TW202248276A - Phenol resin mixture,curable resin composition and cured products thereof - Google Patents

Abstract

A phenol resin mixture containing a phenol resin (A) represented by the following formula (1) or (2) and an alkyl substituted bisphenol compound (B) and having a weight ratio of the component (A) to the component (B) of 95 /5 to 55 /45. (In the formula (1), a plurality of R1 and p are independently present, and R1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amino group, or a phenyl group which may have the same substituent as described above, and p represents a real number of 0 to 3. n is the number of repetitions and is a real number of 1 to 20.) (In the formula (2), a plurality of R1 and p are independently present, R1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, an amino group, or a phenyl group which may have the same substituent as described above, and p represents a real number of 0 to 3. n is the number of repetitions and is a real number of 1 to 20.).

Description

Phenolic resin mixture, curable resin composition and cured product thereof

The present invention relates to phenolic resin mixture, curable resin composition and cured product thereof.

In the field of sealing materials for semiconductors, phenolic resins are used as hardeners for epoxy resins. With its development in recent years, it is required to further improve the moisture resistance, adhesion, and dielectric properties, such as the high purity of the resin composition, the low viscosity for the high filling of fillers (inorganic or organic fillers), and the short Improve various characteristics such as reactivity by forming cycle.

In addition, the shape of the semiconductor package becomes thinner, stacked, systematized, and three-dimensional as it changes, and its wiring is also developing toward narrower pitches and thinner lines. , it will cause the wire to shift (Wire sweep). Furthermore, it imposes a burden on the connecting portion of the wires and causes adverse effects.

Furthermore, in flip-chip packaging, from the aspect of low-cost manufacturing methods, the method of so-called mold underfill (hereinafter referred to as "MUF") that seals at one time without using underfill is attracting attention. In this method, it is necessary to pass the resin through the electrode between the wafer and the package substrate. Since the gap is narrow, the miniaturization of the filler becomes important, and on the other hand, the surface area increases due to the miniaturization of the filler, which causes the viscosity of the system to increase, causing pores (voids) to occur.

In addition, in the sealing resin used in the rewiring layer such as wafer-level packaging, and the related insulating film used in the build-up layer (build up layer), the thickness of the layer must be thin, and it is necessary to reduce the linear expansion coefficient. Since it is filled with fine fillers, it is also required to lower the viscosity of the resin composition.

[Prior Art Literature]

[Non-patent literature]

[Non-Patent Document 1] "2008 Annual Report of the 2008 STRJ Report Semiconductor Roadmap Special Committee", Chapter 8, p1-1, [online], March 2009, JEITA (Company) Electronics and Information Technology Industry Association Semiconductor Technology Blueprint Committee, [retrieved May 30, 2012], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

[Non-Patent Document 2] Nobuyuki Takakura et al., Matsushita Electric Works Technical Bulletin, Vehicle-related Device Technology, High-temperature Operating IC for Vehicles, No. 74, Japan, May 31, 2001, pages 35-40

[Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-41096

[Patent Document 2] Japanese Unexamined Patent Publication No. 2013-87137

Although various methods of reducing the viscosity have been mentioned, generally, a method of reducing the viscosity by reducing the molecular weight of an epoxy resin or a phenol resin is used. However, when the molecular weight of epoxy resin or phenol resin is reduced, the shape tends to become fluid at room temperature (for example, 20°C in this case), and it becomes difficult to handle at room temperature (liquid to gel to semi-solid). etc.), and it will stick when it is made into a resin composition, so it is difficult to store and handle.

Specifically, when a composition manufacturer purchases a material from a resin manufacturer, it must be transported in a frozen state, which consumes a large amount of energy. Also, agglomeration (becoming lumpy) due to temperature rise during transportation can render it inoperable. In addition, even if there is no problem in the transportation process, the composition cannot be used unless it is returned to room temperature when used by the manufacturer of the composition. At this time, there may be problems such as condensation or agglomeration when returning to room temperature. For example, there will be problems such as blockage at the inlet of the feed hopper when feeding. Furthermore, even if the resin composition is pulverized by a ball mill or the like in order to homogeneously mix the resin composition, it cannot be pulverized, and the resin composition may be agglomerated in the kettle to cause damage to the device. Also, the same problem occurs for the completed composition.

