JP6126837B2 - Liquid curable resin composition and use thereof - Google Patents

Description

The present invention relates to a liquid curable resin composition and use thereof. More specifically, a liquid 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, and the like. The present invention also relates to a liquid sealing material and a semiconductor device using the same.

The curable resin composition in a liquid state at room temperature is used for mounting, optical, optical device, display device, mechanical component, electrical / electronic component, automotive component, printing ink, etc. It is widely used for various applications. Such a liquid curable resin composition is usually provided with fluidity by including a volatile component such as an organic solvent or a diluent, but it is desired that the organic solvent is not included as much as possible depending on the application. There is a demand for the development of a resin composition that can exist in a liquid state at room temperature without containing volatile components. Especially for sealing materials used for semiconductor devices and the like, from the viewpoint of reliability and adhesion, there is a need for a solvent-free and liquid curable resin composition that can be filled to every corner of a sealing target. Yes.

As a conventional liquid curable resin composition, for example, Patent Document 1 includes an epoxy resin, a curing agent, and a curing accelerator, the curing agent is an aromatic amine, and the curing accelerator is 1,8-diazabicyclo ( 5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5 and a solvent-free liquid epoxy resin composition which is at least one of these salts are disclosed, and Patent Document 2 Discloses a liquid resin composition containing an epoxy resin, an amine curing agent, a filler, a Lewis base or a salt thereof, and an oxidized carbon black and having a Lewis base of DBU or DBN. Patent Document 3 also includes a cyanate ester, an epoxy resin, a metal complex, and a specific amine compound that have a specific structure and are an amorphous liquid at 50 ° C. and are liquid at 50 ° C. A functional resin composition is disclosed. Furthermore, Patent Document 4 discloses a liquid epoxy resin composition using a compound having an acid anhydride group as a curing agent.

JP 2006-188573 A JP 2012-012431 A JP 2010-254838 A JP-A-1-26625

As described above, various liquid curable resin compositions have been developed. In particular, the curable resin compositions of Patent Documents 1 and 2 are described as being suitable for use as a sealing material for semiconductor devices, but in such a sealing material application, an epoxy resin is used from the viewpoint of high heat resistance. Often used. However, since the conventional epoxy encapsulant using an epoxy resin is approaching the performance limit, the inventors have a high glass transition temperature (Tg), high toughness, and low Attention was focused on a cyanate ester resin having the property of providing a cured product having linear expansion properties. In general, a liquid sealing material using a liquid curable resin composition is formed by kneading a flame retardant or the like as necessary in addition to a resin and an inorganic filler (mainly silica). As a result, when the cyanate ester resin and the inorganic filler are kneaded, the resulting product has a high viscosity, has thixotropy, and does not exhibit fluidity. I found it difficult. Note that the curable resin composition of Patent Document 3 is intended for application to a fiber-reinforced composite material. From Patent Document 3, the problem that occurs when an inorganic filler and a cyanate ester resin are used. Cannot be found. Further, Patent Document 4 discloses a liquid epoxy resin composition using a compound having an acid anhydride group as a curing agent. However, in a liquid sealant, Patent Documents 1 and 2 disclose a curing agent. It is more common to use acid anhydride curing agents than amine curing agents as described.

The present invention has been made in view of the above-described present situation, and is excellent in various physical properties such as heat resistance, and can exist in a liquid state at room temperature even without substantially containing volatile components such as organic solvents and diluents. It aims at providing the liquid curable resin composition which has fluidity | liquidity, the sealing material using the same, and a semiconductor device.

The present inventor has made various studies on materials that can be preferably applied to liquid encapsulant applications and the like. As a result, a curable resin composition containing a cyanate ester resin has a high glass transition temperature (Tg) and high toughness. In addition, it has been noted that a cured product having low linear expansion can be provided. However, as a result of investigation, when a cyanate ester resin is kneaded with an inorganic filler (silica or the like) usually used for a liquid sealing material, a product having high viscosity, thixotropy, and no fluidity is obtained. And found that it is difficult to apply to liquid sealing materials. Therefore, when a basic compound is added to the cyanate ester resin and the inorganic filler, it has been found that the fluidity is improved and a liquid curable resin composition that can be filled to every corner of the sealing target is obtained. The inventors have found that a semiconductor device with high reliability and adhesion can be obtained by using a liquid encapsulant using an adhesive resin composition, and that the above problems can be solved brilliantly. It has been reached.

