JP2008056740A - Thermosetting compound, thermosetting resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable compound having good curability and giving a cured product having excellent soldering resistance, high-temperature preservability and flame-retardancy, a curable resin composition and a semiconductor device. <P>SOLUTION: The thermosetting compound has an oxazine ring on an aromatic group and has a structure expressed by general formula (1) (R1 is an aromatic group having substituent containing carbon-carbon triple bond; when the compound has two or more R1 groups, these groups may be same or different; R2 is selected from hydrogen, carboxyl group, hydroxyl group and ester group; when the compound has two or more R2 groups, these groups may be same or different; m is 1, 2 or 3; and n is an integer of 1-4). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting compound, a thermosetting resin composition containing the same, and a semiconductor device using the same.

  Semiconductor elements such as IC and LSI are mainly sealed with an epoxy resin composition and used in semiconductor devices. In recent years, the market trend of electronic devices has been reduced in size, weight and performance, and in order to respond to this trend, the integration of semiconductor elements has been increasing year by year. Further, surface mounting of semiconductor devices has been promoted, and the semiconductor elements have been increased in size with the high integration of semiconductor elements. The semiconductor devices on which the semiconductor elements are mounted are TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Flat). Package), BGA (Ball Grid Array), etc., and are becoming surface-mount semiconductor devices.

  When a conventional epoxy resin composition for sealing a semiconductor element is applied to these, the semiconductor device is suddenly placed in a high temperature environment of 200 ° C. or higher in the solder dipping or solder reflow process during surface mounting. As a result, shrinkage occurs in the cured product of the resin composition, or moisture absorbed in the cured product explosively vaporizes, and the stress causes cracks in the semiconductor device, and the semiconductor elements and leads constituting the semiconductor device. There is a problem in that peeling occurs at the interface between the frame and the plated portion on the inner lead and the cured product of the epoxy resin composition, and the electrical reliability as a sealing material is significantly reduced. In order to cope with the thermal stress at the time of mounting, the epoxy resin composition is highly filled with an inorganic filler using a low-viscosity resin component to improve the strength and moisture absorption rate of the cured product of the resin composition, As resin components, crystalline epoxy resins such as biphenyl type epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, and the like have been used to impart toughness of cured products. However, since the epoxy resin composition using these epoxy resins has a glass transition temperature of the cured product lower than the conventional one, the storage reliability that allows the semiconductor device to maintain its function in a high temperature atmosphere of about 150 ° C. ( In the following, there is a problem with high temperature storage.

  As a method for improving the high-temperature storage characteristics, there is a method of increasing the glass transition temperature of the resin composition. As a resin composition for semiconductor encapsulation having a high glass transition temperature and obtaining moisture resistance reliability, polyfunctional dihydroxy Attempts have been made to add benzoxazine (see, for example, Patent Document 1), but polyfunctional dihydroxybenzoxazine has poor curability and cannot cope with rapid curability required for recent epoxy resin compositions.

  Further, as a method for solving the above problem, a compound having a benzoxazine ring substituted with a substituent containing a carbon-carbon triple bond has been tried (see, for example, Patent Document 2), but polyfunctional dihydroxybenzoxazine. Like the above, the curability is poor and it cannot cope with the fast curability required for recent epoxy resin compositions. Furthermore, a compound containing a benzoxazine ring having an aromatic group having two or more aromatic rings such as a biphenyl group and a naphthyl group in one molecule has a long chain length between crosslinking points at the time of curing. Since the effect of increasing the glass transition temperature is small, there has been a demand for a method for increasing the glass transition temperature of the resin composition more effectively in actual use.

On the other hand, a phenol resin can be used as a binder having excellent mechanical properties, electrical properties, heat resistance, adhesiveness, etc., and therefore, as a phenol resin composition generally containing hexamethylenetetramine as a crosslinking agent, industrial parts It is widely used for molding materials for automobile parts and electrical parts. Hexamethylenetetramine is used as a crosslinking agent for novolak-type phenolic resins because it is relatively inexpensive and has good curability. However, since it generates decomposition gas during crosslinking, voids are formed inside the molded product. Since problems such as occurrence occur, studies have been made to try to apply a curable resin having a benzoxazine ring as a crosslinking agent for a phenol resin. However, although the curability is poor and improvement studies have been made (for example, see Patent Document 3), the curability and heat resistance levels of hexamethylenetetramine have not reached the level.
Japanese Patent Laid-Open No. 6-321221 JP 2005-82690 A JP 2002-161188 A

  The present invention provides a curable compound, a curable resin composition, and a semiconductor device that can obtain a cured product that has good curability and is excellent in solder resistance, high-temperature storage properties, and flame retardancy. It is.