For the above-mentioned problems, the use of a crystalline epoxy resin has been studied (Patent Document 1). However, there are still problems in that the range of decrease in fluidity is limited during molding, and that it is difficult to maintain handling characteristics due to the breakdown of crystallinity due to mixing with phenolic resin after forming a composition, and the like. Also, in general, when using a crystalline epoxy resin, when melt-kneading with a kneader, if the kneading is not carried out at or above the melting point of the crystalline epoxy resin, the epoxy resin is not sufficiently melted and does not melt. Since it is uniformly dispersed, the molded product of the epoxy resin molding material using this molten mixture becomes non-uniform, and the strength of the molded product varies from part to part, resulting in a decrease in the characteristics of the semiconductor device. However, during melt kneading, if the temperature of the molten mixture is high, the hardening reaction will proceed in the kneader, the fluidity will decrease, and there is a possibility of causing gelatinous products, etc., which will become unfilled during molding. The reason for charging. Or recrystallization is caused due to the high degree of crystallinity. Even if the crystallinity remains after heating and kneading, the residual crystals will be melted first during molding, resulting in low hardenability, burrs or holes, and the surface of the resulting semiconductor device. Possibility of deterioration of formability such as wrinkles easily formed.

On the other hand, although attempts have been made to introduce crystallinity into phenolic resins, there is a problem that it is difficult to obtain a homogeneous resin composition due to partial crystallization due to the high degree of crystallization. In contrast, in order to solve the problem of incomplete dissolution when using a crystalline phenolic compound, Patent Document 2 discloses that a quaternary phosphonium compound in a molten state is used as a solvent, and a crystalline phenolic compound is completely dissolved in the solvent to obtain an insoluble phosphonium compound. A molten mixture with incomplete dissolution and excellent storage stability may occur. However, since the hardening accelerator must be heated and dissolved, it is not possible to add a sufficient amount of the crystalline phenolic compound.

The inventors of the present case conducted a detailed study in view of the aforementioned actual situation and found a phenolic resin mixture that is not viscous at 20° C. and has both fluidity and operability, and thus completed the present invention.

That is, the present invention relates to the following [1] to [5].

[1]

A phenol resin mixture, which contains the phenol resin (A) represented by the following formula (1) or the following formula (2) and the alkyl-substituted bisphenol compound (B), the weight ratio of the component (A) to the component (B) 95/5 to 55/45.

(In formula (1), there are a plurality of R ₁ and p independently present, and R ₁ represents a hydrogen atom, an alkyl group with 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group , an amino group or a phenyl group that may have the same substituent as described above, p is a real number from 0 to 3; n is the number of repetitions, and it is a real number from 1 to 20).

(In formula (2), there are a plurality of R ₁ and p independently present, and R ₁ represents a hydrogen atom, an alkyl group with 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group , an amino group or a phenyl group that may have the same substituent as described above, p is a real number from 0 to 3; n is the number of repetitions, and it is a real number from 1 to 20).

[2]

The phenol resin mixture as described in item [1] above, wherein the alkyl-substituted bisphenol compound (B) has a melting point of 70 to 180°C.

[3]

The phenolic resin mixture described in [1] or [2] above has an ICI melt viscosity (cone and plate method) at 150°C of 0.001 to 0.20Pa. s.

[4]

A curable resin composition comprising the phenol resin mixture described in any one of [1] to [3] above and an epoxy resin.

[5]

A hardened product obtained by hardening the curable resin composition described in [4] above.