Here, the fluidity improvement mechanism by the basic compound is considered as follows.
Inorganic fillers such as silica are generally used as the inorganic filler, but the surface is acidic. By adsorbing the basic compound on the acidic surface, aggregation of the inorganic oxide particles is suppressed, and it is considered that the fluidity is improved without causing thixotropy.

That is, the present invention is a liquid curable resin composition that contains a cyanate ester resin, an inorganic filler, and a basic compound and is in a liquid state.
The present invention is also a liquid sealing material using the liquid curable resin composition.
The present invention is also a semiconductor device using the liquid 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.

[Liquid curable resin composition]
Although the liquid curable resin composition of this invention contains cyanate ester resin, an inorganic filler, and a basic compound, these each component can use 1 type (s) or 2 or more types, respectively. Moreover, as long as these are essential, other components may be included appropriately.

In the present invention, “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, about the said liquid curable resin composition, the viscosity at the time of applying the share of 10s < ^-1 > (s- ¹ means the rotation speed per second) at the measurement temperature of 60 degreeC is 50 Pa.s or less. Preferably it is. Thereby, it becomes a liquid resin composition with higher fluidity, and when used as a sealing material, for example, it becomes possible to fill the sealing material to every corner of the sealing target. More preferably, it is 30 Pa.s or less, More preferably, it is 20 Pa.s or less, Most preferably, it is 10 Pa.s or less. The lower limit of the viscosity is not particularly limited as long as the inorganic filler does not settle. For example, it is preferable that the viscosity when applying a share of 10 s ⁻¹ at 60 ° C. is 0.01 Pa · s or more. More preferably, it is 0.1 Pa · s or more.

The liquid curable resin composition preferably has a viscosity of 100 Pa · s or less at a measurement temperature of 60 ° C. when a share of 0.5 s ⁻¹ is applied. More preferably, it is 60 Pa · s or less, further preferably 50 Pa · s or less, particularly preferably 40 Pa · s or less, and most preferably 20 Pa · s or less. Further, the lower limit of the viscosity in this case may be such that the inorganic filler does not settle, for example, the viscosity when applying a share of 0.5 s ⁻¹ at 60 ° C. is 0.01 Pa · s or more. Is preferred. More preferably, it is 0.1 Pa · s or more. Moreover, it is preferable that the said liquid curable resin composition exists in a liquid state within the range of 0-60 degreeC.
In the present specification, the viscosity of the liquid curable resin composition can be measured, for example, using a TA Instruments rheometer (DISCOVERY HR-1) at a measurement temperature of 60 ° C. in an air atmosphere.

The curable resin composition also preferably has a glass transition temperature (Tg) of 210 ° C. or higher as a cured product. 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.

<Cyanate ester resin>
In the liquid curable resin composition, the cyanate ester resin is preferably a bifunctional or higher polyfunctional compound, that is, one having at least two cyanate groups (—OCN) on average in one molecule.

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

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). 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 (a), 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;
Novolac-type cyanate ester resins such as phenol novolac type and cresol novolak type;
Bisphenol type cyanate ester resin;

Among these, from the viewpoints of heat resistance and curability of the cured product, novolak-type cyanate ester resins and bisphenol-type cyanate ester resins are preferable, and phenol novolac-type cyanate ester resins are preferable. A bisphenol-type cyanate ester resin is more preferable, and a bisphenol E-type cyanate ester resin is more preferable.

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 (a) 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 shape of the 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 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 cyanate ester resin preferably has a weight average molecular weight of 100 to 2,000. 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 2000. When in this range, the liquid state of the liquid curable resin composition can be more stably maintained. More preferably, it is 120-1000, More preferably, it is 200-700.
The molecular weight (number average molecular weight and weight average molecular weight) of the 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).

The content ratio of the cyanate ester resin is preferably 5 to 49% by mass with respect to 100% by mass of the total amount of the liquid curable resin composition. Within this range, it is excellent in various physical properties such as heat resistance, and can be present in liquid form at room temperature even if it does not substantially contain volatile components, and exhibits the effect of the present invention that it has high fluidity more fully. can do. More preferably, it is 8-30 mass%, More preferably, it is 10-20 mass%.

