JP2009292895A - Resin composition for semiconductor sealing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for semiconductor sealing, which does not contain a halogen atom, has high flowability and heat resistance, slight bleeding, a low coefficient of linear expansion, excellent flame retardancy, and reliability as a semiconductor sealing material. <P>SOLUTION: The resin composition for semiconductor sealing comprises: 10-35 mass% of a resin component composed of (A) 100 pts.mass of a non-halogen-based epoxy resin, (B) 20-80 pts.mass of an amino group-containing phosphoric acid ester compound having a bis(aminophenyl)phenyl phosphate structure, (C) 5-80 pts.mass of a diamine compound except the amino group-containing phosphoric acid ester compound; and 65-90 mass% of an inorganic filler. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a semiconductor sealing resin composition using a thermosetting flame retardant component.

In making a semiconductor component, since a cured product having excellent heat resistance, adhesion, electrical insulation and the like can be obtained, it is a mainstream to seal a semiconductor element using an epoxy resin composition. Conventionally, a cresol novolac type as an epoxy resin and a phenol novolac type as a curing agent are excellently used for these semiconductor sealing resin compositions, because they are excellent in heat resistance and moisture resistance.
At this time, the epoxy resin constituting the resin layer of the semiconductor sealing material is added with a halogen compound such as a bromine compound from the viewpoint of fire safety, and imparts flame retardancy and self-extinguishing properties. Have been used.

Halogen compounds exhibit excellent effects in imparting flame retardancy and self-extinguishing properties to epoxy resins and resin compositions, and have a very small adverse effect on the excellent properties of the above epoxy resin compositions. It has been used as a constituent material of a sealing resin composition.
On the other hand, due to increasing interest in environmental problems in recent years, studies have been conducted to eliminate halogen compounds typified by bromine from epoxy resins. This is because halogenated compounds may generate harmful dioxin compounds without proper combustion treatment after disposal. That is, conversion to a resin composition called “halogen-free resin” in which halogens have been eliminated has already progressed in the market.

  Specific methods for making halogen-free resins include a method of adding a flame retardant inorganic filler typified by aluminum hydroxide into an epoxy resin, a phosphoric ester compound or a phosphazene compound that is an addition type flame retardant Have been proposed (Patent Document 1, Patent Document 2), a method using an epoxy resin containing a phosphorus atom, etc. (Patent Document 3, Patent Document 4, Patent Document 5).

JP 2005-008835 A JP 2001-098144 A JP-A-11-279258 JP 2000-309623 A JP 2001-288247 A

The above-described method makes it possible to produce an epoxy resin imparted with flame retardancy without including a halogen compound in the semiconductor sealing resin composition. However, each method has the following problems. .
For example, when using an inorganic filler to ensure flame retardancy, it is necessary to add a large amount of filler to obtain sufficient flame retardancy. Therefore, as a result of using an inorganic filler for flame retardancy of such a resin composition, the problem is that the fluidity of the composition is lowered and the moldability is deteriorated.

Addition-type flame retardants such as phosphate ester compounds and phosphazene compounds reduce the glass transition temperature of cured products (decrease in heat resistance), increase the coefficient of linear expansion, and improve the adhesion reliability with metals due to bleeding. Problems that are greatly reduced have been pointed out, and the reliability of semiconductor components is reduced. In addition, in the case of a method of blending a phosphorus-containing epoxy resin that becomes a reactive flame retardant, the above problem can be solved, but since the phosphorus content is low, blending with only a phosphorus-containing epoxy resin has sufficient flame retardancy. I can't get it.
Therefore, an object of the present invention is to have reliability as a semiconductor sealing material that does not contain a halogen atom, has high fluidity and heat resistance, has little bleed, has a low coefficient of linear expansion, and is excellent in flame retardancy. It is providing the resin composition for semiconductor sealing.