  As a result of intensive investigations in view of the above problems, the present inventors are thermosetting compounds having an oxazine ring on an aromatic group, and a thermosetting compound having a specific structure solves the above problems. As a result, the present invention has been completed.

That is, the present invention
(1) A thermosetting compound having an oxazine ring on an aromatic group, the thermosetting compound having a structure represented by the general formula (1),

（一般式（１）中、Ｒ１は炭素−炭素三重結合を含む置換基を有する芳香族基を示し、複数有する場合、それぞれが同一であっても異なっていてもよい。Ｒ２は水素、カルボキシル基、水酸基及びエステル基の１つから選ばれ、複数有する場合、それぞれが同一であっても異なっていてもよい。ｍは１又は２又は３の整数、ｎは１〜４の整数を示す。）

(In the general formula (1), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and when there are a plurality of them, each may be the same or different. R2 represents hydrogen or a carboxyl group. And selected from one of a hydroxyl group and an ester group, each having the same or different group, m is an integer of 1 or 2 or 3, and n is an integer of 1 to 4.

(2) The thermosetting compound according to item (1), wherein the thermosetting compound has a structure represented by the general formula (2),

（一般式（２）中、Ｒ１は炭素−炭素三重結合を含む置換基を有する芳香族基を示し、複数有する場合、それぞれが同一であっても異なっていてもよい。Ｒ２は水素、カルボキシル基、水酸基及びエステル基の１つから選ばれ、複数有する場合、それぞれが同一であっても異なっていてもよい。ｎは１又は２の整数を示す。）

(In the general formula (2), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and when there are a plurality of them, each may be the same or different. R2 represents hydrogen or a carboxyl group. And when selected from one of a hydroxyl group and an ester group, each may be the same or different, and n represents an integer of 1 or 2.)

(3) The thermosetting compound according to item (2), wherein the thermosetting compound has a structure represented by the general formula (3),

（一般式（３）中、Ｒ１は炭素−炭素三重結合を含む置換基を有する芳香族基を示し、それぞれが同一であっても異なっていてもよい。Ｒ３は、水素、カルボキシル基、水酸基又はエステル基を示す。）

(In general formula (3), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and each may be the same or different. R3 represents hydrogen, a carboxyl group, a hydroxyl group or Indicates an ester group.)

(4) A thermosetting resin composition comprising the thermosetting compound according to any one of items (1) to (3),
(5) The thermosetting resin composition according to (4), wherein the thermosetting resin composition includes a thermosetting resin,
(6) The thermosetting resin composition according to item (5), wherein the thermosetting resin is an epoxy resin,
(7) The thermosetting resin composition according to (5) or (6), wherein the thermosetting resin is a phenol resin.
(8) A semiconductor device in which a semiconductor element is sealed with a cured product of the thermosetting resin composition according to any one of items (4) to (7),
It is.

  According to the present invention, it is possible to provide a curable compound and a curable resin composition that have good curability and are excellent in solder resistance, high-temperature storage stability and flame retardancy when formed into a cured product. A semiconductor device sealed with a cured product has excellent solder resistance and high-temperature storage.

The present invention is a thermosetting compound having a structure represented by the general formula (1), and an aromatic group having a substituent containing a carbon-carbon triple bond on one aromatic ring in the molecule. The present invention relates to a thermosetting compound having one or two substituted oxazine rings and having a substituent selected from hydrogen, a hydroxyl group, a carboxyl group and an ester group on the aromatic ring. Thereby, while being hardened | cured, while being hardened | cured, the hardened | cured material excellent in solder resistance, high temperature storage property, and a flame retardance can be obtained.
Moreover, this invention relates to the thermosetting resin composition containing the said thermosetting compound. Thereby, while being hardened | cured, while being hardened | cured, the hardened | cured material excellent in solder resistance, high temperature storage property, and a flame retardance can be obtained.
Moreover, this invention relates to the semiconductor device by which a semiconductor element is sealed with the hardened | cured material of the said thermosetting resin composition. Thereby, it becomes excellent in solder resistance and high temperature storage property.