<Inorganic filler>
In the said liquid curable resin composition, it does not specifically limit as an 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. Of these, inorganic oxides are preferable. As the inorganic oxide, for example, silica such as fused silica, crystalline silica, and finely divided silica, and metal oxides such as alumina, silicon nitride, and magnesia are preferable. Of these, silica is preferable.
In the present invention, it is appropriate to use an inorganic filler whose surface is acidic, but usually the surface of the inorganic oxide is acidic.

The content of the inorganic filler is preferably 50 to 90% by mass with respect to 100% by mass of the total amount of the liquid 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%.

<Basic compound>
In the liquid curable resin composition, the basic compound is a compound that exhibits 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 this invention of fully suppressing the thickening and thixotropy of a liquid curable resin composition and improving fluidity | liquidity is expressed further. 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.

The content ratio of the basic compound is preferably 0.005 to 5% by mass with respect to 100% by mass of the total amount of the liquid curable resin composition. Within this range, thickening of the liquid curable resin composition is further prevented, and the fluidity can be expressed more. More preferably, it is 0.01-1 mass%, More preferably, it is 0.05-0.5 mass%.

<Other resin components>
The liquid curable resin composition may also contain other resin components in addition to the cyanate ester resin described above. As such other resin components, one or two or more of those which are compatible with the above-described cyanate ester resin, inorganic filler and / or basic compound can be used as appropriate. For example, high heat-resistant curable resins such as bismaleimide resin and benzoxazine resin may be used in addition to epoxy resin, phenol resin, urethane resin, and the like. 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 liquid 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 liquid curable resin composition having more excellent operability 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 cyanate ester resin. More preferably, it has a melting point or softening point of 60 ° 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 improve the curability of the epoxy resin, it is preferable to use a 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, although the upper limit of the functional number is not particularly limited, for example, it is preferably 20 or less.

When the said liquid curable resin composition contains an epoxy resin, it is suitable that the epoxy equivalent in the said liquid 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).

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 a content ratio of other resin components (preferably epoxy resin and / or bismaleimide resin) in the curable resin composition, the total amount of cyanate ester resin and other resin components (that is, the total amount of all resin components) is 100. If it is mass%, it is suitable that it is 0-50 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 liquid curable resin composition may also contain other components other than the components described above, if necessary. For example, curing accelerators; flame retardants; volatile components such as organic solvents and diluents; curing agents; reinforcing materials; coupling agents; stress relieving agents; mold release agents; Various rubber-like materials, photosensitizers, pigments, and the like, and one or more of these can be used. Among these, it is particularly preferable to further include a flame retardant and / or a curing accelerator.

-Curing accelerator-
When the liquid curable resin composition contains a curing accelerator, curing can be further promoted and a cured product having higher mechanical strength can be obtained. Thus, the form which further contains a hardening accelerator is also one of the suitable forms of this invention.
Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole; 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 (dimethoxyphenyl) phosphine, etc. In addition to organophosphorus compounds; organometallic compounds such as aluminum and zirconium; and the like, other examples include heterocyclic amine compounds, boron complex compounds, phosphonium salts, organic ammonium salts, organic sulfonium salts, organic peroxides, and their reactants. 1 type, or 2 or more types of these can be used. Of these, phosphonium salts are preferred. Thereby, it becomes possible to obtain hardened | cured material with more accelerated hardening and higher mechanical strength. Such a form further containing a phosphonium salt is also a preferred form of the present invention.

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 compatibility with the resin.

When the curing accelerator (preferably phosphonium salt) is included, the content ratio is suitably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of all resin components, for example. More preferably, it is 0.005-5 weight part, More preferably, it is 0.008-3 weight part, Most preferably, it is 0.01-1 weight part.
The “total resin component” is a resin in which all the resin components included in the liquid curable resin composition of the present invention, that is, a cyanate ester resin, and other resin components further included as necessary are combined. Means ingredients.

-Flame retardant-
When the said liquid 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-
As described above, the liquid curable resin composition of the present invention can be present in a liquid state at room temperature without containing a volatile component, and is suitably used for applications where it is desired not to contain a volatile component. is there. Therefore, the content of the volatile component in 100% by mass of the liquid 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 in 100% by mass of the liquid curable resin composition. It is suitable that it is below mass%. Thus, the form in which the liquid curable resin composition does not substantially contain a volatile component is also one of the preferred forms of the present invention. When used for applications that may contain volatile components, such as printing ink applications, the liquid curable resin composition may contain volatile components, and such a form is also suitable for carrying out the present invention. One of the forms.
Thus, the liquid curable resin composition of the present invention has a very unique property that it can exist in a liquid state at room temperature, whether or not it contains a volatile component. It has important technical significance.

