JP2014108972A - Curable resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of providing a cured product capable of exhibiting good electrical characteristics and excellent in heat resistance, strength and the like, and to provide a sealant and a semiconductor device using the same.SOLUTION: There is provided a curable resin composition containing a novolak type cyanate ester resin and a phosphonium salt.

Description

The present invention relates to a curable resin composition and its use. More specifically, a curable resin composition used for various applications such as mounting applications, optical applications, optical device applications, display device applications, mechanical component applications, electrical / electronic component applications, automotive component applications, printing ink applications, In addition, the present invention relates to a sealing material and a semiconductor device using the same.

Curable resin compositions that can be cured by heat or active energy rays include, for example, components of various display devices such as liquid crystal display devices, solid-state imaging devices, touch panel display devices, inks, printing plates, printed wiring boards, and semiconductor devices. Various applications have been studied for various uses such as various optical members such as photoresists, electric machines and electronic devices, and curable resin compositions having excellent characteristics required for each use have been developed.

By the way, the cyanate ester resin is a compound having an average of at least two cyanate groups (—OCN) in one molecule, and is known to polymerize while generating a triazine ring structure by cyclization and trimerization. In recent years, application to various industrial fields including electric, mechanical, and automobile fields has been studied.

As a curable resin composition using a conventional cyanate ester resin, for example, a trifunctional or tetrafunctional epoxy resin, a curing agent having a group that reacts with at least two epoxy groups in one molecule, and in one molecule An epoxy resin composition containing a compound having at least two cyanate groups and an inorganic filler (Patent Document 1); a thermosetting resin composition comprising a cyanate ester compound and / or a prepolymer thereof and an epoxy resin in combination. And a thermosetting resin composition in which an organoaluminum compound and a silanol group or an organosilicon compound having an alkoxy group are blended as a curing catalyst (Patent Document 2); an epoxy resin, a phenol resin, a cyanate ester prepolymer having a triazine ring Contains a certain triazine resin, curing accelerator and inorganic filler as essential components An epoxy resin composition for semiconductor encapsulation (Patent Document 3); a resin composition containing a cyanate resin and an epoxy resin, and a cured product of the resin composition having specific physical properties (Patent Document 4); ing. Non-Patent Document 1 discloses a technique of using TPP-MK (tetraphenylphosphonium tetrakis (4-methylphenyl) borate) as a curing accelerator for curing bisphenol A type dicyanate (BADCY). .

International Publication No. 2007/037500 Pamphlet Japanese Patent Laid-Open No. 9-100349 JP 2001-206931 A JP 2012-12555 A

Yokohama National University, Akio Takahashi, “Study on Functional Materials Using Cyanate”, Handouts of Precision Network Polymer Study Group, Society of Polymer Science, Precision Network Polymer Study Group, April 21, 2011

As described above, various curable resin compositions using a cyanate ester resin have been developed. Generally, for curing a cyanate ester resin, a metal complex or metal salt is used as a catalyst, and a phenol or silanol is used as a catalyst auxiliary. Is used (see Patent Documents 1 and 2, etc.). However, when a metal complex or a metal salt is used as an insulating material, the electrical characteristics of the material may not be good. Therefore, there has been room for improvement to obtain a cured product that can exhibit good electrical characteristics and also has excellent heat resistance and strength.

The present invention has been made in view of the above-mentioned present situation, a curable resin composition capable of exhibiting good electrical characteristics and giving a cured product excellent in heat resistance, strength, and the like, and a seal using the same An object is to provide a stopper and a semiconductor device.

The present inventor has conducted various studies on materials that can be preferably applied to the curable resin composition. As a curable resin composition containing a cyanate ester resin, the present inventors have a high glass transition temperature (Tg) and high toughness. In addition, attention was paid to the fact that a cured product having low linear expansion can be provided. And when a novolak type thing is used as a cyanate ester resin, it has been found that a phosphonium salt can suitably act as a curing catalyst (curing accelerator), and when a novolac type cyanate ester resin and a phosphonium salt are used in combination, It has also been found that a cured product can be obtained that exhibits good electrical properties and is excellent in heat resistance and strength. Furthermore, it has been found that if a sealing material using such a curable resin composition is used, a semiconductor device or the like having high reliability and adhesion can be obtained, and the above problems can be solved brilliantly. The present invention has been achieved.

That is, the present invention is a curable resin composition containing a novolac-type cyanate ester resin and a phosphonium salt.
The present invention is also a sealing material using the curable resin composition.
The present invention is also a semiconductor device using the sealing material.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[Curable resin composition]
The curable resin composition of the present invention contains a novolac-type cyanate ester resin and a phosphonium salt, and each of these components can be used alone or in combination of two or more. Moreover, as long as these are essential, other components may be included appropriately.

The shape of the curable resin composition may be liquid or solid at room temperature (25 ° C.), but is particularly preferably liquid at room temperature. Thereby, for example, when a curable resin composition is used as a sealing agent, it is possible to fill every corner of a sealing target, and to obtain a semiconductor device with further improved reliability and adhesion. Is possible. Thus, the form in which the said curable resin composition is a liquid curable resin composition is one of the suitable forms of this invention.

