JP4895076B2 - Aromatic hydrocarbon resin, its production method and its use - Google Patents

Description

  The present invention relates to an aromatic hydrocarbon resin that can be used as a modifier of an epoxy resin composition useful for molding materials, various binders, coating materials, laminated materials, and the like, a process for producing the same, and an epoxy resin composition containing the aromatic hydrocarbon resin. More specifically, the blending improves the flame retardancy and adhesiveness of the epoxy resin composition, and in particular, blends it into the epoxy resin composition for semiconductor encapsulation, thereby providing flame retardancy, low thermal elasticity, dissimilar materials. The present invention relates to an aromatic hydrocarbon resin that can contribute to improvement in adhesion at an interface, a method for producing the same, and an epoxy resin composition containing the aromatic hydrocarbon resin.

  Epoxy resins are used in a wide range of industrial fields, taking advantage of their properties, but the demand for improved performance is becoming stricter year by year. For example, as a sealing material for a semiconductor element, an epoxy resin containing various epoxy resins such as orthocresol novolak type and biphenyl type, a phenol compound type curing agent such as phenol novolac resin and phenol aralkyl resin, and a filler such as silica. Compositions are frequently used. This is the mainstream of mold-type encapsulating resins because it has good curability during thermal curing, and the cured product has moisture resistance, low stress, low viscosity, and low cost. However, in recent years, with the increase in size of LSI chips, thinning / miniaturization of packages, changes in mounting methods, etc., the demand for sealing materials has become higher, and it has become difficult to cope with conventional sealing materials. .

  For example, in order to improve solder heat resistance, it is strongly desired to reduce the elastic modulus during heat and to improve the adhesion between the lead frame, the chip, and the like and the sealing material. Conventionally, bromine compounds and antimony compounds that have been used as flame retardants have been reviewed due to environmental problems, and therefore, there is a need for curing agents and epoxy resins that are difficult to burn and have excellent flame retardancy. That is, there is a demand for a hard-to-burn hardener or epoxy resin that has low hygroscopicity, low elastic modulus at the soldering temperature, excellent adhesiveness, and flame resistance. In order to satisfy these demands, curing agents and epoxy resins having various novel skeletons have been studied. However, the improvement of the curing agent and the epoxy resin alone is limited, and development of additives such as an additive for improving adhesiveness and a halogen-free alternative flame retardant is also being promoted.

  For example, various phosphorus-based flame retardants and metal hydroxides are used as halogen-free alternative flame retardants. Epoxy resin compositions containing these have difficulty in moldability and reliability, It is hard to say that they are fully satisfied with market demands. Inden, coumarone, styrene copolymer resins and the like are known as modifiers for improving adhesiveness (see Patent Document 1). However, the flame retardancy of the epoxy resin composition is deteriorated, or a cured product is used. There were various problems such as plasticizing more than necessary and lowering the glass transition point.

JP-A-1-249824

  Therefore, an object of the present invention is to add to an epoxy resin composition to increase its flame retardancy and to reduce the elastic modulus during heating in order to improve solder heat resistance, and to adhere to a lead frame, chip, etc. It is an object of the present invention to provide a novel modifier capable of improving the properties, a production method thereof, and an epoxy resin composition containing the same.

（式中、Ａは、下記式（３）で示される化合物から生じる２価の芳香族基であり、Ｂは、少なくとも１個の置換可能な水素を有する芳香族炭化水素から生じる１価又は２価の芳香族基であり、ｎは、０以上の整数である。また下記式（３）において、Ｒ^２、Ｒ^３は、それぞれ炭素数１〜６のアルキル基であり、ｑ、ｒはそれぞれ０〜４の整数であり、ｑ個のＲ^２、ｒ個のＲ^３はそれぞれ同一でも異なるものでもよい） That is, the present invention is an aromatic compound represented by the following formula (1), having a softening point of 50 to 150 ° C. according to the ring and ball method (JIS K2207), and an ICI melt viscosity at 150 ° C. of 0.5 to 200 poise. It relates to a hydrocarbon resin.

(In the formula, A is a divalent aromatic group generated from a compound represented by the following formula (3), and B is a monovalent or 2 generated from an aromatic hydrocarbon having at least one replaceable hydrogen. the valence of the aromatic group, n is in an integer of 0 or more. the following equation ^{(3), R 2, R} 3 are each alkyl groups having 1 to 6 carbon atoms, q, r are each (It is an integer of 0 to 4, and q R ² and r R ³ may be the same or different.)