（式中、Ｘ¹〜Ｘ⁵は、それぞれ独立に、水素原子又は炭素数１〜３のアルキル基であり、互いに同一であっても異なっていてもよい）
２．前記（Ｂ）アミノ基含有リン酸エステル化合物が、下記一般式（２）で示される化合物である上記１に記載の半導体封止用樹脂組成物、

（式中、Ｘ¹〜Ｘ⁵は、それぞれ独立に、水素原子又は炭素数１〜３のアルキル基であり、互いに同一であっても異なっていてもよい。）
３．前記（Ｂ）アミノ基含有リン酸エステル化合物が、下記一般式（３）又は（４）で示される化合物である上記２に記載の半導体封止用樹脂組成物、

４．前記非ハロゲン系エポキシ樹脂が、リン含有エポキシ樹脂である上記１〜３のいずれかに記載の半導体封止用樹脂組成物、及び
５．前記無機充填剤が、球状溶融シリカである上記１〜４のいずれかに記載の半導体封止用樹脂組成物、
を提供するものである。 In order to achieve the above object, the present inventors have conducted intensive research and found that the above problems can be solved by a resin composition for semiconductor encapsulation containing a specific amino group-containing phosphate compound. The present invention has been completed based on such findings.
That is, the present invention
1. (A) 100 parts by mass of a non-halogen epoxy resin, (B) 20 to 80 parts by mass of an amino group-containing phosphate compound represented by the following general formula (1), and (C) a diamine compound 5 other than the component (B) A resin composition for encapsulating a semiconductor, comprising 10 to 35% by mass of a resin component consisting of ˜80 parts by mass and 65 to 90% by mass of an inorganic filler,

(Wherein, X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other).
2. The resin composition for semiconductor encapsulation according to 1 above, wherein the (B) amino group-containing phosphate ester compound is a compound represented by the following general formula (2):

(Wherein, X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other.)
3. The resin composition for semiconductor encapsulation according to 2 above, wherein the (B) amino group-containing phosphate ester compound is a compound represented by the following general formula (3) or (4):

4). 4. The resin composition for semiconductor encapsulation according to any one of 1 to 3, wherein the non-halogen epoxy resin is a phosphorus-containing epoxy resin; The resin composition for semiconductor encapsulation according to any one of 1 to 4, wherein the inorganic filler is spherical fused silica,
Is to provide.

  According to the present invention, sufficient flame retardancy can be obtained without containing halogen atoms, and at the same time, flame retardant bleeding does not occur, and the heat resistance, linear expansion coefficient, fluidity, and moldability are excellent. Therefore, it is possible to provide a semiconductor sealing resin composition having excellent long-term reliability.

  The resin composition for semiconductor encapsulation of the present invention comprises (A) a non-halogen epoxy resin, (B) an amino group-containing phosphate ester compound and a resin component composed of a diamine compound other than the component (B) and an inorganic filler. Including.

(A) Non-halogen-based epoxy resin (A) Non-halogen-based epoxy resin used in the resin composition for encapsulating a semiconductor of the present invention is an epoxy resin containing no halogen atom such as bromine in the molecule, In the resin composition used for the resin composition for semiconductor encapsulation, such as linear expansion coefficient, fluidity, moldability, and chemical resistance, it is a material that determines main characteristics. The (A) non-halogen epoxy resin is not particularly limited, but preferably has at least two epoxy groups on average in one molecule. Further, the (A) non-halogen epoxy resin may have, for example, a silicone skeleton, a urethane skeleton, a polyimide skeleton, a polyamide skeleton, and the like, and contains a phosphorus atom, a sulfur atom, a nitrogen atom, and the like. Also good.
Specific examples of such (A) non-halogen epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin. , Catechol-type epoxy resins, dihydroxynaphthalene-type epoxy resins, biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, etc. Phenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl arral Type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, And epoxy resins derived from trivalent or higher phenols such as biphenyl-modified novolac epoxy resins.
In addition, (A) a non-halogen-type epoxy resin may be used independently, and 2 or more types may be mixed and used for it.

  In addition, various phosphorus-containing epoxy resins obtained by reacting a reactive phosphorus compound with the above-described various epoxy resins to bond phosphorus atoms can also be used as the (A) non-halogen epoxy resin. Examples of such reactive phosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA) or diphenylphosphine oxide and benzoquinone or naphthoquinone. Reaction products (following formulas a to d) and the like.