The phenolic resin mixture of the present invention contributes to productivity due to its extremely high fluidity and excellent handling properties, and can be used as insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up substrates, etc.), and carbon fiber-reinforced composite materials (hereinafter also referred to as "CFRP") and various composite materials, adhesives, coatings, etc. In particular, it is useful as a semiconductor sealing material for protecting semiconductor elements.

The phenol resin mixture of the present invention contains a phenol resin represented by the following formula (1) or formula (2) (hereinafter also referred to as component (A)) and an alkyl-substituted bisphenol compound (B) (hereinafter also referred to as component (B)).

(In formula (1), there are a plurality of R ₁ and p independently present, and R ₁ represents a hydrogen atom, an alkyl group with 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group , an amino group or a phenyl group that may have the same substituent as described above, p is a real number from 0 to 3; n is the number of repetitions, and it is a real number from 1 to 20).

(In formula (2), there are a plurality of R ₁ and p independently present, and R ₁ represents a hydrogen atom, an alkyl group with 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group , an amino group or a phenyl group that may have the same substituent as described above, p is a real number from 0 to 3; n is the number of repetitions, and it is a real number from 1 to 20).

R in the aforementioned formula ( ₁ ) and formula (2) is preferably a hydrogen atom, an alkyl group with 1 to 10 carbons, more preferably a hydrogen atom, an alkyl group with 1 to 3 carbons, especially preferably a hydrogen atom. p is preferably a real number of 0 or 1, particularly preferably 0.

The n value in the aforementioned formula (1), formula (2) is the value of the number average molecular weight obtained by the measurement of the gel permeation chromatography (GPC, detector: RI) of phenolic resin, or can be separated by Calculate the area ratio of the respective peaks.

The value of n in the aforementioned formula (1) and formula (2) is usually 1-20, preferably 1.1-20, more preferably 1.1-10. When n is less than 1, the crystallinity is strong, and a homogeneous resin mixture cannot be obtained even by mechanical kneading. On the other hand, when n is greater than 20, the melt viscosity is high, and it is difficult to use from the viewpoint of fluidity and high filler filling.

The phenolic resins represented by the aforementioned formula (1) and formula (2) can be synthesized according to known synthesis methods, and can also be easily obtained from the market. For example, KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., softening point 65° C.) can be obtained as the phenol resin represented by the aforementioned formula (1), and MEHC-7840-4S (manufactured by Meiwa Chemical Co., Ltd., softening point 58-65°C) as the phenol resin represented by the aforementioned formula (2).

In the phenolic resin mixture of the present invention, the mixing method of component (A) and component (B) is not particularly limited, by melt mixing at a temperature of about 150°C or above the melting point of both, using an extruder or a kneader , rolls, etc. and kneading/mixing, etc. below the melting point, whereby a phenolic resin mixture can be obtained.

The weight ratio of component (A) to component (B) is usually 95/5 to 55/45, preferably 92/8 to 55/45, more preferably 90/10 to 60/40. When the weight ratio of the component (A) exceeds 95, fluidity will deteriorate. On the other hand, if the weight ratio of the component (A) is less than 55, a part of the phenolic resin mixture crystallizes unevenly at 20° C., making it difficult to produce a homogeneous cured product of the molding material. That is, by making the weight ratio of component (A) to component (B) 95/5 to 55/45, it is non-viscous at 20°C and has fluidity at high temperature, so it can have both fluidity and handling sex.

From the point of view of fluidity at high temperature, the ICI melt viscosity (cone and plate method) of the phenolic resin mixture of the present invention at 150° C. is preferably 0.001 to 0.20 Pa‧s, more preferably 0.005 to 0.15 Pa‧s, especially Preferably it is 0.01 to 0.10 Pa‧s.

The melting point of component (B) is usually 70 to 180°C, preferably 100 to 180°C, more preferably 120 to 180°C. When it is lower than 70°C, it is afraid that it will stick at room temperature and it will be difficult to handle. When the temperature is higher than 300°C, the crystallization may not be easy to melt during mixing.