上記１価又は２価の芳香族基Ｂとしては、炭素数１〜６のアルキル基で置換されていてもよい芳香族炭化水素、とくに縮合多環芳香族炭化水素から生じる基であることが好ましい。

The monovalent or divalent aromatic group B is preferably a group derived from an aromatic hydrocarbon which may be substituted with an alkyl group having 1 to 6 carbon atoms, particularly a condensed polycyclic aromatic hydrocarbon. .

（式中、Ａは式（１）におけるＡと同じ。またＸはハロゲン、水酸基又はアルコキシ基である。） The present invention also provides 0.1 to 0.9 mol of a compound represented by the following formula (4) in the presence of an acid catalyst with respect to 1 mol of an aromatic hydrocarbon having at least one replaceable hydrogen. The present invention relates to a method for producing an aromatic hydrocarbon resin represented by the above formula (1), characterized by reacting at a ratio.

(In the formula, A is the same as A in formula (1). X is a halogen, a hydroxyl group or an alkoxy group.)

  The present invention also relates to an epoxy resin modifier comprising the above aromatic hydrocarbon resin. Furthermore, this invention relates to the epoxy resin composition formed by mix | blending the said epoxy resin modifier with the epoxy resin in the ratio of 2-100 weight part with respect to 100 weight part of hardening agents. In blending the modifier with the epoxy resin, the modifier can be blended with the curing agent in advance to form a curing agent composition for epoxy resin. The epoxy resin composition preferably contains at least one additive selected from inorganic fillers and curing accelerators, more preferably both additives. Such an epoxy resin composition is preferably used as a sealing material for a semiconductor element in a semiconductor device.

  The aromatic hydrocarbon resin of the present invention has a substantially adverse effect on the curing characteristics and physical properties of the epoxy resin composition by being blended as a modifier in the epoxy resin composition containing the epoxy resin and the curing agent. In this way, flame retardancy and adhesiveness can be improved, and a low elastic modulus during heat can be achieved. Therefore, the epoxy resin composition of the present invention containing this modifier is extremely useful as a sealing material for semiconductor elements in semiconductor devices. According to the present invention, it is also possible to efficiently produce an aromatic hydrocarbon resin useful as a modifier for an epoxy resin composition.

The aromatic hydrocarbon resin of the present invention is represented by the following formula (1), and has an ICI melt viscosity at a softening point of 50 to 150 ° C., preferably 60 to 130 ° C., and 150 ° C. according to the ring and ball method (JIS K2207). Of 0.5 to 200 poise, preferably 1 to 100 poise.

In the above formula, A is a divalent aromatic group generated from a compound represented by the following formula (3), and B is a monovalent or 2 generated from an aromatic hydrocarbon having at least one replaceable hydrogen. Valent aromatic group. Moreover, n is an integer greater than or equal to 0, and the average value of n is about 0.5-10 normally, Preferably it is about 1-5. In the formula (1), (n + 1) A and (n + 2) B may be the same or different. In the following formula (3), R ¹ , R ² and R ³ are each an alkyl group having 1 to 6 carbon atoms, q and r are each an integer of 0 to 4, and q R ² , r Each R ³ may be the same or different.

In the aromatic hydrocarbon resin represented by the formula (1), as the divalent aromatic group A, specifically, biphenyl-4,4′-dimethylene group, biphenyl-2,2′-dimethylene group, biphenyl-4, Typical examples include 2'-dimethylene group, biphenyl-3,2'-dimethylene group, biphenyl-3,3'-dimethylene group, biphenyl-4,3'-dimethylene group. When it has two or more bivalent aromatic groups A, you may be comprised from 2 or more types of these groups. Also specifically monovalent or divalent aromatic group B resulting from an aromatic hydrocarbon having at least one substitutable hydrogen, an aromatic substituted with an alkyl group having 1 to 6 carbon atoms Examples include a group formed by removing two aromatic hydrogen atoms from a hydrocarbon when B is in the molecular chain and one when B is at the molecular end. As the aromatic hydrocarbon , condensed polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene and pyrene are preferable, and naphthalene is particularly preferable. The monovalent or divalent aromatic group B is not limited to a group derived from a condensed polycyclic aromatic hydrocarbon as described above. As described later, a monocyclic aromatic hydrocarbon or a non-condensed polyvalent aromatic group B is used. It may be a group derived from a ring aromatic hydrocarbon . Such a monovalent or divalent aromatic group B may be composed of those derived from the two or more aromatic compounds. More specifically, as the aromatic hydrocarbon resin represented by the formula (1), a compound in which A is a biphenyl-4,4′-dimethylene group and B is a 2,6-naphthylene group or a 2-naphthyl group, Examples thereof include a biphenyl-4,4′-dimethylene group and a compound in which B is a 1,4-naphthylene group or 1-naphthyl group.