これらのリン含有エポキシ樹脂を用いることで、本発明の半導体封止用樹脂組成物の難燃性をさらに向上することができる。

By using these phosphorus-containing epoxy resins, the flame retardancy of the resin composition for semiconductor encapsulation of the present invention can be further improved.

(B) Amino group-containing phosphate ester compound (B) The amino group-containing phosphate ester compound in the present invention is one component of the resin composition for semiconductor encapsulation of the present invention (A) Curing of non-halogen epoxy resin It acts as a flame retardant at the same time as an agent, and is represented by the following general formula (1).

（式中、Ｘ¹〜Ｘ⁵は、それぞれ独立に、水素原子又は炭素数１〜３のアルキル基であり、互いに同一であっても異なっていてもよい）

(Wherein, X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other).

  The method for producing the (B) amino group-containing phosphate ester compound represented by the general formula (1) is not particularly limited, and Journal of Polymer Science Part A , Polymer Chemistry Vol. 35, No. 3 p. 565-574 (1997) and the like. Among these methods, a method in which a nitrophenol compound or aminophenol compound and a dichlorophosphate compound are reacted in an aprotic organic solvent is preferable, and in particular, an aminophenol compound represented by a predetermined general formula and a predetermined The method of reacting a dichlorophosphoric acid compound represented by the general formula in an aprotic organic solvent in the presence of a basic compound can be easily prepared by a one-step reaction. In terms of surface. As the basic compound, one or more selected from an organic basic compound and an inorganic basic compound can be used.

  (B) The aminophenol compound preferably used for production of an amino group-containing phosphate compound is represented by the following general formula (i).

  Examples of such aminophenol compounds include o-aminophenol, m-aminophenol, and p-aminophenol. The aminophenol compound may have a substituent such as an alkyl group and an alkoxy group.

  (B) The dichlorophosphoric acid compound preferably used for manufacture of an amino-group-containing phosphate ester compound is represented by the following general formula (ii).

In said formula, X < ¹ > -X < ⁵ > is a hydrogen atom or a C1-C3 alkyl group each independently, and may mutually be same or different.
Examples of such dichlorophosphoric acid compounds include phenyl dichlorophosphoric acid, 2-methylphenyl dichlorophosphoric acid, 4-methylphenyl dichlorophosphoric acid, 2,6-dimethylphenyl dichlorophosphoric acid, 2,4,6-trimethyl. Examples thereof include phenyldichlorophosphoric acid, 4-ethylphenyldichlorophosphoric acid and 4-propylphenyldichlorophosphoric acid.

  The ratio of the aminophenol compound and the dichlorophosphate compound is preferably 1.0 to 3.0 mol of the aminophenol compound per mol of chlorine atom of the dichlorophosphate compound, and 1.1 to 1. More preferably, it is 6 moles. If the aminophenol compound is less than 1.0 mol, the desired yield of the (B) amino group-containing phosphate ester compound may not be obtained, and the halogenated dichlorophosphate compound is mixed into the product. there's a possibility that. When the aminophenol compound exceeds 3.0 mol, the amount of unreacted aminophenol compound is too large, which is not economical.

(B) Examples of the organic basic compound preferably used for the production of an amino group-containing phosphate compound include pyridines such as pyridine, collidine and lutidine, nitrogen-containing cyclic compounds such as DBU and DBN, diethylamine, triethylamine, N , N-dimethylaniline and other amines, N, N, N ′, N′-tetramethylguanidine and the like. Examples of the inorganic basic compound include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, and the like. Among these, alkali metal carbonates such as pyridines, amines, sodium carbonate and potassium carbonate are preferable because they can increase the selectivity of the reaction and reduce the amount of side reaction products.
1.0-4.0 mol is preferable with respect to 1 mol of chlorine atoms of a dichlorophosphate compound, and the usage-amount of a basic compound has more preferable 1.1-3.0 mol. If the amount of the basic compound used is less than 1.0 mol, chlorine ions generated in the reaction cannot be sufficiently trapped, and the reaction system may become acidic and the reaction rate may decrease. On the other hand, when the usage-amount of a basic compound exceeds 4.0 mol, since there are too many basic compounds, it is not economical.