Hereinafter, the thermosetting compound of the present invention will be sequentially described.
The thermosetting compound of the present invention has a structure represented by the general formula (1), and has an aromatic group having a substituent containing a carbon-carbon triple bond on one aromatic ring in the molecule. And a compound having one or two oxazine rings substituted with a hydrogen atom, a hydroxyl group, a carboxyl group and an ester group on the aromatic ring.

  The thermosetting compound is a thermosetting compound having an oxazine ring on an aromatic group and has a structure represented by the general formula (1). Among these, an oxazine ring is used. Those having the structure represented by the general formula (2) having two have two crosslinking points due to the opening of the benzoxazine ring and two crosslinking points due to the ethynyl group as the bridging part, thereby improving the glass transition temperature. Preferred above. In addition, as the substituent R2 on the aromatic group having an oxazine ring, at least one is preferably a hydroxyl group in terms of accelerating curing, and is a compound having a structure represented by the general formula (3). It is more preferable.

  In the structures represented by the general formulas (1) to (3), the ester group as R2 or R3 may be any ester group having a hydrocarbon group from C1 to C15, and has a desired viscosity. The softening point may be appropriately selected according to the miscibility with other compositions.

Examples of the substituent containing a carbon-carbon triple bond include an ethynyl group, a propargyl ether group, a phenylethynyl group, and a diethynyl group.
Examples of the aromatic group in the aromatic group having a substituent containing a carbon-carbon triple bond include a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, and an anthracenyl group.
Specific examples of the aromatic group having a substituent containing a carbon-carbon triple bond include an ethynylphenyl group, an ethynylnaphthyl group, an ethynylbiphenyl group, an ethynylanthracenyl group, a propargyletherphenyl group, and a propargylethernaphthyl group. And propargyl ether anthracenyl group, phenylethynylphenyl group, phenylethynylnaphthyl group, phenylethynylbiphenyl group and phenylethynylanthracenyl group. Among these, an ethynylphenyl group, an ethynylnaphthyl group, and an ethynylanthracenyl group are preferable.

  The thermosetting compound of the present invention includes a primary amine compound having an aromatic group having a substituent containing a carbon-carbon triple bond, and a phenol optionally having a substituent selected from a carboxyl group, a hydroxyl group and an ester group It can be obtained by reacting a compound having a functional hydroxyl group with an aldehyde in a solvent or without a solvent.

  Examples of the primary amine compound having an aromatic group having a substituent containing a carbon-carbon triple bond include ethynylaniline, ethynylaminonaphthalene, ethynylaminoanthracene, aminophenylpropargyl ether, aminonaphthalenepropargyl ether, aminoanthracene. Examples include propargyl ether, aminodiphenylacetylene, and aminodiphenylbutadiyne. Of these, ethynylaniline, ethynylaminonaphthalene and ethynylaminoanthracene are preferred.

  Examples of the compound having a phenolic hydroxyl group which may have a substituent selected from a carboxyl group, a hydroxyl group and an ester group include catechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, 1,2,4-trile. Gallic acid esters such as hydroxybenzene, gallic acid, gallic acid methyl ester, hydroxybenzoic acid, hydroxybenzoic acid ester, dihydroxybenzoic acid, dihydroxybenzoic acid ester, phloroglucin carboxylic acid, phloroglucin carboxylic acid ester, and these Derivatives and the like. Among these, catechol, resorcinol, hydroquinone, pyrogallol, gallic acid ester and phloroglucinol are preferable. In particular, as the compound having a phenolic hydroxyl group used for the thermosetting compound having the structure represented by the general formula (3), any commercially available gallic acid ester can be suitably used.

  Examples of the formaldehydes include formalin, paraformaldehyde, acetaldehyde, and benzaldehyde. Among these, formalin and paraformaldehyde are preferable.

  Examples of the solvent include methyl ethyl ketone, toluene, 1-propanol, 2-propanol, 1-butanol, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Alternatively, it can be used as a mixed solvent.

  As a manufacturing method of the thermosetting compound of this invention, for example with respect to 1 mol of phenolic hydroxyl groups of the compound which has the phenolic hydroxyl group which may have the substituent chosen from the said carboxyl group, a hydroxyl group, and an ester group. 1 mol of a primary amine compound having an aromatic group having a substituent containing a carbon-carbon triple bond and 2 mol of the formaldehyde are reacted, and after completion of the reaction, the solvent is distilled off if necessary. Accordingly, it is obtained by performing an alkali washing operation and removing the unreacted components.

