured into a mold for casting. It is hardened by heating. When the obtained epoxy resin composition is solid, it is cast after melting, or molded using a transfer molding machine or the like, and further cured by heating. The curing temperature and time are 80 to 200° C. and 2 to 10 hours. As a curing method, it is possible to cure at a high temperature all at once, but it is preferable to raise the temperature stepwise to proceed the curing reaction. Specifically, the initial curing is performed at 80 to 150°C, and the post curing is performed at 100 to 200°C. The curing step is preferably carried out by raising the temperature in 2 to 8 steps, more preferably 2 to 4 steps.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone to prepare a curable resin composition varnish, which is made of glass fiber To obtain a cured product of the epoxy resin composition of the present invention by hot press-molding a prepreg obtained by impregnating a base material such as Bonn fiber, polyester fiber, polyamide fiber, alumina fiber, and paper and heating and drying. You can In this case, the solvent is used in an amount of usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

Specific applications of these compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRPs, etc.), insulating materials (including printed circuit boards, wire coatings, etc., as well as sealing materials, Examples include encapsulating materials, cyanate resin compositions for substrates), additives such as acrylic acid ester resins as resist curing agents, and other resins. In the present invention. It is particularly preferable to use as an insulating material for electronic materials (a sealing material including a printed circuit board, a wire coating, etc., as well as a sealing material, a cyanate resin composition for a substrate).

Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general offices, and medical, as well as adhesives for electronic materials. Among them, adhesives for electronic materials include interlayer adhesives for multi-layer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfill, BGA reinforcing underfill, anisotropic conductive film ( ACF), an anisotropic conductive paste (ACP), and other mounting adhesives.

As the encapsulant and the substrate, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer molding encapsulation, potting encapsulations for ICs, LSIs such as COB, COF, TAB, etc., Examples include underfill for flip chips, sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, CSP, and package substrates. It is also suitable for use as a circuit board or module board that requires functionality.

The epoxy resin composition of the present invention is particularly preferably used for semiconductor devices.
The semiconductor device is the IC package group mentioned above.
The semiconductor device of the present invention can be obtained by encapsulating a silicon chip provided on a support such as a package substrate or a die with the epoxy resin composition of the present invention. The molding temperature and the molding method are as described above.

Next, the present invention will be described in more detail with reference to Examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analytical methods used in the examples are described below.
Epoxy equivalent: conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: according to JIS K 7117-2 (ISO 3219) Softening point: according to JIS K 7234 Total chlorine: according to JIS K 7243-3 (ISO 21672-3) Chloride ion: JIS K 7243-1 (ISO 21672) -1) Compliant with GPC:
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The connected eluent is tetrahydrofuran. The flow rate is 0.5 ml/min.
Column temperature is 40℃
Detection: RI (differential refraction detector)

(Example 1)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was subjected to nitrogen purging, and a phenol resin ((a)/(b)=1.3, n=produced in accordance with WO 2007/007827). 1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1 (GPC measurement), hydroxyl group equivalent 134 g/eq., softening point 93° C.) 132 parts , 4,4'-biphenol 29.3 parts (1 mol equivalent of the hydroxyl group of the phenol resin (A) is 0.32 times mol of the hydroxyl group of the biphenol (B)), 541 parts of epichlorohydrin (4.5 parts) (Mole equivalent to phenol resin) and 124 parts of dimethyl sulfoxide were added, dissolved under stirring, and heated to 40 to 45°C. Next, 54.6 parts of flaky sodium hydroxide was added portionwise over 90 minutes, and further reacted at 40° C. for 1 hour, 60° C. for 1 hour, and 70° C. for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, washed with 300 parts of water, and then heated to 70°C. After adding 17 parts of 30% by weight aqueous sodium hydroxide solution under stirring and reacting for 1 hour, water was washed until the water for washing the oil layer became neutral, and the resulting solution was depressurized using a rotary evaporator. By distilling off methyl isobutyl ketone and the like, 201 parts of the epoxy resin mixture (EP1) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP1) was 192 g/eq. The melt viscosity at a softening point of 95° C. and 150° C. (ICI melt viscosity cone #1) was 0.11 Pa·s. Further, as a result of measuring the obtained epoxy resin mixture (EP1) by gel permeation chromatography, it was confirmed that the epoxy resin of biphenol was contained at 15.3 area %, and n=0 in the above formula (1). It was confirmed that 28.8 area% of the epoxidized product of No. 1 and 17.6 area% of the epoxidized product of n=1 were contained.