(B) As an aprotic organic solvent preferably used for the production of an amino group-containing phosphate ester compound, for example, aromatic solvents such as benzene, toluene and xylene; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and diethylene glycol dimethyl ether And ether systems such as acetonitrile; and nitrile systems such as acetonitrile. Among these, acetonitrile is preferable because it is excellent in solubility of the aminophenol compound and the dichlorophosphate compound.
The amount of the aprotic organic solvent used is not particularly limited as long as it can dissolve the aminophenol compound and the dichlorophosphate compound.

  (B) In the method for producing an amino group-containing phosphate ester compound, the order of addition of the above components is not particularly limited, but side reactions are suppressed and the yield of (B) the amino group-containing phosphate ester compound is increased. From the viewpoint, it is preferable to dissolve or disperse the inorganic basic compound in the aprotic organic solvent in which the aminophenol compound is dissolved, and then slowly add the dichlorophosphate compound.

The reaction temperature varies depending on the type of aprotic organic solvent used, but is generally preferably 40 to 100 ° C. When the reaction temperature is 40 ° C. or higher, the reaction rate is good, and when it is 100 ° C. or lower, products due to side reactions tend to decrease.
Although reaction time changes with the usage-amounts of the said component, etc., generally 0.5 to 10 hours are preferable. When the reaction time is 0.5 hour or longer, the aminophenol compound and the dichlorophosphate compound react sufficiently. On the other hand, when the reaction time is 10 hours or less, side reactions are unlikely to occur, the yield is excellent, and economically preferable.

After completion of the reaction, the (B) amino group-containing phosphate ester compound can be isolated from the reaction product by a known method such as filtration and washing.
Specifically, impurities such as a catalyst and a generated salt are removed from the reaction product by filtering the reaction product. Subsequently, after concentrate | evaporating a filtrate under reduced pressure, a solid substance is deposited by adding a lot of water to this filtrate. Next, an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like is added and stirred well to solubilize the unreacted aminophenol compound contained in the solid matter in water. Next, after filtering the solid, the solid is washed with water or the like and dried to obtain (B) an amino group-containing phosphate compound.
The (B) amino group-containing phosphate ester compound does not have a halogen atom in the molecule and does not generate dioxins when heated during processing and incinerated after use. It can be used for a resin composition for semiconductor encapsulation.

  Among the (B) amino group-containing phosphate compounds represented by the above general formula (1), the use of the (B) amino group-containing phosphate compounds represented by the following general formula (2) is excellent. A resin composition for semiconductor encapsulation having flame retardancy is obtained.

In the general formula (2), X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different.
In addition, among the (B) amino group-containing phosphate compounds represented by the above general formula (2), when a compound represented by the following chemical formula (3) is used, the semiconductor encapsulation having particularly excellent flame retardancy A resin composition is obtained. Moreover, when the compound represented by following Chemical formula (4) is used, in addition to the said flame retardance, the resin composition for semiconductor sealing excellent also in hydrolysis resistance will be obtained.

  The blending amount of the (B) amino group-containing phosphate ester is 20 to 80 parts by mass, preferably 30 to 70 parts per 100 parts by mass of the (A) non-halogen epoxy resin so as not to impair flame retardancy. Part by mass. If the amount is less than 20 parts by mass, the flame retardancy is lowered, and if it exceeds 80 parts by mass, the water resistance is lowered. Furthermore, the phosphorus content in the resin composition for semiconductor encapsulation of the present invention, including the above-described phosphorus-containing epoxy resin used as the non-halogen epoxy resin (A), is in the range of 0.8 to 3.5% by mass. It is preferable to mix | blend so that it may become. When the phosphorus content is 0.8% by mass or more, flame retardancy is improved. Moreover, physical properties, such as adhesiveness, improve that phosphorus content is 3.5 mass% or less.