In addition, the melting point can be obtained from the endothermic peak temperature using, for example, a commercially available differential scanning calorimeter (DSC).

Moreover, in order to improve fluidity, the molecular weight of component (B) should be small, specifically, preferably 200-400, more preferably 214-400.

Moreover, the hydroxyl equivalent weight of component (B) is preferably 100 to 200 g/eq., more preferably 110 to 175 g/eq., particularly preferably 120 to 150 g/eq.

Component (B) is not particularly limited as long as it is a bisphenol compound having an alkyl substituent. Specific examples include bisphenol A resins, bisphenol F resins, bisphenol E resins, and bisphenol Z resins having alkyl substituents. Alkyl substituted bisphenol A resins and bisphenol F resins are applicable. type resin.

Also, in component (B), the number of substituted alkyl groups is preferably 2-6. From the viewpoint of crystallinity, the number of substituted alkyl groups is preferably an even number of 2, 4, or 6. The substituted alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, phenyl, and allyl.

Specifically, dimethyl bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, diethyl bisphenol A, tetraethyl bisphenol A, diphenyl bisphenol A, dimethyl Bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, diethyl bisphenol F, tetraethyl bisphenol F, diphenyl bisphenol F, etc.

In the present invention, when the substituted alkyl group is methyl or ethyl, it is preferably a 4-6 substituted bisphenol compound, and if it is phenyl or allyl, it is preferably a 2-substituted bisphenol compound. If it is a methyl or ethyl disubstituted type with a small alkyl group, the reactivity is high, and even when the molecular weight is small and the initial viscosity is low, the reactivity is high, and as a result, fluidity may be lowered.

On the other hand, if the substituent is a large phenyl group or an allyl group, the effect is large, and if four substitutions are made, the reaction may be difficult to react. The total carbon number of the substituent is preferably 2-12, particularly preferably 4-10.

The component (B) used in this invention can use a commercial item, and can also use the thing manufactured by a well-known method. As commercially available products, specific compounds include, for example: 3,3'-dimethyl-4,4'-bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd. Melting point 136°C Molecular weight 256.34 Hydroxyl equivalent 128 substituents The total carbon number of 2), 3,3'-dimethyl-4,4'-bisphenol F (Tokyo Chemical Industry Co., Ltd. melting point 126 ° C molecular weight 228.29 hydroxyl equivalent 114 total carbon number of substituents 2), 3, 3',5,5'-tetramethyl-4,4'-bisphenol A (made by DEEPAK, melting point 165°C, molecular weight 284.40, hydroxyl equivalent, 142 substituents, total carbon number 4), 3,3',5,5'- Tetramethyl-4,4'-bisphenol F (made by DEEPAK, melting point 175°C, molecular weight 284.40, hydroxyl equivalent, 128 substituents, total carbon number 4), etc., but not limited thereto.

The curable resin composition of the present invention contains an epoxy resin.

Specific examples of usable epoxy resins include: novolak-type epoxy resins, bisphenol A-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol aralkyl-type epoxy resin etc. Specific examples include: bisphenol A, bisphenol S, sulfur diphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'- Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalene diol, ginseng-(4-hydroxyphenyl)methane, 1,1 , 2,2-tetra(4-hydroxyphenyl)ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, Benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furan aldehyde, 4,4'-bis(chloromethyl)-1,1' -biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl) Condensation products of benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl ether compounds derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, Glycidyl ester-based epoxy resins, silsesquioxane-based epoxy resins (with glycidyl groups in the siloxane structure of chain, ring, ladder, or at least two of these mixed structures) , and/or epoxy resin with epoxy cyclohexane structure) and other solid or liquid epoxy resins, but not limited thereto.

However, the softening point when all the epoxy resins used are melt-mixed is preferably from 40 to 180°C. Particularly preferred is 40 to 150°C.