Next, the thermosetting resin composition of the present invention will be described.
The thermosetting resin composition of the present invention contains the thermosetting compound obtained above, and can further contain a thermosetting resin. Examples of such thermosetting resins include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, bismaleimide resins, cyanate resins, polyimide resins, and alkyd resins.

  Examples of the epoxy resin used in the present invention include monomers, oligomers and polymers having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. Novolac epoxy resin, cresol novolac epoxy resin, hydroquinone epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, stilbene epoxy resin, triphenolmethane epoxy resin, alkyl-modified triphenolmethane Type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy Shi resins, naphthalene type epoxy resins, naphthol aralkyl type epoxy resins. Having a phenylene and / or biphenylene skeleton, it no problem is used singly or in admixture. Among these, from the viewpoint of improving the reliability of the cured resin properties and ensuring fluidity during molding, a phenylene and / or biphenylene skeleton that is excellent in physical properties such as low melt viscosity and heat strength of the cured product. It is preferable to use the phenol aralkyl type epoxy resin which has.

  Examples of the phenol resin used in the present invention include those having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene and / or biphenylene skeleton, naphthol aralkyl resin having phenylene and / or biphenylene skeleton, bisphenol compound, etc. These may be used alone or in combination.

When the thermosetting resin composition of the present invention is a phenol resin composition, it is a molding material that uses one or both of a phenol novolac resin and a phenol aralkyl resin as a main component among the phenol resins. As a binder for friction materials, castings, grindstones, etc., it is preferable from the viewpoints of cost, curability, heat resistance and high temperature reliability. Thereby, it is possible to obtain curability equivalent to or exceeding that of a conventional phenol resin composition containing hexamethylenetetramine, and in the cured product, characteristics excellent in heat resistance and high-temperature storage can be obtained. .
In addition, these phenol resins can be used as a curing agent for the epoxy resin. In that case, from the viewpoint of improving the reliability of the cured resin properties and ensuring fluidity during molding, the phenol resin has a low melt viscosity and is cured. It is preferable to use a phenol aralkyl resin having a phenylene and / or biphenylene skeleton that is excellent in physical properties such as hot strength of the product.

When the thermosetting resin composition of the present invention contains the thermosetting resin in addition to the thermosetting compound, the thermosetting resin composition can be appropriately blended.
When the thermosetting resin composition of the present invention is a composition containing an epoxy resin as the thermosetting resin, the content of the thermosetting compound of the present invention includes an epoxy resin and the phenol resin as a curing agent. In this case, 0.1 to 100 parts by weight is preferable with respect to 100 parts by weight in total with the phenol resin, but more preferably 0.5 to 50 parts by weight. Although it can be used outside the above range, if it is less than the lower limit, the effect of the high temperature storage characteristics may be reduced. On the other hand, if it exceeds the upper limit, the curability may be lowered.

  When the said thermosetting resin composition is a composition containing a phenol resin as the said thermosetting resin, as content of the thermosetting compound of this invention, it is 10-2000 with respect to 100 weight part of phenol resins. Part by weight is preferable, but a range of 50 to 1000 parts by weight is more preferable. Although it can be used outside the above range, if it is less than the lower limit, the effect of the high temperature storage characteristics may be reduced. On the other hand, if it exceeds the upper limit, the curability may be lowered.

  In addition to the above components, fillers such as inorganic fillers and organic fillers can be used for the thermosetting resin composition of the present invention. Examples of the inorganic filler include powdered materials such as glass beads, glass powder, calcium carbonate, talc, silica, alumina, aluminum hydroxide, clay, and mica, and fibers such as glass fibers, aramid fibers, and carbon fibers. One or more of these can be used, and examples of the organic filler include wood powder, plywood powder, thermosetting resin cured powder, and pulverized cloth. Although the above can be used, it is not limited to these.

  In the inorganic filler, when the thermosetting resin composition of the present invention is used in a semiconductor device, for example, silica such as fused spherical silica, fused crushed silica and crystalline silica, alumina, titanium white, talc, calcium carbonate, clay, Examples include mica. Among these, fused silica is preferable, and the particle shape is preferably spherical. As the filler, spherical silica of 1 to 100 μm is more preferable. These inorganic fillers may be used alone or in combination. Moreover, these may be surface-treated with a coupling agent.