In this specification, “liquid” means being in a liquid state at room temperature (25 ° C.). Specifically, it means that crystals are not precipitated at room temperature (25 ° C.) and that the fluid is not a highly viscous fluid. This state may be confirmed visually, but is judged by viscosity. It is also possible to do. For example, the curable resin composition preferably has a viscosity at a measurement temperature of 60 ° C. of 100 Pa · s or less. Thereby, it becomes a liquid resin composition with higher fluidity. More preferably, it is 50 Pa.s or less, More preferably, it is 40 Pa.s or less, Most preferably, it is 20 Pa.s or less. Moreover, the minimum of a viscosity is not specifically limited, For example, what is necessary is just a grade which an inorganic filler does not settle. For example, the viscosity at 60 ° C. is preferably 0.01 Pa · s or more. More preferably, it is 0.1 Pa · s or more.
The viscosity of the curable resin composition can be measured using a rheometer (DISCOVERY HR-1) manufactured by TA Instruments, for example, at a measurement temperature of 60 ° C. and in an air atmosphere.

The curable resin composition also preferably has a glass transition temperature (Tg) of 210 ° C. or higher. Thereby, it becomes possible to give the hardened | cured material which was further excellent in heat resistance. More preferably, it is 220 degreeC or more, More preferably, it is 230 degreeC or more, Most preferably, it is 240 degreeC or more, Most preferably, it is 250 degreeC or more.
In the present specification, Tg of the curable resin composition is measured, for example, using a dynamic viscoelasticity measuring device (RSA-III) manufactured by TA Instruments, in a temperature rising rate of 5 ° C./min, in an air atmosphere. can do.

<Novolac type cyanate ester resin>
In the curable resin composition, the novolak-type cyanate ester resin is a compound having a novolak structure and having an average of at least two cyanato groups (—OCN) in one molecule (that is, polyfunctional having an average of two or more functions). Compound). From the viewpoint of increasing Tg, it is preferable that the average functional number is large, and from the viewpoint that it is difficult to develop thixotropy, it is preferable that the average functional number is small. Therefore, the average functional number of the novolak-type cyanate ester resin Is preferably set appropriately in consideration of these balances.

As said novolak-type cyanate ester resin, the compound represented by the following general formula (a) is suitable, for example.

In the general formula (a), R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, or a halogen group (X). p represents an integer of 1 to 25. p is preferably 1 to 21. In particular, from the viewpoint of more effectively obtaining a liquid curable resin composition, p is more preferably 1 to 10.

It does not specifically limit as a compound represented by the said general formula (a), For example, a phenol novolak-type cyanate ester resin, a cresol novolak-type cyanate ester resin, etc. are mentioned. Of these, phenol novolac type cyanate ester resins are preferred.

As the novolak-type cyanate ester resin, a multimer (for example, trimer, pentamer) formed by cyclization of a cyanate group of the compound represented by the general formula (a) to form a triazine ring structure. Can also be used. Among these, a trimer is preferable from the viewpoint of operability and solubility in other curable resins. A technique for obtaining a multimer may be performed by a normal technique.

The shape of the novolac-type cyanate ester resin is preferably liquid at room temperature (25 ° C.), but may be solid (including semi-solid). When it is solid, it is preferable that it has high compatibility or has a melting point or softening point of 100 ° C. or lower in consideration of melt kneading with other resin components as described later. . More preferably, it has a melting point or softening point of 60 ° C. or lower.
The melting point means the temperature (° C.) at which the crystals melt and become liquid in an inert atmosphere. Therefore, amorphous compounds and those already in liquid form at room temperature do not have a melting point. The melting point of the novolak-type cyanate ester resin can be measured, for example, by differential scanning calorimetry (DSC). The softening point (° C.) can be measured according to JIS K7234 (1986). For example, it can be measured using a thermal softening temperature measuring device (product name “ASP-MG4”, manufactured by Meitec). Can do.

The novolak cyanate ester resin preferably has a weight average molecular weight of 100 to 3500. That is, it is preferable that the weight average molecular weight of the cyanate ester resin before being subjected to the curing reaction is 100 to 3500. Within this range, the physical properties derived from the curable resin composition can be more stably exhibited. More preferably, it is 120 or more, More preferably, it is 150 or more, More preferably, it is 200 or more, Especially preferably, it is 250 or more, Most preferably, it is 300 or more, More preferably, it is 3000 or less. Especially, from a viewpoint of obtaining a liquid curable resin composition more effectively, it is preferable that a weight average molecular weight is 2000 or less, More preferably, it is 1000 or less, More preferably, it is 900 or less.
The molecular weight (number average molecular weight and weight average molecular weight) of the novolac-type cyanate ester resin can be determined, for example, by GPC (gel permeation chromatography) measurement under the following measurement conditions.

<GPC measurement conditions for molecular weight>
Measuring instrument: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: “TSK-GEL SUPER HZM-N 6.0 * 150” x 4 manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Flow rate: 0.6 mL / min Temperature: 40 ° C.
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

<Phosphonium salt>
The curable resin composition also contains one or more phosphonium salts. This makes it possible to sufficiently cure the novolac cyanate ester resin while satisfactorily expressing the electrical characteristics of the curable resin composition.