（式中、Ａは式（１）におけるＡと同じ。またＸはハロゲン、水酸基又はアルコキシ基である。）で示される化合物を、酸触媒の存在下、式（１）で示される芳香族炭化水素樹脂１モルに対し、式（４）で示される化合物を０．１〜０．９モル、好ましくは０．２〜０．７モルの割合で反応させることによって製造することができる。 The aromatic hydrocarbon resin represented by the formula (1) includes an aromatic compound having at least one replaceable hydrogen and the following formula (4):

(In the formula, A is the same as A in formula (1). X is a halogen, a hydroxyl group or an alkoxy group.) In the presence of an acid catalyst, the compound represented by formula (1) is converted to an aromatic carbonized compound. It can manufacture by making the compound shown by Formula (4) react in the ratio of 0.1-0.9 mol with respect to 1 mol of hydrogen resins, Preferably it is 0.2-0.7 mol.

The aromatic hydrocarbon having at least one substitutable hydrogen is an aromatic hydrocarbon which may be substituted with an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms. Preferred are condensed polycyclic aromatic hydrocarbons. Specific examples of such a condensed polycyclic aromatic hydrocarbon include naphthalenes such as naphthalene, methylnaphthalene, ethylnaphthalene, propylnaphthalene, dimethylnaphthalene, diethylnaphthalene, and dipropylnaphthalene, and three rings such as anthracene, phenanthrene, and pyrene. The above condensed polycyclic aromatic hydrocarbons and alkyl substituted derivatives thereof, coal tar, coal tar pitch, petroleum naphtha cracked tar, ethylene bottom oil, ethylene bottom pitch, etc. Examples thereof include a mixture containing a mixture as a main component. Examples of the aromatic hydrocarbon having at least one replaceable hydrogen include monocyclic rings such as xylenes, trimethylbenzenes, tetramethylbenzenes and diethylbenzenes in addition to the condensed polycyclic aromatic hydrocarbons as described above. aromatic hydrocarbons and, biphenyl, biphenyl ether, biphenyl sulfide, Ru can be used non-condensed polycyclic aromatic compounds such as biphenyl sulfone.

  Specific examples of the compound represented by the above formula (4) include 4,4′-bischloromethylbiphenyl, 4,2′-bischloromethylbiphenyl, 2,2′-bischloromethylbiphenyl, 4,3 ′. -Bischloromethylbiphenyl, 3,3'-bischloromethylbiphenyl, 3,2'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,2'-bisbromomethylbiphenyl, 2,2 ' -Bisbromomethylbiphenyl, 4,3'-bisbromomethylbiphenyl, 3,3'-bisbromomethylbiphenyl, 3,2'-bisbromomethylbiphenyl, 4,4'-bisiodomethylbiphenyl, 4,2 ' -Bisiodomethylbiphenyl, 2,2'-bisiodomethylbiphenyl, 4,3'-bisiodomethylbiphenyl, 3,3'- Bishalomethyl aromatic compounds such as suodomethyl biphenyl, 3,2′-bisiodomethyl biphenyl, 4,4′-bishydroxymethyl biphenyl, 4,2′-bishydroxymethyl biphenyl, 2,2′-bishydroxymethyl biphenyl 4,3′-bishydroxymethylbiphenyl, 3,3′-bishydroxymethylbiphenyl, bishydroxymethyl aromatic compounds such as 3,2′-bishydroxymethylbiphenyl, 4,4′-bismethoxymethylbiphenyl, 4 , 2′-bismethoxymethylbiphenyl, 2,2′-bismethoxymethylbiphenyl, 4,3′-bismethoxymethylbiphenyl, 3,3′-bismethoxymethylbiphenyl, 3,2′-bismethoxymethylbiphenyl, etc. Bisalkoxymethyl aromatic compounds It can be mentioned.