  In the present invention, the content (blending amount) of the filler used arbitrarily is appropriately blended. For example, 200 parts per 100 parts by weight of the total amount of the epoxy resin, the curing agent, and the thermosetting compound of the present invention. It is preferably ˜3600 parts by weight.

  Further, in the thermosetting resin composition of the present invention, in addition to the thermosetting compound, optionally, the thermosetting resin, and optionally, an inorganic filler, if necessary, for example, the thermosetting resin Curing agent and curing accelerator for curable resin, epoxy silane such as 3-glycidyloxypropyltrimethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, aminosilane such as N-phenyl-3-aminopropyltrimethoxysilane Coupling of ureidosilanes such as 3-ureidopropyltriethoxysilane, silane coupling agents such as alkylsilane, vinylsilane and phenyltrimethoxysilane, titanate coupling agents, aluminum coupling agents, aluminum / zirconium coupling agents Agent, carbon black and ben Colorants such as LA, brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide and phosphorus compounds and other flame retardants, low stress components such as silicone oil and silicone rubber, and natural waxes such as carnauba wax , Synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate, metal salts of the higher fatty acids and mold release agents such as paraffin, ion catchers such as magnesium, aluminum, titanium and bismuth, bismuth antioxidants You may make it mix | blend (mix) various additives, such as.

  The thermosetting resin composition of the present invention comprises, in addition to the thermosetting compound, optionally, the thermosetting resin, and optionally, an inorganic filler, and other additives as necessary. Also obtained by mixing uniformly at room temperature, and after mixing by heating and kneading using a kneader such as a roll, a kneader, a kneader and a twin screw extruder, followed by cooling and pulverization Obtainable. Moreover, when the thermosetting resin composition obtained above is a powder, it can be used as a pressure tablet by a press or the like in order to improve workability in use.

The semiconductor device of the present invention seals a semiconductor element by curing and molding the thermosetting resin composition obtained above as a molding resin by a molding method such as transfer molding, compression molding, injection molding, or the like. Stop and get.
The semiconductor device of the present invention thus obtained is excellent in solder resistance, moisture resistance reliability, high temperature storage property, and flame retardancy.

  The preferred embodiments of the thermosetting compound, the thermosetting resin composition, and the semiconductor device of the present invention have been described above, but the present invention is not limited thereto.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this.

[Synthesis example of thermosetting compound]
Although the synthesis example of the thermosetting compound of this invention is shown below, reaction temperature and reaction time are not necessarily limited.

[Thermosetting compound A]
In a 0.5 L flask, 30 g (0.26 mol) of m-ethynylaniline and 129 g of 1,4-dioxane were added and dissolved by stirring. Next, 41.6 g of formaldehyde solution (36-38% aqueous solution) was added dropwise and mixed at room temperature for 30 minutes. Thereafter, 14.1 g (0.13 mol) of catechol was added and reacted at 90 ° C. for 8 hours with stirring. After completion of the reaction, the precipitate was filtered, and the filtrate was distilled under reduced pressure to obtain 38.2 g of thermosetting compound A represented by the following formula (4).

[Thermosetting compound B]
In the synthesis of thermosetting compound B, 24.1 g (0.13 mol) of gallic acid monohydrate was used instead of 14.1 g (0.13 mol) of catechol, and 144 g was used instead of 129 g of 1,4-dioxane. In the same manner as in the synthesis of the thermosetting compound A, 46.2 g of the thermosetting compound B represented by the following formula (5) was obtained.

[Thermosetting compound C]
In the synthesis of thermosetting compound C, 23.6 g (0.13 mol) of gallic acid methyl ester was used instead of 14.1 g (0.13 mol) of catechol, and 143 g was used instead of 129 g of 1,4-dioxane. In the same manner as in the synthesis of the thermosetting compound A, 47.2 g of a thermosetting compound C represented by the following formula (6) was obtained.

[Thermosetting compound D]
In the synthesis of the thermosetting compound D, instead of 30 g (0.26 mol) of m-ethynylaniline, 30 g (0.23 mol) of p-aminophenylpropargyl ether and 14.1 g (0.13 mol) of catechol were substituted. The heat represented by the following formula (7) in the same manner as the synthesis of thermosetting compound A, except that 24.1 g (0.11 mol) of pyrogallol and 121 g instead of 129 g of 1,4-dioxane were used. 43.6 g of curable compound E was obtained.