The phosphonium salt is, for example, PH ₄ ⁺ X ⁻ , RPH ₃ ⁺ X ⁻ , R ₂ PH ₂ ⁺ X ⁻ , R ₃ PH ⁺ X ⁻ , and / or R ₄ P ⁺ X ⁻ (wherein R is Are the same or different and each represents an organic residue, and X represents a halogen atom. In addition, although it does not specifically limit as an organic residue represented by R, For example, it is preferable that it is a C1-C30 alkyl group or an aryl group, and these groups may have a substituent. Good. It does not specifically limit as a halogen atom, For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

Specific examples of the phosphonium salt include organic phosphorus compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tris (dimethoxyphenyl) phosphine, and hydrogen halides. In addition to compounds obtained by reaction with alkyl halides, etc., triphenylphosphine / triphenylborate, tetraphenylphosphine / tetraphenylborate, tributylhexadecylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxide, tetrabutyl Phosphonium acetate, tetraphenylphosphonium bromide, methyl triphenylphosphonium bromide, ethyl triphenylphosphonium bromide Mido, n-propyl triphenylphosphonium bromide, i-propyl triphenylphosphonium iodoide, n-butyl triphenylphosphonium bromide, methoxymethyl triphenylphosphonium chloride, benzyl triphenylphosphonium chloride, tetraphenylphosphonium chloride, Preferred examples include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetra-p-tolylborate, tri-tert-butylphosphonium / tetraphenylborate, and triphenylphosphine / triphenylborane. Among these, tetraphenylphosphonium tetra-p-tolylborate is most preferable from the viewpoint of further promoting the curing.

The content ratio of the phosphonium salt is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of all resin components contained in the curable resin composition, for example. More preferably 0.005 parts by weight or more, still more preferably 0.008 parts by weight or more, particularly preferably 0.01 parts by weight or more, more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less, Particularly preferred is 2 parts by weight or less, and most preferred is 1.5 parts by weight or less.
The “total resin component” is a combination of all the resin components contained in the curable resin composition of the present invention, that is, a novolac-type cyanate ester resin, and other resin components further contained as necessary. It means a resin component.

<Other resin components>
The curable resin composition may also contain other resin components in addition to the novolak cyanate ester resin described above. As such other resin components, those that are compatible with the above-described novolak cyanate ester resin can be used singly or in combination of two or more. For example, high heat-resistant curable resins such as bismaleimide resin and benzoxazine resin, in addition to epoxy resin, cyanate ester resin other than novolak-type cyanate ester resin, phenol resin, urethane resin, and the like can be given. Among these, it is preferable to use an epoxy resin or a bismaleimide resin from the viewpoints of heat resistance and reactivity. Thus, the form in which the curable resin composition further contains an epoxy resin and / or a bismaleimide resin is also a preferred form of the present invention. More preferably, it contains at least an epoxy resin.

Here, when an epoxy resin is used, a cured product having more excellent heat resistance can be obtained. In addition, when the above-described high heat-resistant curable resin is used, it includes a wide gap semiconductor material such as silicon carbide (SiC) or gallium nitride (GaN) and has a high operating upper limit temperature. A particularly suitable cured product can be obtained. For example, when a bismaleimide resin is used, properties such as durability and heat resistance of the cured product are further improved.

The shape of the other resin component is preferably liquid at room temperature (25 ° C.), but may be solid (including semi-solid). When it is solid, it is preferable that it has high compatibility or has a melting point or softening point of 100 ° C. or lower in consideration of melt kneading with the novolak-type cyanate ester resin. More preferably, it has a melting point or softening point of 80 ° C. or lower.

The said epoxy resin is a compound which contains at least 1 type of group selected from the group which consists of an epoxy group and a glycidyl group in a molecule | numerator, for example, the following compound etc. are mentioned.
Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) and epihalohydrin; and the epoxy resin with bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Further, high molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction; phenols (phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, suphenol S, etc.), formaldehyde, aceto Artehydride, propionaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, par A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by condensation reaction of polyphenols obtained by condensation reaction with xylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and epihalohydrin; tetra Aromatic crystalline epoxy resin obtained by condensation reaction of methylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. with epihalohydrin; in addition to the aromatic crystalline epoxy resin, the above bisphenols, tetramethylbiphenol, tetra High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of methyl bisphenol F, hydroquinone, naphthalene diol, etc .; Trisphenol type epoxy Resins; Bisphenols as described above, alicyclic glycols with hydrogenated aromatic skeleton (tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, etc.) or mono / polysaccharides (ethylene glycol, diethylene glycol, triethylene glycol) , Tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its Multimer, glucose, fructose, lactose, maltose, etc.) and fat obtained by condensation reaction with epihalohydrin An aliphatic glycidyl ether type epoxy resin; a high molecular weight aliphatic glycidyl ether type epoxy resin obtained by further subjecting the aliphatic glycidyl ether type epoxy resin to an addition reaction with the above bisphenol; (3,4-epoxycyclohexane) methyl 3 Epoxy resin having an epoxycyclohexane skeleton such as', 4'-epoxycyclohexylcarboxylate; glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid, etc. with epihalohydrin; hydantoin Or a tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by condensation reaction of cyanuric acid, melamine, benzoguanamine and the like with epihalohydrin; Among these epoxy resins, glycidyl ether type epoxy resins having an aromatic moiety are preferable.

In order to further enhance the curability of the epoxy resin, it is preferable to use a polyfunctional compound (also referred to as a polyfunctional epoxy compound) containing two or more epoxy groups and / or glycidyl groups in one molecule. More preferably, it is a polyfunctional compound containing 3 or more epoxy groups and / or glycidyl groups in one molecule, that is, a trifunctional or more polyfunctional epoxy compound, thereby further improving the Tg of the curable resin composition. Therefore, it becomes possible to give a cured product having further improved heat resistance. Thus, the form in which the epoxy resin is a polyfunctional compound having three or more functional groups is also one of the preferred forms of the present invention. Moreover, the upper limit of the functional number is not particularly limited, but is preferably 10 or less, for example.

When the said curable resin composition contains an epoxy resin, it is suitable that the epoxy equivalent in the said curable resin composition is 80-400 g / mol. More preferably, it is 90-300 g / mol, More preferably, it is 100-200 g / mol.