(C) Diamine compounds other than the above component (B) The resin composition for encapsulating a semiconductor of the present invention has a (C) component other than the above (B) component from the viewpoint of adjusting the heat resistance, flexibility, etc. of the cured product. A diamine compound (hereinafter abbreviated as (C) diamine compound).
Examples of the (C) diamine compound that can be used in the present invention include hexamethylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, m-xylenediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, diaminodiphenylmethane, and Bis (4-aminophenyl) sulfone and the like can be mentioned. These (C) diamine compounds can be used alone or in combination. The compounding quantity of such (C) diamine compound is 5-80 mass parts with respect to 100 mass parts of (A) non-halogen-type epoxy resin, Preferably it is 10-50 mass parts, More preferably, it is 10-40. Part by mass.

  The resin composition for encapsulating a semiconductor according to the present invention is a resin comprising (A) a non-halogen epoxy resin, (B) an amino group-containing phosphate compound represented by the general formula (1), and (C) a diamine compound. It contains 10 to 35% by mass, preferably 10 to 30% by mass, and more preferably 20 to 30% by mass. When the blending amount of the resin component is less than 10% by mass, the fluidity is deteriorated, and when it exceeds 35% by mass, the linear expansion coefficient and flame retardancy are deteriorated.

(Inorganic filler)
The resin composition for semiconductor encapsulation of the present invention further contains an inorganic filler. The inorganic filler that can be used in the present invention is not particularly limited and may be a known one, such as fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, magnesium hydroxide, and the like. Fused silica, among them, metal oxides such as aluminum hydroxide and magnesium hydroxide that also act as flame retardant aids, fused silica and crystalline silica excellent in low linear expansion, electrical insulation, and low hygroscopicity are preferred. In particular, fused silica is preferred. The fused silica can be used in either crushed or spherical shape, but it is preferable to mainly use the spherical fused silica in order to increase the blending amount of the fused silica and to suppress the increase in the melt viscosity of the molding material. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
The resin composition for semiconductor encapsulation of the present invention contains 65 to 90% by mass of an inorganic filler, preferably 70 to 90% by mass, and more preferably 70 to 80% by mass. When the blending amount of the inorganic filler is less than 65% by mass, the linear expansion coefficient and flame retardancy deteriorate, and when it exceeds 90% by mass, the fluidity deteriorates.

(Other ingredients)
(1) Other curing agent The resin composition for semiconductor encapsulation of the present invention may contain a curing agent in addition to (B) the amino group-containing phosphate ester compound and (C) the diamine compound. Examples of such a curing agent include a phenol resin, a melamine resin, a polyamide resin, a polyisocyanate, and the like, which are curing agents for non-halogen epoxy resins.

(2) Curing accelerator The resin composition for semiconductor encapsulation of the present invention comprises (B) an amino group-containing phosphate ester compound and the amino group of the (C) diamine compound, and (A) a non-halogen epoxy resin. From the viewpoint of accelerating the crosslinking reaction, a curing accelerator can be included.
Examples of the curing accelerator that can be used in the present invention include organic acids such as salicylic acid, benzoic acid, phthalic acid, isophthalic acid, benzenesulfonic acid, and p-toluenesulfonic acid, boron trifluoride monomethylamine, and trifluoride. Examples include Lewis acids such as boron piperidine, and these can be used alone or in combination. Further, imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole may be used.
The blending amount of the curing accelerator is not particularly limited as long as it does not impair the characteristics of the flame retardant resin composition of the present invention. Generally, (B) an amino group-containing phosphate ester compound, ( 0.1-5 mass parts is preferable with respect to a total of 100 mass parts of C) diamine compound and (A) non-halogen epoxy resin, and 0.2-3 mass parts is preferable. The effect by mix | blending a hardening accelerator is fully acquired as the compounding quantity of this hardening accelerator is 0.1 mass part or more. On the other hand, when the blending amount of the effect accelerator is 5 parts by mass or less, a sufficient pot life can be obtained.