(Example 2 and Comparative Example 1)
The epoxy resin mixture (EP1) obtained as described above or a comparative epoxy resin (EP2: phenol resin was changed to 172 parts in Example 1 without addition of biphenol), an epoxy resin and a curing agent were used. (P-1: Phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.), P-2: Phenol aralkyl resin (Mirex XLC-3L manufactured by Mitsui Chemicals, Inc.)) is mixed in an equivalent amount and cured. Catalyst (curing accelerator: triphenylphosphine (manufactured by Hokuko Kagaku Co., Ltd. TPP)) and, if necessary, filler (molten silica Takimori MSR-2122% filler amount in the table is a proportion of the total epoxy resin composition) Was mixed and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition. This curable resin composition was crushed with a mixer and further tableted with a tablet machine. This tabletted curable resin composition was transfer-molded (175° C.×60 seconds), and after demolding, cured at 160° C.×2 hours+180° C.×6 hours to obtain a test piece for evaluation.
Using this test piece for evaluation, the physical properties of the cured product were measured as follows. Depending on the evaluation items of the physical properties of the cured product, the types of curing agents used are as shown in Table 1 below, and the amount of the curing accelerator used is 1 for the epoxy resin weight in the sample used for the evaluation of heat resistance and shrinkage. %, and 2% based on the weight of the epoxy resin in the sample used for the evaluation of flame retardancy. The test results are also shown in Table 1 below.

<TMA measurement conditions>
Thermomechanical measuring device TA-instruments, Q400EM
Measurement temperature range: 40°C to 280°C
Temperature rising rate: 2°C/min <Flame resistance test>
-Judgment of flame retardance: It carried out based on UL94. However, the test was conducted with a sample size of 12.5 mm width×150 mm length and a thickness of 0.8 mm.
・After-flame time: Total after-flame time after 10 times of contact with a set of 5 samples <hardening shrinkage>
Compliant with JISK-6911 (molding shrinkage)

Contrary to Comparative Example 1, despite containing an epoxidized product of biphenol, heat resistance is maintained, shrinkage is improved, and in the flame retardancy test, the burning time is shortened even if the curing agent is changed. Therefore, the epoxy resin composition of the present invention can have both high heat resistance and flame retardancy.

(Example 3)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was subjected to nitrogen purging, and a phenol resin ((a)/(b)=1.3, n=produced in accordance with WO 2007/007827). 1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1 (GPC measurement), hydroxyl equivalent of 134 g/eq., softening point 93° C.) 97. 8 parts, 25.1 parts of 4,4′-biphenol (the hydroxyl group of biphenol (B) is 0.37 times mol per 1 mol equivalent of hydroxyl group of phenol resin (A)), 555 parts of epichlorohydrin (6 Mole equivalent to phenol resin) and 55.5 parts of methanol were added, dissolved under stirring, and heated to 70°C. Next, 42 parts of flaky sodium hydroxide was added portionwise over 90 minutes, and then the reaction was carried out at 70° C. for 1 hour. After completion of the reaction, the organic layer obtained was washed with water, and then the excess organic solvent such as epichlorohydrin was distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70°C. Under stirring, 10 parts of 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the water for washing the oil layer became neutral, and the resulting solution was depressurized using a rotary evaporator. By distilling off methyl isobutyl ketone and the like, 161 parts of the epoxy resin mixture (EP3) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin mixture (EP3) was 192 g/eq. The melt viscosity at a softening point of 82° C. and 150° C. (ICI melt viscosity cone #1) was 0.07 Pa·s. Further, as a result of measuring the obtained epoxy resin mixture (EP3) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in an amount of 12.0 area %, and n=0 in the formula (1). It was confirmed that 24.4 area% of the epoxidized product of No. 1 and 16.5 area% of the epoxidized product of n=1 were contained.