The curable resin composition of the present invention may contain an inorganic filler. Inorganic fillers include: crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, magnesium silicate, steatite , spinel, titanium dioxide, talc and other powders or these spheroidized beads, etc., but not limited to these. These may be used individually, and may use 2 or more types. In the present invention, when it is intended to be used as a semiconductor sealing material, crystalline silica, fused silica, and alumina are preferable from the viewpoint of characteristic balance.

The content of these inorganic fillers is preferably used in an amount of 70 to 96% by mass relative to 100% by mass of the curable resin composition of the present invention. Most preferably, it is 70 to 93% by mass. In the present invention, because the fluidity is extremely high, if the amount of the inorganic filler is too small, the balance between the inorganic filler and the resin will be out of balance, and there will be parts with more and less inorganic fillers in the molded body of the resin composition. Poor properties.

Also, when the content of the inorganic filler exceeds 96%, fluidity cannot be exhibited, which is unfavorable.

In the curable resin composition of the present invention, the phenol resin mixture is used as a hardener for epoxy resin. In the present invention, not only the phenol resin mixture of the present invention may be used as the curing agent, but other curing agents may also be used in combination.

Examples of other curing agents that can be used include phenolic compounds, amine compounds, acid anhydride compounds, amide compounds, and carboxylic acid compounds other than the phenol resin of the present invention. Examples of phenolic resins and phenolic compounds include bisphenol A, bisphenol F, bisphenol S, terpene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 4,4'- Dihydroxy-3,3',5,5'-tetramethylbiphenyl, 3,3'-dimethyl-4,4'-biphenol, 4,4'-dihydroxy-3,3'-bis Phenyldiphenyl, 3,3'-diallyl-4,4'-diphenyl, hydroquinone, resorcinol, naphthalene diol, ginseng-(4-hydroxyphenyl)methane, 1,1,2,2-(4-hydroxyphenyl)ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, Acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furan aldehyde, 4,4'-bis(chloromethyl)-1 ,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis(methyl Polycondensates such as oxymethyl)benzene and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, polyphenols such as condensates of terpene and phenols, but are not limited thereto. These may be used individually, and may use 2 or more types.

Preferred phenolic resins can include phenol aralkyl resins (resins with an aromatic alkylene structure), particularly preferably resins with the following characteristics: having a structure selected from at least one of phenol, naphthol, and cresol , the alkylene part that becomes its connecting group is at least one selected from benzene structure, biphenyl structure, and naphthalene structure (specifically, Zylock, naphthol-Zylock, phenol-biphenylene novolac resin, cresol- biphenylene novolac resin, phenol-naphthyl novolak resin, etc.).

Amine compounds and amide compounds include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, Nitrogen-containing compounds such as amines, polyamide resins synthesized from dimers of linolenic acid and ethylenediamine.

Examples of acid anhydride compounds and carboxylic acid compounds include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, formic anhydride, Gennadic Anhydride, Nadic Anhydride, Hexahydrophthalic Anhydride, Methylhexahydrophthalic Anhydride, Butane Tetracarboxylic Anhydride, Bicyclo[2,2,1]heptane-2,3-dicarboxylate Anhydrides, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other acid anhydrides; various alcohols, methanol Carboxylic acid resin obtained by the addition reaction of modified polysiloxane and the aforementioned acid anhydride.

Other examples include imidazole, boron trifluoride-amine complexes, compounds of guanidine derivatives, and the like.

The above-mentioned other curing agents are not limited to these, and these may be used alone, or two or more of them may be used. In the present invention, it is preferable to use a phenolic compound especially from the viewpoint of reliability.

In the curable resin composition of the present invention, the amount of epoxy resin and curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of epoxy groups in all epoxy resins. When it is less than 0.7 equivalent with respect to 1 equivalent of epoxy groups, or when it exceeds 1.2 equivalent, hardening may be incomplete and favorable cured physical properties may not be acquired.

The curable resin composition of the present invention may further contain a curing accelerator.