  (A) Non-halogen epoxy resin described above, (B) amino group-containing phosphate ester compound, (C) diamine compound, inorganic filler, and component added according to purpose The semiconductor sealing resin composition is blended at a predetermined ratio, and then generally mixed by a mixer or the like, and further prepared by kneading in a molten state with a kneader or a heating roll. A product obtained by cooling and solidifying the kneaded product can be used for sealing a semiconductor element after having properties suitable for a semiconductor manufacturing process, such as powder and pellets. The method for sealing the semiconductor element is not particularly limited, and may be formed by a known method such as transfer molding.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, these Examples do not limit this invention at all.

<Preparation of amino group-containing phosphate ester compound>
Synthesis Example 1 (Preparation of bis (4-aminophenyl) phenyl phosphate (hereinafter sometimes abbreviated as 4-APP))
197 g (1.42 mol) of p-nitrophenol, 135 g of anhydrous pyridine, 310 g of anhydrous acetonitrile were charged into a four-necked flask equipped with a stirrer, a dry nitrogen inlet tube, a thermometer, a dropping funnel and a condenser. The inside of the neck flask was made into a dry nitrogen atmosphere. Next, while vigorously stirring the inside of the flask, 150 g (0.710 mol) of phenyldichlorophosphoric acid was slowly added dropwise to the contents, followed by heating under reflux for 1 hour. Next, the reaction solution was cooled to room temperature and then slowly poured into 3 L of cold water to precipitate crystals. The obtained crystals were filtered, washed thoroughly with water, and dried at 90 ° C. for 24 hours to obtain 281 g (0.68 mol) of bis (4-nitrophenyl) phenyl phosphate (yield 95). %).
Next, 250 g (0.60 mol) of bis (4-nitrophenyl) phenyl phosphate, 624 g of dioxane, and 50 g of Raney nickel catalyst (Ni—Al alloy) dispersed in 70 g of dioxane are charged into an autoclave equipped with a stirrer. It is. Subsequently, hydrogenation reaction was performed at 50 degreeC and the pressure of 80 kg / cm < ² > for 5 hours. After a further 2 hours of reaction after the consumption of hydrogen stopped, excess hydrogen was evacuated from the autoclave. The reaction solution was filtered, concentrated, and poured into 5 L of 2% diethylamine aqueous solution. Next, the precipitated solid was filtered and washed thoroughly with water. Then, the solid was dried at 90 ° C. for 24 hours to obtain 192 g of 4-APP (yield 85%) represented by the above chemical formula (3).

Synthesis Example 2 (Preparation of 4-APP)
A mixture of 165 g (1.66 mol) anhydrous potassium carbonate and 700 g dehydrated acetonitrile and 101 g (0.926 mol) p-aminophenol was added to a stirrer, dry nitrogen inlet tube, thermometer, dropping funnel and A four-necked flask equipped with a condenser was charged and the inside of the four-necked flask was made into a dry nitrogen atmosphere. The temperature was raised to 60 to 65 ° C. while stirring the contents, and then a mixed solution of 65.1 g (0.309 mol) of phenyldichlorophosphoric acid and 60 g of dehydrated acetonitrile was slowly added dropwise to the contents. After completion of the dropwise addition, the mixture was further heated to reflux for 1 hour, and then the reaction solution was cooled to room temperature. The formed salt and potassium carbonate were removed by filtration and washed with 50 ml of acetonitrile. The obtained filtrate was concentrated under reduced pressure and then poured into about 600 ml of water. Subsequently, about 600 ml of 5% potassium carbonate aqueous solution was added and stirred for 30 minutes, and then the precipitated solid was filtered, washed carefully with water, and then dried. The obtained solid was recrystallized using methanol to obtain 66.6 g of 4-APP represented by the above chemical formula (3) (yield 65%).

Synthesis Example 3 (Preparation of bis (4-aminophenyl) -2,6-dimethylphenyl phosphate (hereinafter sometimes abbreviated as 4-ADMP))
107.7 g (0.882 mol) of 2,6-dimethylphenol, 80.7 ml (0.884 mol) of phosphorus oxychloride and 1.5 g of anhydrous calcium chloride were added to a stirrer, a dry nitrogen inlet tube, a thermometer, and dropwise. A four-necked flask equipped with a funnel and a condenser was charged and the inside of the four-necked flask was set to a dry nitrogen atmosphere. The contents were heated to reflux with stirring for 15 hours, and the reaction product obtained was distilled under reduced pressure to obtain 119.4 g (yield 56.7%) of 2,6-dimethylphenyl obtained above. Dichlorophosphoric acid was obtained.