(Example 4)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was subjected to nitrogen purging, and a phenol resin ((a)/(b)=1.3, n=produced in accordance with WO 2007/007827). 1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1 (GPC measurement), hydroxyl group equivalent 134 g/eq., softening point 93° C.) 101. 8 parts, 4,2'-biphenol 22.3 parts (the hydroxyl group of the biphenol (B) is 0.316 times mol to the hydroxyl group equivalent of the phenol resin (A) 1 mol equivalent), epichlorohydrin 555 parts (6 (Lequivalent to phenol resin) and 125 parts of dimethylsulfoxide were added, dissolved under stirring, and heated to 40 to 45°C. Next, 42 parts of flaky sodium hydroxide was added portionwise over 90 minutes, and further reacted at 40° C. for 1 hour, 60° C. for 1 hour, and 70° C. for 1 hour. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, washed with 300 parts of water, and then heated to 70°C. Under stirring, 10 parts of 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the water for washing the oil layer became neutral, and the resulting solution was depressurized using a rotary evaporator. Methyl isobutyl ketone and the like were distilled off underneath to obtain 159 parts of the epoxy resin mixture (EP4) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP4) was 189 g/eq. The melt viscosity at a softening point of 98° C. and 150° C. (ICI melt viscosity cone #1) was 0.08 Pa·s. In addition, as a result of measuring the obtained epoxy resin mixture (EP4) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in an amount of 14.9 area %, and n=0 in the formula (1). It was confirmed that 29.3 area% of the epoxidized product of No. 1 and 18.6 area% of the epoxidized product of n=1 were contained.

(Examples 5 and 6)
The epoxy resin mixture (EP3, EP4) or the comparative epoxy resin (EP2) obtained above is used as a curing agent (P-3: phenol novolac (H-1 manufactured by Meiwa Kasei Co., Ltd.)) and a curing catalyst ( Curing accelerator: triphenylphosphine (manufactured by Kitako Chemical Co., Ltd., TPP) was blended in a ratio (equivalent amount) shown in Table 2 and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition. This curable resin composition was crushed with a mixer and further tableted with a tablet machine. This tabletted curable resin composition was transfer-molded (175° C.×60 seconds), and after demolding, cured at 160° C.×2 hours+180° C.×6 hours to obtain a test piece for evaluation. Using this test piece for evaluation, the physical properties of the cured product were measured as follows. The test results are also shown in Table 2.

<TMA measurement conditions>
Thermomechanical measuring device TA-instruments, Q400EM
Measurement temperature range: 40°C to 280°C
Temperature rising rate: 2°C/min <Peel strength>
・180°C peeling test conforms to JIS K-6854-2 Using rolled copper foil

From the above results, it is understood that the cured product of the epoxy resin composition of the present invention has improved toughness while maintaining high heat resistance. That is, in the epoxy resin composition of the present invention, both high heat resistance and toughness of the cured product can be achieved.

(Example 7)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was subjected to nitrogen purging, and a phenol resin ((a)/(b)=1.3, n=produced in accordance with WO 2007/007827). 1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1 (GPC measurement), hydroxyl equivalent 134 g/eq., softening point 93° C.) 109. 9 parts, 16.8 parts of 4,4'-biphenol (the hydroxyl group of the biphenol (B) is 0.22 times mol per 1 mol equivalent of the hydroxyl group of the phenol resin (A)), 463 parts of epichlorohydrin (5 (Equivalent of phenol resin) and 100 parts of dimethylsulfoxide were added, dissolved under stirring, and heated to 40 to 45°C. Next, 42 parts of flaky sodium hydroxide was added portionwise over 90 minutes, and further reacted at 40° C. for 1 hour, 60° C. for 1 hour, and 70° C. for 1 hour. After the reaction was completed, excess solvents such as epichlorohydrin were distilled off under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, washed with 300 parts of water, and then heated to 70°C. Under stirring, 10 parts of 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the water for washing the oil layer became neutral, and the resulting solution was depressurized using a rotary evaporator. Methyl isobutyl ketone and the like were distilled off underneath to obtain 169 parts of the epoxy resin mixture (EP5) of the present invention. The epoxy equivalent of the obtained epoxy resin mixture (EP5) was 189 g/eq. The melt viscosity at a softening point of 83° C. and 150° C. (ICI melt viscosity cone #1) was 0.07 Pa·s. In addition, as a result of measuring the obtained epoxy resin mixture (EP5) by gel permeation chromatography, it was confirmed that the biphenol epoxy resin was contained in an amount of 11.0 area %, and n=0 in the formula (1). It was confirmed that 29.1 area% of the epoxidized product of No. 1 and 17.7 area% of the epoxidized product of n=1 were contained.