[Thermosetting compound E]
In the synthesis of the thermosetting compound E, in place of 14.1 g (0.13 mol) of catechol, 29.2 g (0.13 mol) of bisphenol A, and 151 g of 129 g of 1,4-dioxane were used. In the same manner as the synthesis of the thermosetting compound A, 62.0 g of a thermosetting compound E represented by the following formula (8) was obtained.

[Thermosetting compound F]
In the synthesis of the thermosetting compound F, 30 g (0.32 mol) of aniline was substituted for 30 g (0.26 mol) of m-ethynylaniline, and 20.3 g of pyrogallol was substituted for 14.1 g (0.13 mol) of catechol. 0.16 mol), except that 154 g was used instead of 129 g of 1,4-dioxane, and the thermosetting compound F represented by the following formula (9) was 47 in the same manner as in the synthesis of the thermosetting compound A. .8 g was obtained.

[Thermosetting compound G]
As the thermosetting compound G, Fa type benzoxazine represented by the following formula (10) composed of bisphenol F and aniline manufactured by Shikoku Kasei Kogyo Co., Ltd. was used.

  Next, using the thermosetting compound obtained above, an epoxy resin composition was prepared and various characteristics were evaluated. The measurement method and test method for each characteristic were as follows.

[Evaluation method of epoxy resin composition]
(1) Spiral Flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C., an injection pressure of 6.86 MPa, and a curing time of 2 minutes. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity.

(2) Curing torque Using a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type), the torque after 175 ° C., 90 seconds after the start of heating, and 300 seconds later was determined, and the curing torque ratio: (90 seconds Later torque) / (torque after 300 seconds) was calculated. The torque in the curast meter is a parameter of thermal stiffness, and the higher the curing torque ratio, the better the curability. Units%.

(3) Measurement of glass transition temperature (Tg) Using a transfer molding machine, a test piece (width 2 mm × length 30 mm × thickness 1.0 mm) at a mold temperature of 175 ° C., an injection pressure of 6.86 MPa, and a curing time of 120 seconds. ) And post-cured at 175 ° C. for 4 hours.
For measurement, dynamic viscoelasticity is measured by applying a dynamic viscoelasticity measuring device (DMS6100, manufactured by Seiko Instruments Inc.) while increasing the temperature at a rate of 5 ° C./min and applying a strain of a frequency of 10 Hz. The glass transition temperature (Tg) was determined from the peak value.

(4) Resistance to solder cracking A 100-pin TQFP (Thin Quad Flat Package) semiconductor package was allowed to stand for 168 hours in an environment of 85 ° C. and 85% relative humidity, and then immersed in a solder bath at 260 ° C. for 10 seconds. . The presence or absence of internal cracks and peeling was measured using an ultrasonic flaw detector, and the determination was made based on the number of chip peeling and internal cracks in 10 packages. The smaller the number of cracks and the peeling rate, the better the solder crack resistance.

(5) High temperature storage characteristics A 16-pin DIP (Dual Inline Package) semiconductor package was processed at 185 ° C. for 1000 hours, and the electrical resistance of the internal IC chip was measured. The case where the electric resistance circuit, which is usually 0.6Ω, deteriorates to an electric resistance of 1Ω or more is regarded as defective, and the number of defects in 10 packages was measured.

(6) UL94 flame retardancy Using a transfer molding machine, a test piece (127 mm × 12.7 mm × 1.6 mm thickness) was molded at a mold temperature of 175 ° C., an injection pressure of 6.86 MPa, and a curing time of 120 seconds. After curing at 175 ° C. for 8 hours, measurement was performed according to the UL-94 vertical method to determine flame retardancy.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
As described below, an epoxy resin composition containing the thermosetting compound was prepared, and a semiconductor device was manufactured.

(Examples 1-4, Comparative Examples 1-4)
Biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000P, where the number of repeating units: 3 indicates an average value), Biphenyl aralkyl type phenol resin (Maywa Kasei Co., Ltd., MEH-7801SS) However, the number of repeating units: 3 represents an average value.), Thermosetting compounds A to G, fused spherical silica (average particle size 15 μm), carbon black, natural carnauba wax, silane coupling agent (GE Toshiba Silicone) Co., Ltd., A-186), triphenylphosphine were respectively blended according to Table 1, first mixed at room temperature, then kneaded at 105 ° C. for 8 minutes using a hot roll, and then cooled and ground. An epoxy resin composition (thermosetting resin composition) was obtained.

  Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.

The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.

The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .

  The evaluation results were as shown in Table 1.

As can be seen from the results shown in Table 1, each of Examples 1 to 4 has a high glass transition temperature (Tg), and as a result, exhibits excellent high-temperature storage characteristics, solder resistance, and flame retardancy. The curability was also sufficient.
On the other hand, Comparative Examples 1-4 had a low glass transition temperature (Tg), and the high-temperature storage characteristics deteriorated.

Subsequently, the phenolic resin composition was produced using the thermosetting compound obtained above, and various characteristics were evaluated. The measurement method and test method for each characteristic were as follows.
[Method for evaluating phenolic resin composition]
(1) Gelation time It measured using 1g of resin on the hotplate heated at 175 degreeC. It was judged that the shorter the gelation time, the faster the curing rate.

(2) Curing torque The maximum torque at 175 ° C. was measured using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type). The larger this value, the better curability was judged.

(3) Measurement of glass transition temperature (Tg) Using a transfer molding machine, a test piece (width 9 mm × length 45 mm × thickness 3 mm) was measured at a mold temperature of 175 ° C., an injection pressure of 3.92 MPa, and a curing time of 120 seconds. What was shape | molded and post-cured at 175 degreeC for 4 hours was used.
For the measurement, a dynamic viscoelasticity is measured by applying a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.) at a rate of 5 ° C./min while applying a strain of a frequency of 10 Hz. The glass transition temperature (Tg) was determined from the peak value.

[Preparation of phenol resin composition]
A phenol resin composition containing the thermosetting compound was prepared as follows.

(Examples 5-8, Comparative Examples 5-8)
Thermosetting resins A to G, hexamethylenetetramine and phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-53195) were blended according to Table 2, pulverized and mixed with a table crusher, and a phenol resin composition (thermosetting) Resin composition).

  The evaluation results were as shown in Table 2.

  As can be seen from the results shown in Table 2, Examples 5 to 8 exhibited high curing torque and glass transition temperature, and the curing rate was sufficient. On the other hand, Comparative Examples 5 and 7 resulted in a slow curing rate and a low curing torque and glass transition temperature. In Comparative Example 6, the curing speed was high and the curing torque was relatively high, but the glass transition temperature was low. In Comparative Example 8, both the curing speed and the curing torque were sufficient, but due to the generation of voids due to the decomposition of hexamethylenetetramine, a molded product that could be measured with a dynamic viscoelasticity measuring apparatus could not be obtained.

  The thermosetting resin composition using the thermosetting compound of the present invention has good curability, excellent solder resistance and flame retardancy, and particularly excellent high-temperature storage characteristics. Furthermore, a semiconductor device sealed with a cured product using the thermosetting composition of the present invention is excellent in solder resistance, moisture resistance reliability, and high-temperature storage, and is also useful for a surface-mount type semiconductor device.

Claims (8)

A thermosetting compound having an oxazine ring on an aromatic group and having a structure represented by the general formula (1).

(In the general formula (1), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and when there are a plurality of them, each may be the same or different. R2 represents hydrogen or a carboxyl group. And selected from one of a hydroxyl group and an ester group, each having the same or different group, m is an integer of 1 or 2 or 3, and n is an integer of 1 to 4. The said thermosetting compound is a thermosetting compound of Claim 1 which has a structure represented by General formula (2).

(In the general formula (2), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and when there are a plurality of them, each may be the same or different. R2 represents hydrogen or a carboxyl group. And when selected from one of a hydroxyl group and an ester group, each may be the same or different, and n represents an integer of 1 or 2.) The said thermosetting compound is a thermosetting compound of Claim 2 which has a structure represented by General formula (3).

(In general formula (3), R1 represents an aromatic group having a substituent containing a carbon-carbon triple bond, and each may be the same or different. R3 represents hydrogen, a carboxyl group, a hydroxyl group or Indicates an ester group.)   The thermosetting resin composition containing the thermosetting compound of any one of Claims 1 thru | or 3.   The thermosetting resin composition according to claim 4, wherein the thermosetting resin composition includes a thermosetting resin.   The thermosetting resin composition according to claim 5, wherein the thermosetting resin is an epoxy resin.   The thermosetting resin composition according to claim 5 or 6, wherein the thermosetting resin is a phenol resin.   A semiconductor device in which a semiconductor element is sealed with a cured product of the thermosetting resin composition according to claim 4.