When the liquid curable resin composition contains a volatile component, the volatile component is not particularly limited, and a commonly used one may be used. 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 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 liquid 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 material-
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.

[Method for producing liquid curable resin composition]
The liquid curable resin composition of the present invention may be prepared so as to include a cyanate ester resin, an inorganic filler, and a basic compound. For example, the liquid curable resin composition is preferably prepared as follows. That is, after melt-kneading the cyanate ester resin and other resin components blended as necessary into the reaction vessel at, for example, 40 to 200 ° C., the inorganic filler, the basic compound, and blended as necessary. It is preferable to obtain by adding other components simultaneously or sequentially and kneading using a mixer, a kneader, a roll, a single screw extruder kneader, a twin screw extruder kneader or the like as appropriate. 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 liquid curable resin composition of this invention can be made into hardened | cured material by thermosetting, for example. 70-250 degreeC is suitable for a curing temperature, for example, More preferably, it is 100-220 degreeC. 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 liquid curable resin composition of the present invention (cured product formed from the liquid curable resin composition of the present invention) is also a preferred embodiment of the present invention.

The cured product is obtained from the liquid curable resin composition of the present invention, has a high glass transition temperature, a small linear expansion coefficient, excellent mechanical strength, severe conditions such as high temperature and high pressure, and high humidity. Since changes over time in various physical properties are sufficiently small even after exposure to the environment, various physical properties can be stably expressed.For example, mounting applications, optical applications, opto device applications, display device applications, machine component applications, electrical / It is useful for various applications such as electronic 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 liquid curable resin composition is a composition that can exist in a liquid state at room temperature without containing a volatile component such as an organic solvent. Therefore, the liquid curable resin composition is required to contain no volatile component. It will be particularly preferably used. That is, it is more preferable to use it for an electronic packaging material. In particular, the liquid curable resin composition can be used very suitably for a liquid sealing material. Thus, the liquid sealing material which uses the said liquid curable resin composition is also one of this invention. A semiconductor sealing material is particularly preferable as the liquid 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 liquid sealing material is also one aspect of the present invention.

The liquid sealing material is, for example, a member used when sealing a semiconductor component (element), but, for example, a curing accelerator or a stable material as long as the effects of the present invention are not impaired. An agent, a release agent, a coupling agent, a colorant, a plasticizer, a plasticizer, various rubbery materials, a photosensitizer, a filler, a flame retardant, a pigment, and the like can be included. Moreover, since the liquid sealing material may cause problems when it contains a large amount of volatile components, it is desired that the liquid sealing material does not contain volatile components. For example, the liquid sealing material contains 100% by mass of the liquid sealing material. The content of 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.

Specific examples of the semiconductor device using the liquid sealing material include, for example, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, and a support member such as a semiconductor chip, a transistor, a diode, and a thyristor. Active elements; passive elements such as capacitors, resistors, coils, etc. are mounted, and necessary portions are sealed with the liquid sealing material of the present invention. As a method for sealing the element with the liquid 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 liquid sealing material of the present invention into a reinforcing material or applying the liquid sealing material to a base material, drying it appropriately, and then curing it. The liquid curable resin composition in this case preferably further includes a curing accelerator (curing catalyst), a flame retardant, a filler, and the like as necessary.

Since the liquid curable resin composition of the present invention is configured as described above, it is excellent in various physical properties such as heat resistance, and is liquid at room temperature even when substantially free of volatile components such as organic solvents and diluents. It has a high fluidity. Therefore, it is useful for various uses such as a sealing material, and in particular, a liquid sealing material using the sealing material can fill the sealing material to every corner to be sealed. This is extremely useful from the viewpoint of the reliability and adhesion of the object to be sealed.