The reaction of the aromatic hydrocarbon having at least one replaceable hydrogen and the compound represented by the above formula (4) is performed in the presence of an acid catalyst. Examples of the acid catalyst include hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, diethylsulfuric acid, zinc chloride, and aluminum chloride. When the compound represented by formula (4) is a compound having a halomethyl group, the reaction starts in the presence of a slight amount of water, and a hydrogen halide is generated by the condensation reaction. By using it, reaction can be advanced.

In the reaction of an aromatic hydrocarbon having at least one substitutable hydrogen with the compound represented by the above formula (4), an aromatic hydrocarbon having a desired degree of polymerization (ICI melt viscosity at 150 ° C.) and a softening point In order to obtain a resin, 0.1 to 0.9 mol, preferably 0.2 to 0, of the compound represented by formula (4) is used per 1 mol of an aromatic hydrocarbon having at least one replaceable hydrogen. It is better to use at a ratio of 7 mol. That is, when the amount of the compound represented by formula (4) is increased from the above range, the resulting aromatic hydrocarbon resin has an excessively high softening point and melt viscosity, and may be partially gelled. Moreover, when the usage-amount of the compound shown by Formula (4) is less than the said range, since an unreacted aromatic compound increases, it is unpreferable. Moreover, although the usage-amount of an acid catalyst changes also with the kind, when reaction rate and economical efficiency are considered, what is necessary is just to make it exist about 10 ppm -8% in a reaction system. In particular, when the aromatic hydrocarbon resin obtained is used for a semiconductor encapsulant, it is desirable to reduce the remaining amount of the acid catalyst as much as possible. Therefore, it is preferable to use about 20 to 200 ppm of trifluoromethanesulfonic acid as the acid catalyst.

  The reaction temperature is about 60 to 200 ° C., and the reaction time is about 1 to 20 hours, although it varies depending on the reaction temperature. The reaction can be performed under conditions of two or more stages having different reaction temperatures, such that the reaction is initially performed at a relatively low temperature and the subsequent stage is performed at a relatively high temperature. After completion of the reaction, the acid catalyst used in the reaction can be neutralized with a base as necessary. Various bases can be used for such purposes, but when an aromatic hydrocarbon resin as a reaction product is used as a modifier for a semiconductor encapsulant, 1,8 It is preferable to use amines such as diazabicyclo (5,4,0) undecene-7 (DBU) and various imidazoles. After completion of the reaction, an unreacted raw material such as an aromatic compound having at least one substitutable hydrogen can be removed as necessary. Examples of the method for removing the aromatic compound include a method in which heat treatment is performed at 130 ° C. or higher under reduced pressure, a method by steam distillation, or a method in which unreacted substances are separated using a suitable solvent.

In general, mixed aromatic hydrocarbon resins having various values of n reacted at various positions on the aromatic ring of an aromatic hydrocarbon having one substitutable hydrogen can be obtained by the method as described above. For example, when the aromatic hydrocarbon having at least one substitutable hydrogen is naphthalene, the 1- and 4-positions of the naphthalene ring are relatively preferentially substituted, but other positions such as 2-position, 3- Also substituted at the 5th, 6th, 7th, 8th, etc. positions. In the general formula (1), n may be 0 or more, and depending on the reaction raw material ratio, a very high molecular weight, for example, n may be included up to about 1000. Aromatic carbonization with a softening point of 50 to 150 ° C., preferably 60 to 130 ° C., and an ICI melt viscosity at 150 ° C. of 0.5 to 200 poise, preferably 1 to 100 poise according to the JIS method (JIS K2207) A hydrogen resin can be obtained. In this case, the average value of n is usually about 0.5 to 10, preferably about 1 to 5. The aromatic hydrocarbon resin of the present invention having such properties is useful as an epoxy resin modifier, and an epoxy resin composition containing an appropriate amount in an epoxy resin composition containing an epoxy resin and a curing agent. It is possible to improve the flame retardancy and adhesion of the resin and to lower the elastic modulus during heat.