139 g (1.00 mol) of p-nitrophenol, 94.9 g of anhydrous pyridine, 300 g of anhydrous acetonitrile were charged into a four-necked flask equipped with a stirrer, a dry nitrogen inlet tube, a thermometer, a dropping funnel and a condenser. The inside of the four-neck flask was a dry nitrogen atmosphere. Next, 119.4 g (0.50 mol) of 2,6-dimethylphenyldichlorophosphoric acid was slowly dropped into the contents while vigorously stirring the inside of the flask, followed by heating under reflux for 1 hour. Next, the reaction solution was cooled to room temperature and then slowly poured into 2 L of cold water to precipitate crystals. The obtained crystals were filtered, washed thoroughly with water, and dried at 90 ° C. for 24 hours to obtain 204.5 g (0.46 mol) of bis (4-nitrophenyl) -2,6-dimethylphenyl phosphate. Was obtained (yield 92%).
Next, 120 g (0.27 mol) of bis (4-nitrophenyl) -2,6-dimethylphenyl phosphate, 300 g of dioxane, 30 g of Raney nickel catalyst (Ni—Al alloy) dispersed in 30 g of dioxane was added to a stirrer. The autoclave marked with was charged. Subsequently, the hydrogenation reaction was performed at 50 ° C. and a pressure of 80 kg / cm ² for 2 hours. After a further 2 hours of reaction after the consumption of hydrogen stopped, excess hydrogen was evacuated from the autoclave. The reaction solution was filtered, concentrated, and poured into 3 L of 2% diethylamine aqueous solution. Next, the precipitated solid was filtered and washed thoroughly with water. Next, the solid was dried at 90 ° C. for 24 hours to obtain 86 g of 4-ADMP (yield 83%) represented by the above chemical formula (4).

<Preparation of resin composition>
Examples 1-4
Each component was mixed by the compounding ratio shown in Table 1, and they were melt-kneaded with a 90 degreeC hot roll, and the resin composition for semiconductor sealing of Examples 1-4 was obtained.
The obtained resin composition for encapsulating a semiconductor was pressure-molded in a mold at 190 ° C. for 1 hour at a pressure of 30 kg / cm ² to prepare a test cured product.

Comparative Examples 1-3
Each component was mixed by the compounding ratio shown in Table 1, and they were melt-kneaded with a 90 degreeC hot roll, and the resin composition of Comparative Examples 1-3 was obtained.
The obtained resin composition was pressure-molded in a mold at 190 ° C. for 1 hour at a pressure of 30 kg / cm ² to prepare a test cured product.

<Materials used>
Each compounding component used in Examples 1 to 4 and Comparative Examples 1 to 3 is as follows.
[(A) Non-halogen epoxy resin]
Cresol novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: EPICLON N-680, epoxy equivalent = 208 g / equivalent)
Phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: FX-305, epoxy equivalent = 485, phosphorus content: 3.0 mass%)
[Curing agent]
Phenol novolac resin (manufactured by Showa Polymer Co., Ltd., trade name: BRG-555, hydroxyl group equivalent = 103)
[(C) Diamine compounds other than amino group-containing phosphate compounds]
Bis (4-aminophenyl) sulfone (Tokyo Chemical Industry Co., Ltd., DDS)
[Additive phosphorus flame retardant]
1,3-phenylenebis (di-2,6-xylenyl phosphate) (phosphate ester flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200, phosphorus content: 9.0% by mass)
Phenoxyphosphazene (Otsuka Chemical Co., Ltd., trade name: SPE-100)
[Curing accelerator]
Boron trifluoride monoethylamine (Wako Pure Chemical Industries, F3BMEA)
Triphenylphosphine (Hokuko Sangyo Co., Ltd., TPP)
[Inorganic filler]
Spherical fused silica (manufactured by Tatsumori Co., Ltd., MSR-2212)

<Test method>
The characteristics of the thermosetting resin compositions and cured products produced in the examples and comparative examples were evaluated by the following measurements.