Specific examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol , 1,8-diaza-bicyclo(5,4,0)undecene-7 and other tertiary amines, triphenylphosphine and other phosphines, tetrabutylammonium salt, triisopropylmethylammonium salt , trimethyldecylammonium salt, cetyltrimethylammonium salt and other quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts and other quaternary phosphonium salts. The counter ion of the 4th grade salt is a halogen, an organic acid ion, a hydroxide ion, etc. Although not specifically specified, it is especially preferable to be an organic acid ion, a hydroxide ion. Examples thereof include metal compounds such as tin octylate and the like. The compounding quantity of the hardening accelerator used as needed is 0.01-5.0 mass parts with respect to 100 mass parts of epoxy resins.

Furthermore, release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers may be added to the curable resin composition of the present invention. And other preparations, various thermosetting resins.

Furthermore, a binder resin can also be formulated in the curable resin composition of the present invention as required. Examples of binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, and polyimides. resin, polysiloxane resin, etc., but not limited thereto. The blending amount of the binder resin is preferably within the range of not impairing the flame retardancy and heat resistance of the hardened product. Depending on the amount used, it is usually 0.05 to 50 parts by mass, preferably 0.05 parts by mass, relative to 100 parts by mass of the resin component. to 20 parts by mass.

The curable resin composition of the present invention can be formulated with known maleimide compounds according to the needs. Specific examples of usable maleimide compounds include: 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide Amine, 2,2'- Bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Laimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylene bismaleimide Laimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, biphenyl aralkyl type horse Laimide, etc., but not limited to these. These may be used individually, and may use 2 or more types together. When formulating the maleimide-based compound, a hardening accelerator may be mixed as needed, and radical polymerization initiators such as the aforementioned hardening accelerators, organic oxides, azo compounds, and the like can be used.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at a predetermined ratio, and is usually pre-cured at 130 to 180°C for 30 to 500 seconds, and then heated at 150 to 200°C. , 2 to 15 hours for post-curing, thereby performing a sufficient hardening reaction, and obtain the hardened product of the present invention. Also, after uniformly dispersing or dissolving the components of the curable resin composition in a solvent or the like, post-curing may be performed to remove the solvent.

The curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, high adhesion, low dielectric coefficient, and low dielectric loss tangent. Specifically, it can be used as a material for all electrical/electronic parts such as insulating materials, build-up boards (printed wiring boards, boards for BGA, build-up boards, etc.), sealing materials, and photoresists. In addition, in addition to molding materials and composite materials, it can also be used in coating materials, adhesives, 3D printing and other fields. Especially in semiconductor sealing, reflow resistance becomes an advantageous characteristic.

A semiconductor device is sealed with the curable resin composition of the present invention. Examples of semiconductor devices include: Dual Inline Package (DIP, Dual Inline Package), Quad Flat Package (QFP, Quad Flat Package), Ball Grid Array (BGA, Ball Grid Array), Chip Size Package (CSP, Chip Size Package), Small Package (SOP, Small Out-Line Package), Thin Small Outline Package (TSOP, Thin Small Outline Package), Thin Quad Flat Package (TQFP, Thin Quad Flat Package), etc.

The preparation method of the curable resin composition of the present invention is not particularly limited, and may be prepared by dispersing or dissolving each component in a solvent, mixing them uniformly and distilling off the solvent if necessary, or prepolymerizing. For example, the phenol resin mixture of the present invention is heated in the presence or absence of a solvent, and hardeners such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenol resins, acid anhydride compounds, and other additives are added. for pre-polymerization. For the mixing or prepolymerization of the components, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reactor with a stirring device is used in the presence of a solvent.