The bismaleimide resin is not particularly limited as long as it is a compound having two or more maleimide groups in the molecule, and includes, for example, a cocondensate of bismaleimide and an aldehyde compound. More than seeds can be used.
Examples of the bismaleimide include 4,4′-diphenylmethane bismaleimide, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-m-phenylene bismaleimide, and N, N. '-P-phenylenebismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1,1,3,3 3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N′-p, p′-diphenyldimethylsilylbismaleimide, N, N′-4,4′-diphenyl ether Bismaleimide, N, N′-methylenebis (3-chloro-p-phenylene) bismaleimide, N, N′-4,4′-diphenylsulfone Maleimide, N, N′-4,4′-dicyclohexylmethane bismaleimide, N, N′-dimethylenecyclohexane bismaleimide, N, N′-m-xylene bismaleimide, N, N′-4,4′-diphenyl Examples include cyclohexane bismaleimide and N-phenylmaleimide.
Examples of the aldehyde compound include formaldehyde, acetaldehyde, benzaldehyde, hydroxyphenyl aldehyde, and the like.

The bismaleimide resin may also be a compound represented by the following general formula (1).

In the formula, R ⁵ represents the following formula:

The bivalent group represented by these is represented. Q ¹ is a group directly connected to two aromatic rings, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, and an oxide. It represents at least one group selected from the group consisting of groups.

Specific examples of the bismaleimide resin represented by the general formula (1) include 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, 1, 1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2- [4- (3-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 4,4-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-male Dophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, General formula (2):

(Wherein Q ² represents a divalent group comprising an aromatic ring which may have a substituent. N represents the number of repetitions and is an average of 0 to 10). Etc. are suitable.
Specifically, Q ² is preferably a divalent group such as a phenyl group, a biphenyl group, or a naphthyl group (such as a phenylene group, a biphenylene group, or a naphthylidene group).

As the cyanate ester resin other than the novolak-type cyanate ester resin, a bifunctional or higher polyfunctional compound, that is, one having at least two cyanate groups (—OCN) on average in one molecule is preferable. From the viewpoint of increasing Tg, a higher average functional number is preferable, and from the viewpoint of making thixotropic properties less likely to be expressed, a lower average functional number is preferable. Therefore, the average functional number of the cyanate ester resin is It is preferable to set appropriately considering these balances.

As the cyanate ester resin other than the novolac-type cyanate ester resin, for example, a compound represented by the following general formula (b) is suitable.

In the general formula (b), R ¹ and R ² are the same as the symbols in the general formula (a). R ³ is the same or different and represents an organic group represented by the following chemical formula. R ⁴ is the same or different and represents an organic group represented by the following chemical formula. m is 0 or 1. n represents an integer of 0 to 10.

Although it does not specifically limit as a compound represented by the said general formula (b), For example, the following compound etc. are mentioned.
Bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (3-methyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) -1 , 1-ethane, bis (4-cyanatophenyl) -2,2-ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanato Phenyl) methane, di (4-cyanatophenyl) ether, di (4-cyanatophenyl) thioether, 4,4- {1,3-phenylenebis (1-methylethylidene)} bisphenylcyanato, 4,4 -Dicyanatophenyl, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1'-bis- (p-cyanatophenyl) -ethane , 2,2'- (P-cyanatophenyl) propane, 4,4′-methylenebis (2,6-dimethylphenylcyanato), 2,2′-bis (p-cyanatophenyl) hexafluoropropane, α, α′-bis Cyanate ester resins of dihydric phenols such as (4-cyanatophenyl) -m-diisopropylbenzene;
Cyanate esters of trivalent phenols such as tris (4-cyanatephenyl) -1,1,1-ethane, bis (3,5-dimethyl-4-cyanatephenyl) -4-cyanatephenyl-1,1,1-ethane resin;
Bisphenol type cyanate ester resin;

As the cyanate ester resin, a multimer (for example, trimer or pentamer) formed by cyclization of a cyanate group of the compound represented by the general formula (b) to form a triazine ring structure is used. You can also Among these, a trimer is preferable from the viewpoint of operability and solubility in other curable resins. A technique for obtaining a multimer may be performed by a normal technique.

The other resin component preferably has a weight average molecular weight of 150 to 20,000. That is, it is preferable that the weight average molecular weight of the resin component before being subjected to the curing reaction is 150 to 20000. Within this range, the risk of volatilization is further suppressed, and the viscosity can be made more appropriate. More preferably, it is 180-15000, More preferably, it is 200-10000.
The weight average molecular weight of the resin component can be determined, for example, by GPC (gel permeation chromatography) measurement under the measurement conditions described above.

As the content ratio of the other resin components (preferably epoxy resin and / or bismaleimide resin) in the curable resin composition, the total amount of the novolac-type cyanate ester resin and the other resin components (that is, the total amount of all resin components) Is 100% by mass, it is preferably 0 to 50% by mass. More preferably, it is 5-40 mass%, More preferably, it is 10-30 mass%, Most preferably, it is 15-25 mass%.

<Other ingredients>
The curable resin composition of the present invention may also contain other components other than the above-described components as necessary. For example, inorganic fillers; flame retardants; volatile components such as organic solvents and diluents; curing accelerators (curing accelerators other than phosphonium salts); curing agents; reinforcing materials; coupling agents; stress relieving agents; Stabilizers; colorants; plasticizers; flexible agents; various rubbery materials; photosensitizers; pigments; and the like, and one or more of these can be used. Among these, it is particularly preferable to further include an inorganic filler and / or a flame retardant. It is also preferable to further contain a basic compound described later.