(Example 8)
The epoxy resin mixture (EP5) or the comparative epoxy resin (EP2) obtained above was prepared in accordance with the curing agent (P-4: phenol resin used in Example 1 according to WO 2007/007827). Phenol resin ((a)/(b)=1.3, n=1.5, (RP structure)/(RR structure)=2.15, (RP structure)/(PP structure)=2.1(GPC (Measurement), hydroxyl equivalent of 134 g/eq., softening point 93° C.), and curing catalyst (curing accelerator: triphenylphosphine (TPP manufactured by Kitako Chemical Co., Ltd.)) in the proportions (equivalents) of Table 3 and mixing The mixture was uniformly mixed and kneaded using a roll to obtain a curable resin composition. This curable resin composition was crushed with a mixer and further tableted with a tablet machine. This tabletted curable resin composition was transfer-molded (175° C.×60 seconds), and after demolding, cured at 160° C.×2 hours+180° C.×6 hours to obtain a test piece for evaluation.
Using this test piece for evaluation, the physical properties of the cured product were measured as follows. The test results are also shown in Table 2.

<TMA measurement conditions>
Thermomechanical measuring device TA-instruments, Q400EM
Measurement temperature range: 40°C to 280°C
Temperature rising rate: 2°C/min

<Hygroscopicity>
Evaluated by% increase in weight after leaving for 24 hours in a high temperature and high humidity tank at 85°C and 85%

<Heat decomposition characteristics measurement conditions>
Part of the obtained test piece is pulverized by a cycle mill, made into powder, passed through a 100 μm mesh and sieved to a particle size of 75 μm mesh on, and a sample of 5-10 mg is taken and the thermogravimetric reduction temperature is measured with TG-DTA. It was confirmed. The weight reduction temperature of 5% was used as an index.
Measured with TG-DTA (Td5)
Measurement sample: powder (100μm mesh, 75μm mesh on) 5-10mg
Measurement conditions: Temperature rising rate 10°C/min Air flow 200 ml/min 5% weight loss temperature was measured.

From the above results, it can be seen that the epoxy resin of the present invention is able to maintain high heat resistance while maintaining high characteristics in spite of the fact that the epoxy resin of the present invention has a significantly low viscosity of less than half. That is, the epoxy resin of the present invention is a resin capable of improving various properties such as heat resistance, which are difficult to achieve at the same time.

Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the Japanese patent application (Japanese Patent Application No. 2013-189035) filed on September 12, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated in their entirety.

Since the cured product of the epoxy resin mixture of the present invention has excellent heat resistance, water absorption characteristics, and flame retardancy, it can be used as an insulating material for electric and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.) and CFRP. It is useful for various composite materials, adhesives, paints, etc.

Claims (8)

The phenol resin (A) and the biphenol (B) represented by the following formula (1) are obtained by reacting with epihalohydrin at the same time, and in the area% of gel permeation chromatography (GPC) measurement, the epoxidized product of the biphenol (B) An epoxy resin mixture having a content of 5 to 19 area% and having a structure in which the structure of the phenol resin (A) and the structure of the biphenol (B) are connected by epihalohydrin.

(In the formula, the ratio (molar ratio) of (a) and (b) is (a)/(b)=1 to 2.5 , and n represents the number of repetitions.) The epoxy resin according to claim 1, wherein the ratio of the phenol resin (A) to the biphenol (B) is such that the hydroxyl group of (B) is 0.08 to 0.33 times the molar amount of the hydroxyl group equivalent of 1 (A). Resin mixture. The epoxy resin mixture according to claim 1 or 2, which has a softening point of 80 to 100°C. The epoxy resin mixture according to any one of claims 1 to 3, which has an ICI melt viscosity (corn plate method) at 150°C of 0.05 to 0.30 Pa·s. A curable resin composition containing the epoxy resin mixture according to claim 1 and a curing agent. An epoxy resin composition containing the epoxy resin mixture according to any one of claims 1 to 4 and a curing catalyst. A cured product obtained by curing the curable resin composition according to claim 5. A semiconductor device obtained by encapsulating a semiconductor chip with the curable resin composition according to claim 5.