As a method of uniformly mixing without using a solvent, etc., kneading and mixing at a temperature in the range of 50 to 100°C using a kneader, roller, planetary mixer, etc., to obtain a uniform curable resin composition things. The resulting curable resin composition can also be formed into a cylindrical ingot by a molding machine such as a tablet press after being pulverized, or as a granular powder or a powder-like molded body, or by making these compositions on the surface The support is melted and molded into a sheet shape with a thickness of 0.05 mm to 10 mm to form a curable resin composition molded body. The obtained molded product becomes a non-stick molded product at 0 to 20°C, and even if it is stored at -25 to 0°C for more than one week, the fluidity and hardening properties will hardly decrease.

The obtained molded body can be molded into a hardened product by a transfer molding machine or a compression molding machine.

An organic solvent may be added to the curable resin composition of the present invention to form a varnish-like composition (hereinafter also simply referred to as varnish). It is also possible to dissolve the curable resin composition of the present invention in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethicone, etc. Solvents such as methyl acetamide and N-methylpyrrolidone are used as varnishes, impregnated with substrates such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, alumina fibers, paper, etc., and heated and dried. The prepreg is then hot press-molded to form a cured product of the curable resin composition of the present invention. At this time, the amount of the solvent generally accounts for 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present invention and the solvent. If the amount of solvent is less than this range, the viscosity of the varnish will increase and workability will deteriorate, and if the amount of solvent is large, it will cause holes in the hardened product. Moreover, if it is a liquid composition, it can also be in this state, for example, the cured resin containing carbon fiber can be obtained by resin transfer molding (RTM, Resin Transfer Molding) method.

The cured product of the present invention can be used in various applications.

For example, in addition to adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, other additives to resins, etc. Examples of the adhesive include adhesives for electronic materials in addition to those for civil engineering, construction, automobiles, general office work, and medical treatment. Among these, adhesives for electronic materials include: interlayer adhesives for multilayer substrates such as build-up substrates, adhesives for semiconductors such as die bonding agents, underfills, underfills for BGA reinforcement, and anisotropic conductive films. (ACF), anisotropic conductive paste (ACP) and other mounting adhesives, etc.

In particular, in the present invention, although it is mainly used as a sealing material for semiconductors, it may also be used as a method of using the composition as a substrate or as a mold underfill (MUF).

Specifically, the main applications of the currently used sealants include: potting, impregnation, and transfusion for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc. Mold sealing, sealing of IC packages such as QFP, BGA, and CSP during mounting (including underfill for reinforcement), etc.

[Example]

Next, the present invention will be described more specifically by way of examples, and the following "parts" are parts by mass unless otherwise specified. In addition, the present invention is not limited to these Examples.

Various analysis methods used in Examples are described below.

ICI melt viscosity: based on JIS K 7117-2 (ISO3219)

[Examples 1 to 6, Comparative Examples 1 to 4]

Using a mixing roller, KAYAHARD GPH-65 (the phenolic resin represented by the aforementioned formula (1), manufactured by Nippon Kayaku Co., Ltd., melting point 65° C.), MEHC-7840-4S (the aforementioned formula (2) ) represented by phenol resin, manufactured by Meiwa Chemical Co., Ltd., melting point 58-65°C), 3,3',5,5'-tetramethyl-4,4'-bisphenol A (abbreviation: TMBPA, manufactured by DEEPAK, melting point 165°C molecular weight 284.40 hydroxyl equivalent 142 total carbon number of substituents 4), 3,3',5,5'-tetramethyl-4,4'-bisphenol F (abbreviation: TMBPF, manufactured by DEEPAK melting point 175°C molecular weight 284.40 Hydroxyl equivalent 128 total carbon number of substituent 4), and 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl (abbreviation: TMBP, manufactured by Tokyo Chemical Industry Co., Ltd. Melting point 223 -225°C Molecular weight 242.32 Total carbon number of substituents 4) Melt mixing was carried out at 150°C for 30 minutes to prepare a phenol resin mixture.

[Appearance Observation]

The appearance of the obtained phenol resin mixture at room temperature (20° C.) was visually observed.

Those whose appearance was in a uniform state without crystal lumps were evaluated as ◯, and those with crystal lumps were evaluated as x.