  Examples of the epoxy resin used for blending the aromatic hydrocarbon resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, and phenol. Glycidyl ether type epoxy resin, glycidyl ester such as biphenyl aralkyl type epoxy resin, epoxidized aralkyl resin by xylylene bond such as phenol, naphthol, dicyclopentadiene epoxy resin, dihydroxynaphthalene type epoxy resin, triphenolmethane type epoxy resin Examples thereof include epoxy resins having two or more epoxy groups in the molecule, such as type epoxy resins and glycidylamine type epoxy resins. These epoxy resins may be used alone or in combination of two or more. Among these epoxy resins, in consideration of moisture resistance, low elastic modulus during heat, flame retardancy, etc., bifunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, A polyfunctional epoxy resin having many aromatic rings such as an epoxidized aralkyl resin by a xylylene bond such as phenol or naphthol is preferred.

  Various types of curing agents can be blended in the epoxy resin. For example, a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, an imidazole curing agent, a catalyst curing agent, and other known curing agents can be used. In particular, when used for semiconductor encapsulants, phenol novolak resins, phenol aralkyl resins, phenol naphthyl aralkyl resins, phenol biphenyl aralkyl resins, various naphthol novolak resins, naphthol aralkyl resins, triphenolmethane type novolak resins, dicyclopentadiene. It is preferable to use a phenolic curing agent such as a type novolac resin. The above curing agents can be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the curing agent is such that the equivalent ratio of the functional group / epoxy group of the curing agent is 0.5 to 1.5, considering the moldability and physical properties of the cured product. In particular, it is preferably blended so as to be in the range of 0.8 to 1.2. Moreover, it is effective to mix | blend the said aromatic hydrocarbon resin in the ratio of 2-100 weight part with respect to 100 weight part of hardening | curing agents, Preferably it is 5-50 weight part. That is, if the blending amount of the aromatic hydrocarbon resin is too small, the modification effect is difficult to be expressed. On the other hand, if the blending amount is excessive, the curability decreases, the glass transition temperature decreases, the aromatic hydrocarbon resin mold. This is not preferable because it causes adverse effects such as bleeding. Of course, the aromatic hydrocarbon resin can be blended into the epoxy resin separately from the curing agent, but prior to blending into the epoxy resin, a composition with the curing agent is prepared and this is the epoxy resin. It can also be blended.

  In the epoxy resin composition of the present invention, other additives such as a curing accelerator, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a flame retardant aid, a low stress agent, and the like as necessary. Can be added or reacted in advance. It is particularly desirable to use a curing accelerator in combination. Moreover, when using as a semiconductor sealing material, use of an inorganic filler is essential.

  As the curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol resin curing agent can be used. For example, a tertiary amine, a quaternary ammonium salt, an imidazole and its boron salt, organic A phosphine compound and its boron salt, a quaternary phosphonium salt, etc. can be mentioned. More specifically, tertiary amines such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazoles such as imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, Examples thereof include organic phosphine compounds such as (p-methylphenyl) phosphine and tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, and tetraphenylphosphonium tetranaphthoic acid borate. Of these, organic phosphine compounds and quaternary phosphonium quaternary borate salts are preferred from the viewpoint of low water absorption and reliability. The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of curing characteristics and various physical properties.

  Examples of inorganic fillers to be blended when used for semiconductor encapsulation include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia , Barium sulfate and the like can be mentioned, and amorphous silica, crystalline silica and the like are particularly preferable. In order to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing. In the epoxy resin composition for semiconductor encapsulation, it varies depending on the type of inorganic filler, but considering the solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., inorganic filling It is preferable to mix the agent in such a proportion that it accounts for 60 to 93% by weight of the total composition.