-Inorganic filler-
When the said curable resin composition contains an inorganic filler, it becomes a more suitable thing by the sealing material etc. of a mounting board | substrate. Thus, the form which further contains an inorganic filler is also one of the suitable forms of this invention.

It does not specifically limit as said inorganic filler, What is necessary is just to use what is used by the sealing material use of a normal mounting substrate, etc. 1 type, or 2 or more types. For example, it is preferable to use silica such as fused silica, crystalline silica, and finely divided silica, and metal oxides such as alumina, silicon nitride, and magnesia. Of these, silica is preferable.

When the said inorganic filler is included, it is suitable that the content rate shall be 50-90 mass% with respect to 100 mass% of total amounts of curable resin composition. By using a large amount of the inorganic filler in this way, for example, when used to obtain a sealing material for a mounting substrate, it becomes possible to sufficiently prevent the substrate from being warped after curing. More preferably, it is 60-85 mass%, More preferably, it is 65-80 mass%.

-Flame retardant-
When the said curable resin composition contains a flame retardant, the hardened | cured material more excellent in the flame retardance can be obtained, and it becomes a more suitable thing for semiconductor sealing material use. Thus, the form which contains a flame retardant is also one of the suitable forms of this invention.

Although it does not specifically limit as said flame retardant, What is necessary is just to use what is used normally by 1 type, or 2 or more types, A non-halogen compound and a non-antimony compound are suitable. For example, phosphorus-containing compounds such as phosphate esters, triphenylphosphine oxide, red phosphorus; nitrogen-containing compounds such as melamine, melamine derivatives, melamine-modified phenol resins, cyanuric acid derivatives, isocyanuric acid derivatives, triazine ring-containing compounds; phosphazenes, Phosphorus and nitrogen-containing compounds such as cyclophosphazenes; zinc compounds such as zinc oxide, zinc borate, molybdenum zinc and zinc stannate; metal oxides such as iron oxide and molybdenum oxide; metals such as magnesium hydroxide and aluminum hydroxide And hydroxides; metal complex compounds such as dicyclopentadienyl iron; and the like. Among these, phosphorus and nitrogen-containing compounds are preferable, and phosphazenes are more preferable. This makes it possible to obtain a cured product that is more excellent in flame retardancy. Thus, the form which further contains phosphazenes is also one of the suitable forms of this invention.

The content ratio of the flame retardant (preferably phosphazenes) is preferably 2 to 30 parts by weight with respect to 100 parts by weight of the total amount of all resin components, for example. More preferably, it is 5 to 20 parts by weight.

-Volatile component-
The curable resin composition of the present invention can exist in a liquid state at room temperature without containing a volatile component. Thus, when it is a liquid curable resin composition, it can be used suitably also for the use for which it is desired not to contain a volatile component. Therefore, the content of the volatile component in 100% by mass of the curable resin composition is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially. “Substantially free of volatile components” means that the content of volatile components is less than the amount capable of dissolving the composition, for example, 1 mass in 100 mass% of the curable resin composition. % Or less is preferable. Thus, the form in which the said curable resin composition does not contain a volatile component is also one of the suitable forms of this invention. In addition, when used for applications that may contain volatile components, such as printing ink applications, the curable resin composition may contain volatile components, and such a form is also a preferred embodiment of the present invention. It is one of.
The volatile component content can be obtained, for example, by heating for 1 hour at 170 ° C. in an oven in an air atmosphere and reducing the weight as the volatile component.

When the said curable resin composition contains a volatile component, it does not specifically limit as the said volatile component, What is necessary is just to use normally. Examples thereof include a solvent containing a compound having at least one structure selected from the group consisting of an ether bond, an ester bond and a nitrogen atom.

Examples of the compound having an ether bond include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, and benzyl ethyl. Ether, diphenyl ether, dibenzyl ether, peratrol, propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, thionel, 1,2-dimethoxyethane, 1,2-di Ethoxyethane, 1,2-dibutoxyethane, glycerin ether, crown ether, methylal, acetal, methyl cellosol , Ethyl cellosolve, butyl cellosolve, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, Triethylene glycol monomethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol propyl ether Propylene glycol butyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2- Methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 2-phenoxyethanol, 2- (Benzyloxy) ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. are preferred It is.

Examples of the compound having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-acetate Butyl, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate , Ethylene glycol monoacetate, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, dimethyl carbonate, diethyl carbonate, dipropyl carbonate Dibutyl carbonate, butyric acid ester, isobutyric acid ester, isovaleric acid ester, stearic acid ester, benzoic acid ester, ethyl cinnamate, abietic acid ester, adipic acid ester, γ-butyrolactone, shu Acid esters, malonic acid esters, maleic acid esters, tartaric acid esters, citric acid esters, sebacic acid esters, phthalic acid esters, ethylene diacetate and the like are suitable.

Examples of the compound containing the nitrogen atom include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, Benzonitrile, α-tolunitrile, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, 2 -Pyrrolidone, N-methylpyrrolidone, ε-caprolactam and the like are preferred.

Examples of the compound having a plurality of structures selected from the group consisting of the ether bond, ester bond and nitrogen atom include N-ethylmorpholine, N-phenylmorpholine, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. , Phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether Acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, tripropylene glycol methyl ether acetate are preferable. Among these compounds, one or more kinds can be used.