[stickiness]

The sticky feeling on the surface of the obtained ingot was evaluated. The evaluation method is to press the obtained ingot with a finger for 10 seconds to evaluate the adhesion degree of the coating film.

○. ． ． Non-stick dry finish.

△. ． ． Sticky but does not stick to fingers.

×． ． ． Very sticky and clings to fingers.

[Table 1]

[Example 7, 8, Comparative Example 5]

[Swirl test]

Using a mixing roller, the epoxy resin, the phenolic resin mixture (Examples 5, 6 and Comparative Example 2), the silica filler, and the hardening accelerator were kneaded at 80° C. for 25 minutes at the ratios shown in Table 2 for mixing. Then, a swirl test was performed under the following conditions using an Archimedes screw mold and a transfer molding machine.

Mold: obtained according to EMMI-1-66

Mold temperature: 175°C

Transfer pressure: 70kgf/cm ²

Pressure: 5t press, pot diameter: 30mm

Injection time: 1 second

Forming time: 120 seconds

[gelation time]

Put an appropriate amount of the curable resin composition listed in Table 2 on a hot plate at 175°C with a metal spatula, stir with a metal spatula, and measure the time until the sample loses its adhesiveness and can be peeled off the hot plate or the adhesiveness disappears .

In the swirl test, the larger the value, the better the fluidity. The gel time is the time until fluidity is lost when the sealing material is heated at a fixed temperature, and it can be appropriately selected regarding the hardening characteristics.

[Table 2]

NC-3000: biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 277g/eq)

MSR-2102: High-purity positive spherical silica filler (manufactured by Longsen Co., Ltd.)

TPP: Triphenylphosphine (manufactured by Junzheng Chemical Co., Ltd.)

From Tables 1 and 2, it can be confirmed that the phenol resin mixture of the present invention is excellent in handleability and fluidity.

Although the present invention has been described in detail with reference to specific aspects, it is understood by those skilled in the art that various changes and corrections can be made without departing from the spirit and scope of the present invention.

In addition, this case is based on the Japanese patent application filed on March 23, 2021 (Japanese Patent Application No. 2021-048213), and the entire content thereof is incorporated by reference. In addition, all the reference documents cited here are based on the whole content.

[industrial availability]

From the above, it can be seen that the phenol resin mixture of the present invention has high fluidity and handleability, and is excellent in productivity and moldability. Therefore, the curable resin composition of the present invention can be used as insulating materials for electric and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.) and carbon fiber reinforced composite materials (hereinafter also referred to as "CFRP"). Various composite materials, adhesives, coatings, etc. In particular, it is useful as a semiconductor sealing material for protecting semiconductor elements.

Claims (5)

A phenol resin mixture, which contains the phenol resin (A) represented by the following formula (1) or the following formula (2) and an alkyl-substituted bisphenol compound (B), the weight ratio of the component (A) to the component (B) 95/5 to 55/45;

In formula (1), a plurality of R ₁ and p exist independently, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group or a phenyl group that may have the same substituent as described above, p is a real number from 0 to 3; n is a repeating number, which is a real number from 1 to 20;

In formula (2), a plurality of R ₁ and p exist independently, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbons, a hydroxyl group, a methoxy group, an ethoxy group, a nitro group, a nitrile group, An amino group or a phenyl group which may have the same substituent as above, p is a real number from 0 to 3; n is a repeating number, which is a real number from 1 to 20. The phenol resin mixture according to claim 1, wherein the melting point of the alkyl-substituted bisphenol compound (B) is 70 to 180°C. The phenolic resin mixture as described in Claim 1 or 2, wherein the ICI melt viscosity (cone and plate method) at 150 is 0.001 to 0.20 Pa‧s. A curable resin composition, which contains the phenol resin mixture and epoxy resin according to any one of claims 1 to 3. A cured product obtained by curing the curable resin composition described in Claim 4.