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. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

(Simple test)
Examples 1-3, Comparative Example 1
Bisphenol E type cyanate ester (LECy, manufactured by Lonza) 58.2 g and curing accelerator (tetraphenylphosphonium tetra-p-tolylborate; TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) 0.6 g It is melt-kneaded in 5 minutes. In addition, 240 g of silica (manufactured by Micron), 0.6 g of silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical), and carbon black (ET-NSB-001 (A), large Nissei Kagaku Kogyo Co., Ltd.) (0.6 g) was stirred with a planetary mixer for 1 hour to obtain compositions.
After each additive shown in Table 1 was added to each composition obtained in the amount shown in Table 1 (not added in Comparative Example 1), the mixture was stirred for 3 minutes with Awatori Kentaro (Sinky Corporation). went. For each of the compositions thus obtained (liquid compositions 1 to 3 and comparative composition 1), a rheometer (DISCOVERY HR-1) manufactured by TA Instruments was used, and the measurement temperature was 60 ° C., air Under the atmosphere, the viscosity was measured with a shear rate of 10 s ⁻¹ and 0.5 s ⁻¹ . The results are shown in Table 1.
In Table 1, the addition amount of the additive means the content (% by mass) of the additive in the total amount of 100% by mass of each composition.

From the simple test results of Examples 1 to 3 and Comparative Example 1 in Table 1, it was confirmed that the basic compound has an effect of improving fluidity. It should be noted that pyridine and triethylamine were more effective in improving fluidity than DBU. However, this is because the molecular weight is small, so even if the same addition amount (mass%), the number of molecules is large or kneading is easy. It is done.

Next, as Example 4 and Comparative Example 2, examination was performed with a composition close to the actual usage pattern. In Example 4, DBU was selected as the basic compound because it considered odor and volatilization during kneading under reduced pressure.

Example 4
Add 105 g of bisphenol E type cyanate ester (LECy, manufactured by Lonza) and 25 g of trisphenol methane type epoxy (EPPN501H, manufactured by Nippon Kayaku Co., Ltd.) to a separable flask, and use a Max blend type stirring blade, 250 rpm, 80 ° C. Then, 1.1 g of a curing accelerator (tetraphenylphosphonium tetra-p-tolylborate; TPP-MK, manufactured by Hokuko Chemical Co., Ltd.) was added and stirred at 80 ° C. for 5 minutes to melt.
Next, in a planetary mixer, 59 g of the resin mixture obtained above, 216 g of inorganic filler (silica; manufactured by Micron), 24 g of inorganic hydroxide (Z-10, manufactured by Tateho Chemical), 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] undec-7-7 EN (DBU) 0.3g was added and it stirred at 1 kPa for 1 hour, and the liquid composition 4 was obtained.
The obtained liquid composition 4, using a TA Instruments rheometer (DISCOVERY HR-1), measurement temperature 60 ° C., under an air ^atmosphere, 10s ^{-1 (s} -1: per second The viscosity was measured by applying a share of 0.5 s ⁻¹ . The results are shown in Table 2. In addition, Tg of Example 4 was 241 degreeC.

Comparative Example 2
A comparative composition 2 was obtained in the same manner as in Example 4 except that DBU was not added. About the obtained comparative composition 2, the viscosity was measured in the same manner as in Example 4. The results are shown in Table 2.

Also from Table 2, it was confirmed that the basic compound has an effect of improving fluidity.
In the above-described embodiments, DBU, pyridine or triethylamine is used as the basic compound and silica is used as the inorganic filler. However, a basic compound and an inorganic filler (particularly those having an acidic surface) are used. As long as the fluidity is improved and improved without causing thickening or thixotropy, the mechanism is the same. Therefore, if a basic compound and an inorganic filler (especially those having an acidic surface) are used in the presence of a cyanate ester resin, it can be said that the advantageous effects of the present invention are exhibited.

Claims (5)

Cyanate ester resins, comprising an inorganic filler and a basic compound, a curable resin composition Ru liquid der,
Basic compound include pyridine, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,5-Jiazabi cyclo [4,3,0] non-5-ene, 1,4 Jiazabi cyclo [2,2,2] octane, and, Ri least 1 Tanedea selected from the group consisting of phosphine compounds,
The liquid curable resin composition, wherein the content of the inorganic filler is 50 to 90% by mass with respect to 100% by mass of the total amount of the liquid curable resin composition. The liquid curable resin composition according to claim 1, further comprising an epoxy resin and / or a bismaleimide resin. 3. The liquid curable resin according to claim 1, wherein a content ratio of the basic compound is 0.005 to 5 mass% with respect to 100 mass% of the total amount of the liquid curable resin composition. Composition. A liquid encapsulant comprising the liquid curable resin composition according to any one of claims 1 to 3 . A semiconductor device comprising the liquid sealing material according to claim 4 .