-Curing accelerator-
Examples of the curing accelerator other than the phosphonium salt include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, and the like. Imidazole compounds; tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7; triphenylphosphine, tributylphosphine, tri (p -Methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenylborate, tetraphenylphosphine / tetraphenylborate, tributylhexadecylphosphonium bromide, tris (dimethoxyph Nyl) phosphine and other organic phosphorus compounds; aluminum and zirconium and other organic metal compounds; and others, heterocyclic amine compounds, boron complex compounds, organic ammonium salts, organic sulfonium salts, organic peroxides, their reactants, etc. These can be used, and one or more of these can be used.

-Curing agent-
It does not specifically limit as said hardening | curing agent, What is necessary is just to use what is used normally 1 type, or 2 or more types. For example, acid anhydrides, polyhydric phenols, amines and the like can be mentioned. Among them, it is preferable to use acid anhydrides, polyhydric phenols and / or amines. Thereby, the curable resin composition is more fully cured, and it becomes possible to give a cured product that is more excellent in various physical properties such as heat resistance.

Examples of the acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabromophthalic anhydride, trialkyltetrahydrophthalic anhydride, 2,4-diethyl glutaric anhydride, hymic anhydride (5-norbornene-2,3-dicarboxylic anhydride Product), methyl hymic acid anhydride, methyl nadic acid anhydride (methyl-5-norbornene-2,3-dicarboxylic acid anhydride), chlorendic acid anhydride, diphenic acid anhydride, 3,4-dimethyl-6- (2-Methyl-1-propenyl) -1,2,3,6-tetrahydride Monofunctional acid anhydrides such as phthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride; pyromellitic dianhydride, Maleated alloocimene, benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetrabisbenzophenone tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexene tetracarboxylic dianhydride , Biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-Dicarboxyphenyl) methane dianhydride, 2,2-bis (3 Bifunctional acid anhydrides such as 4-dicarboxyphenyl) propane dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; and acid anhydrides having a free acid such as γ-aconitic anhydride, glycolic anhydride, trimellitic anhydride, polyazeline acid anhydride, and the like.

Examples of the polyhydric phenols include phenol novolac resin, cresol novolac resin, triphenolmethane type phenol resin, terpene modified phenol resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenylene skeleton, biphenylene skeleton or naphthylene skeleton. And phenol aralkyl resins having a phenylene skeleton or a biphenylene skeleton, bisphenol compounds, and the like. In addition, from the viewpoint of curability, the hydroxyl equivalent of the polyhydric phenols is preferably 90 to 250 g / eq, for example.

The polyhydric phenols are preferably compounds having an aralkyl group containing a phenylene skeleton, biphenylene skeleton or naphthylene skeleton in the structure. A cured product obtained using such a compound has a low elastic modulus under a high temperature environment, and can also achieve low water absorption due to low phenolic hydroxyl groups, thus further improving solder reflow resistance. It becomes possible to do. In addition, since a compound containing a naphthylene skeleton has a high glass transition temperature and a low coefficient of linear expansion, for example, when the cured product is applied to a semiconductor device, it exhibits a sufficiently low warpage. It becomes possible.
The polyhydric phenols are more preferably the following general formula (3):

(In the formula, R ⁷ represents a phenylene group, a biphenylene group, or a naphthylene group. —R ⁶ (OH) — represents a hydroxyphenylene group, a 1-hydroxynaphthylene group, or a 2-hydroxynaphthylene group. R ⁸ And R ⁹ are groups introduced into R ⁶ and R ⁷ respectively, and are the same or different and each represent a hydrocarbon group having 1 to 10 carbon atoms, and the average value of p is a number of 1 to 10 , Q is an integer of 0 to 5, and r is an integer of 0 to 5). Such a compound is preferably 10% by mass or more with respect to 100% by mass of the total amount of the polyhydric phenols, and thereby can further exhibit solder reflow resistance and low warpage. More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more.
In the case where -R ⁶ (OH)-is a hydroxynaphthylene group, as described above, the effect of improving the low warpage can be obtained by increasing the glass transition temperature and decreasing the linear expansion coefficient. Since it has a large amount of aromatic carbon, it is possible to improve the flame resistance.

As said amine, what has 1 or 2 or more of primary amines or secondary amines in a molecule | numerator is preferable, for example, diethylenetriamine, trielalentetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2- Aliphatic amines such as methylpentamethylenediamine; cycloaliphatic amines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornene dimine, 1,2-diaminocyclohexane; N-amino Piperazine-type amines such as ethylpiperazine and 1,4-bis (2-amino-2-methylpropyl) piperazine; m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, Methylene bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetramethyl-4 , 4′-diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane, 2,4-diaminotoluene, diaminobenzene, methylenedianiline, bis (chloroanilino) methane, oxy And aromatic amines such as dianiline, bis (hydroxyanilino) methane, bis [(aminophenoxy) phenyl] sulfone, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, and dimethyldiaminobiphenyl. Among these amines, aromatic amines are preferable from the viewpoint of increasing the strength of the cured product and the glass transition temperature.

The content of the curing agent may be set as appropriate depending on the type of the curing agent and the curable resin composition, and is preferably 2 to 65 parts by weight with respect to 100 parts by weight of the total resin components, for example. It is. More preferably, it is 5-60 weight part, More preferably, it is 10-50 weight part.

-Reinforcement-
It does not specifically limit as said reinforcing material, What is necessary is just to use what is used normally 1 type, or 2 or more types. Examples thereof include glass fiber, carbon fiber, polyaramid fiber, and the like, and these woven fabrics and nonwoven fabrics can be suitably used.