[Flame retardance]
Each of the thermosetting resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was cured by heating and pressing to obtain a cured product having a thickness of 9 mm. This cured product was subjected to a combustion test based on the UL standard UL94V method, and divided into V-0 to V-3 according to the combustibility.
The flame retardancy evaluation by the oxygen index was determined in accordance with “Test method for flammability by the oxygen index” of JIS K7201-2. In this evaluation, the larger the value of the oxygen index, the greater the flame retardancy.

[Glass transition temperature (Tg)]
Tg was measured by thermomechanical analysis (TMA). The TMA measurement was performed using TAS200 manufactured by Rigaku Corporation.

[Linear expansion coefficient]
Similar to the measurement of Tg, the measurement was performed by TMA. For the TMA measurement, TAS200 manufactured by Rigaku Corporation was used, and the linear expansion coefficient was measured from the expansion coefficient in the Z-axis direction. Here, α1 means a linear expansion coefficient of Tg-50 ° C to Tg-10 ° C.

[Melt viscosity]
The melt viscosity was measured with an ICI viscometer. For viscosity measurement, a cone plate viscometer CV-1 manufactured by SMT Engineering Co., Ltd. was used, and the melt viscosity at 120 ° C. was measured.

  As shown in Table 1, the flame retardant resin compositions of Examples 1 to 4 containing the amino group-containing phosphate compound were good in all of the melt viscosity, Tg, linear expansion coefficient, and flame retardancy. On the other hand, the resin composition of Comparative Example 1 has neither the amino group-containing phosphate ester of the present invention nor the conventional additive-type flame retardant, a low oxygen index, and flame retardancy (UL-94). In the test, the test piece is completely burned, and thus cannot be evaluated. In addition, in the resin compositions of Comparative Examples 2 and 3 in which a condensed phosphate ester compound or a phosphazene compound, which is an additive type flame retardant, was blended, the flame retardancy was good, but the Tg decreased and the linear expansion coefficient increased. It was observed. It is conceivable that the deterioration of these physical properties is caused by the fact that the phosphorus-containing compound is not incorporated into the crosslinked structure at the time of curing or the bleeding out from the cured product. Furthermore, in the melt viscosity, the flame retardant resin compositions of Examples 1 to 4 containing an amino group-containing phosphate compound are low in comparison with Comparative Examples 1 to 3 using a phenol novolac resin as a curing agent. The moldability was good.

  As described above, the semiconductor sealing resin composition of the present invention is more suitable in terms of flame retardancy, physical properties, and moldability than a resin composition containing a phenol novolac resin that has been suitably used as a conventional curing agent. Can be used for

  The present invention provides a thermosetting resin composition that does not contain a halogen atom and has high flame retardancy, and is useful as a semiconductor sealing material.

Claims (5)

(A) 100 parts by mass of a non-halogen epoxy resin, (B) 20 to 80 parts by mass of an amino group-containing phosphate compound represented by the following general formula (1), and (C) a diamine compound 5 other than the component (B) The resin composition for semiconductor sealing characterized by including 10-35 mass% of resin components which consist of -80 mass parts, and 65-90 mass% of inorganic fillers.

(Wherein, X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other). The resin composition for semiconductor encapsulation according to claim 1, wherein the (B) amino group-containing phosphate ester compound is a compound represented by the following general formula (2).

(Wherein, X ^{1 to} X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other.) The resin composition for semiconductor encapsulation according to claim 2, wherein the (B) amino group-containing phosphate ester compound is a compound represented by the following general formula (3) or (4).

  The resin composition for semiconductor encapsulation according to claim 1, wherein the non-halogen epoxy resin is a phosphorus-containing epoxy resin.   The resin composition for semiconductor encapsulation according to claim 1, wherein the inorganic filler is spherical fused silica.