-Coupling agent-
The coupling agent is not particularly limited, and one or more commonly used ones may be used. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, etc. A silane coupling agent etc. are mentioned.

-Basic compounds-
When the curable resin composition contains a basic compound, for example, when the curable resin composition is in a liquid state, the fluidity is further improved, and the liquid that can be sufficiently filled up to every corner to be sealed. It can be a curable resin composition. Thus, the form which further contains a basic compound is also one of the suitable forms of this invention.

The said basic compound is a compound which shows basicity. Specifically, an amine compound, a phosphine compound, and the like are preferable, and one or more can be used. Of these, amine compounds are preferred.
As the basic compound, those which are liquid at room temperature (25 ° C.) are particularly suitable.

Examples of the amine compound include compounds having no nitrogen-containing ring structure such as triethylamine, tri-n-butylamine, N-methylpiperidine, N, N, N ′, N′-tetramethylethylenediamine, and N-methylmorpholine. Pyridine, pyridine, picoline, quinoline, isoquinoline, N-alkylpyrrole, N-alkylimidazole, 1,8-diazabicyclo [5,4,0] undec-7-ene (also referred to as DBU), 1,5-diazavincro [4 , 3,0] non-5-ene (also referred to as DBN), 1,4-diazavincro [2,2,2] octane (also referred to as DABCO (R)) and the like (compounds containing nitrogen) Also referred to as a compound). Among these, nitrogen-containing cyclic compounds are preferable, pyridine, DBU, DBN, and DABCO (R) are more preferable, and pyridine and DBU are more preferable. In consideration of odor and volatilization during kneading under reduced pressure, DBU is most suitable. The amine compound may be in the form of a salt.

Examples of the phosphine compound include triphenylphosphine, phenylphosphine, diphenylphosphine, and the like.

As the basic compound, those in which the pKa (acid dissociation constant) of the conjugate acid of the compound is 3 to 13 are preferable. Thereby, the effect of sufficiently suppressing the thickening and thixotropy of the curable resin composition and enhancing the fluidity is further exhibited. The pKa is more preferably 4 to 13.
Among the above basic compounds, for example, the pKa of DBU conjugate acid is 12.5, the pKa of DBN conjugate acid is 12.7, and the pKa of conjugated acid of pyridine is 5.25.

When using the said basic compound, it is suitable that the content rate shall be 0.005-5 mass% with respect to 100 mass% of total amounts of curable resin composition. When it exists in this range, the thickening of the said curable resin composition will be suppressed more, and fluidity | liquidity can be expressed more. More preferably, it is 0.01-1 mass%, More preferably, it is 0.05-0.5 mass%.

[Method for producing curable resin composition]
The curable resin composition of the present invention may be prepared so as to include a novolac-type cyanate ester resin and a phosphonium salt. For example, the curable resin composition is preferably prepared as follows. That is, after melting and kneading the novolac-type cyanate ester resin and other resin components blended as necessary into the reaction vessel at, for example, 40 to 200 ° C., other components such as an inorganic filler are used as necessary. Are preferably added simultaneously or sequentially and kneaded as appropriate using a mixer, kneader, roll, single screw extruder kneader, twin screw extruder kneader or the like. Moreover, it is good also as obtaining by performing a solvent-removal process as needed, after mixing suitably with an organic solvent at the time of mixing of a resin component.

[Cured product]
The curable resin composition of this invention can be made into hardened | cured material by thermosetting, for example. The curing temperature is, for example, preferably 70 to 300 ° C, more preferably 100 to 250 ° C. Moreover, 1-15 hours are suitable for hardening time, More preferably, it is 2-10 hours. The thermosetting reaction may be performed in two or more stages.

As for the shape of the said hardened | cured material, molded objects, such as a deformed product, a film, a sheet | seat, a pellet, etc. are mentioned, for example. Such a cured product of the curable resin composition of the present invention (cured product formed from the curable resin composition of the present invention) is also a preferred embodiment of the present invention.

The cured product is obtained from the curable resin composition of the present invention, and thus has a high glass transition temperature, a small linear expansion coefficient, excellent mechanical strength, a severe environment such as high temperature and high pressure, and high humidity. Since the time-dependent changes in various physical properties are sufficiently small even after being exposed to the bottom, various physical properties can be stably expressed. For example, mounting applications, optical applications, optical device applications, display device applications, machine component applications, electrical / electronics It is useful for various applications such as parts, automobile parts, and printing ink. Specifically, it is preferably used for electronics mounting materials such as sealing materials, potting materials, underfill materials, conductive pastes, insulating pastes, die pond materials, printing inks and the like. Among them, the curable resin composition can be a composition that can exist in a liquid state at room temperature without containing a volatile component such as an organic solvent. In this case, the electronic packaging material is required not to contain a volatile component. It will be used particularly suitably for such applications. That is, it is more preferable to use it for an electronic packaging material. Moreover, the said curable resin composition can be used very suitably for a sealing material, and when the said curable resin composition is a liquid especially, it is especially useful for a liquid sealing agent. Thus, the sealing material using the said curable resin composition is also one of this invention. A semiconductor sealing material is particularly preferable as the sealing material. Moreover, the semiconductor device or printed wiring board formed using the said hardened | cured material is also contained in the preferable form of this invention. A semiconductor device using the sealing material is also one aspect of the present invention.

The sealing material is a member used when, for example, semiconductor components (elements) are sealed, but, for example, a curing accelerator and a stabilizer as needed within a range not impairing the effects of the present invention. , Release agents, coupling agents, colorants, plasticizers, plasticizers, various rubbery materials, photosensitizers, fillers, flame retardants, pigments, and the like. Moreover, since the sealing material may cause problems when it contains a large amount of volatile components, it is desired that the sealing material does not contain volatile components. For example, the content of volatile components in 100% by mass of the sealing material is desired. The amount is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially.

Specifically, as a semiconductor device using the sealing material, for example, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, a transistor, a diode, a thyristor, etc. An active element; a passive element such as a capacitor, a resistor, a coil; and the like are mounted, and a necessary part is sealed with the sealing material of the present invention. As a method for sealing the element with the sealing material, for example, a normal method such as a low-pressure transfer molding method, an injection molding method, or a compression molding method may be used.

In addition, examples of printed wiring boards configured using the above cured products include composite type laminated boards (single-sided, double-sided, multilayer, etc.), glass epoxy type laminated boards, aramid epoxy type laminated boards, metal-based wiring boards, build-ups, and the like. A type wiring board etc. are mentioned. These can be obtained, for example, by impregnating the sealing material of the present invention in a reinforcing material or applying the sealing material to a base material, drying it appropriately, and then curing it. It is preferable that the curable resin composition in this case further includes a flame retardant, a filler, and the like as necessary.

Since the curable resin composition of the present invention has the above-described configuration, it can provide a cured product that can exhibit good electrical characteristics and is excellent in heat resistance, strength, and the like. Therefore, it is useful for various uses such as a sealing material, and a sealing material using this is extremely useful from the viewpoint of reliability and adhesion of a sealing object such as a semiconductor device.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
In addition, about the novolak-type cyanate ester resin used in the following example, the result of having measured the weight average molecular weight (Mw) by GPC under the measurement conditions mentioned above is as follows.
Novolac-type cyanate ester (PT-15, manufactured by Lonza): 489
Novolac-type cyanate ester (PT-60, manufactured by Lonza): 2870
Bisphenol A type cyanate ester (BADCy, manufactured by Lonza): 264

Example 1
46.4 g of novolak cyanate ester (PT-15, manufactured by Lonza), 11.5 g of trisphenolmethane type epoxy (EPPN501H, manufactured by Nippon Kayaku Co., Ltd.), and phosphazene (flame retardant; SPE-100, manufactured by Otsuka Chemical Co., Ltd.) ) 6.5 g was added to a separable flask and melt-kneaded at 80 ° C., and then 0.6 g of phosphonium salt (tetraphenylphosphonium tetra-p-tolylborate; TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) was added. Stir at 5 ° C. for 5 minutes to melt.
Next, in a planetary mixer, 57.9 g of the resin mixture obtained above, 210 g of inorganic filler (silica; manufactured by Micron), 24 g of inorganic hydroxide (Z-10, manufactured by Tateho Chemical Co., Ltd.), silane coupling Agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.6 g, carbon black (ET-NSB-001 (A), manufactured by Dainichi Seika Kogyo Co., Ltd.) 0.6 g, 1,8-diazabicyclo [5,4,0] undeca 7-ene (DBU) 0.3g was added, and it stirred under pressure reduction conditions (1 kPa) for 1 hour, and obtained the composition. This composition was liquid.
The obtained composition was cured at 120 ° C. for 1.5 hours and then cured at 200 ° C. for 3 hours. The Tg was 249 ° C.

Comparative Example 1
A cured product was obtained in the same manner as in Example 1 except that 0.3 g of cobalt acetylacetonate was used instead of the phosphonium salt. Tg was 220 ° C.

Example 2
12.0 g of novolak-type cyanate ester (PT-60, manufactured by Lonza), 2.1 g of trisphenolmethane type epoxy (EPPN501H, manufactured by Nippon Kayaku Co., Ltd.), and phosphazene (flame retardant; SPE-100, manufactured by Otsuka Chemical Co., Ltd.) ) 0.8 g, phosphonium salt (tetraphenylphosphonium tetra-p-tolylborate; TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) 0.2 g, inorganic filler (silica; manufactured by Micron) 80.7 g, inorganic hydroxide (Z-10, manufactured by Tateho Chemical Co., Ltd.) 4.3 g, silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 g, carbon black (ET-NSB-001 (A), manufactured by Dainichi Chemical Industries) 0 .3 g and 0.5 g of the release agent were added to a plastic container, shaken, and then melt-kneaded at 80 ° C. with three rolls.
After the obtained composition was pulverized, it was pressure-formed at 175 ° C. and 5 MPa for 6 minutes, and post-cured at 250 ° C. in a nitrogen atmosphere for 3 hours. When TMA (thermomechanical analysis) of the obtained cured product was measured, Tg was 285 ° C.

Comparative Example 2
Except for using 11.6 g of bisphenol A type cyanate ester (BADCy, manufactured by Lonza) as the cyanate ester resin and 2.3 g of trisphenol methane type epoxy (EPPN501H, manufactured by Nippon Kayaku Co., Ltd.) as the epoxy resin, A cured product was produced under the same conditions as in Example 2.
When TMA of the obtained cured product was measured, Tg was 231 ° C.

Claims (4)

A curable resin composition comprising a novolac-type cyanate ester resin and a phosphonium salt. Furthermore, epoxy resin and / or bismaleimide resin are contained, The curable resin composition of Claim 1 characterized by the above-mentioned. A sealing material comprising the curable resin composition according to claim 1. A semiconductor device comprising the sealing material according to claim 3.