  Examples of coupling agents include silane coupling agents such as vinyl silane, amino silane, and epoxy silane, and titanium coupling agents. Examples of mold release agents include carnauba wax, paraffin wax, stearic acid, and montanic acid. Examples of the carboxyl group-containing polyolefin wax and the colorant include carbon black. Examples of flame retardants include halogenated epoxy resins, halogen compounds, phosphorus compounds, and the like, and flame retardant aids include antimony trioxide. Examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

  As a general method for preparing an epoxy resin as a molding material, a predetermined ratio of each raw material is sufficiently mixed by, for example, a mixer, kneaded by a hot roll or a kneader, and then cooled and solidified. Can be pulverized to an appropriate size and tableted if necessary. The molding material thus obtained can be used to manufacture a semiconductor device by sealing the semiconductor element by, for example, low-pressure transfer molding. Curing of the epoxy resin composition can be performed, for example, in a temperature range of 100 to 250 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples.
[Example 1]
A flask was charged with 127.5 g (0.996 mol) of naphthalene, 100.0 g (0.398 mol) of 4,4′-bischloromethylbiphenyl and 45.5 g of methanol, and the temperature was raised with stirring. The reaction was carried out for 5 hours at 110 ° C. for 1.5 hours and further at 160 ° C. for 8 hours. Hydrogen chloride produced during the reaction was discharged out of the system and neutralized. After completion of the reaction, the mixture was treated under reduced pressure (50 Torr) at 190 ° C. for 3 hours to obtain 141.3 g of aromatic hydrocarbon resin 1 having the following properties.
Unreacted 4,4'-bischloromethylbiphenyl not detected Unreacted naphthalene not detected (GC analysis)
ICI melt viscosity at 150 ° C 51 poise Softening point (JIS K2207) 119 ° C
Average value of n calculated from the reacted raw material 2.3

A GPC chart of the aromatic hydrocarbon resin 1 is shown in FIG. The component composition ratio of each degree of polymerization of the aromatic hydrocarbon resin 1 calculated from the chart of FIG. 1 was as follows.
n = 0 27.6%
n = 1 20.2%
n = 2 14.0%
n = 3 or more 38.2%

[Example 2]
141.1 g (1.102 mol) of naphthalene, 83.0 g (0.331 mol) of 4,4′-bischloromethylbiphenyl and 44.6 g of methanol were charged into a flask, and the temperature was raised with stirring. In a state where the system was uniformly dissolved at 68 ° C., 0.224 g of a 10% aqueous solution of trifluoromethanesulfonic acid was added, and kept at 110 ° C. for 4 hours. The condensed water produced during the reaction was removed from the system. After completion of the reaction, 0.227 g of a 10% aqueous solution of DBU was added for neutralization, and then treated under reduced pressure (50 Torr) at 190 ° C. for 3 hours to obtain 124 g of an aromatic hydrocarbon resin 2 having the following properties.
Unreacted 4,4'-bischloromethylbiphenyl Not detected Unreacted naphthalene 0.1% (GC analysis)
ICI melt viscosity at 150 ° C 5 poise Softening point (JIS K2207) 93 ° C
Average value of n calculated from the reacted raw material 1.5

Moreover, the component composition ratio of each polymerization degree of the aromatic hydrocarbon resin 2 computed from a GPC chart was as follows.
n = 0 38.7%
n = 1 24.7%
n = 2 15.9%
n = 3 or more 20.7%

[Examples 3-4, Comparative Examples 1-2]
Biphenol type epoxy resin YX-4000H represented by the following formula (5) as an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 190 g / eq), phenol aralkyl resin HE100C- represented by the following formula (6) as a curing agent 10 (Air Water Chemical Co., Ltd., hydroxyl equivalent 168 g / eq) or biphenyl aralkyl resin HE200C-10 represented by the following formula (7) (Air Water Chemical Co., Ltd., hydroxyl equivalent 205 g / eq) After blending the aromatic hydrocarbon resin 1 obtained in Example 1 as a modifier, fused silica, triphenylphosphine, silane coupling agent and carnauba wax in the proportions shown in Table 1, and mixing them well, 85 By kneading for 5 minutes with two rolls at ℃ ± 3 ℃, cooling and grinding, To obtain a composition.

Next, this epoxy resin composition was molded with a transfer molding machine at a pressure of 100 kgf / cm ² at 175 ° C. for 2 minutes and then post-cured at 180 ° C. for 6 hours to obtain a cured epoxy resin. Each cured product was used as a test piece for adhesive strength, flexural modulus, glass transition temperature (Tg), and flame retardancy test. Each test was performed according to the following. The results are shown in Table 1.

(1) Adhesive strength After molding an epoxy resin on a metal plate plated with Ni-Pd-Au with a transfer molding machine, post-cure at 180 ° C for 6 hours to obtain a molded product (2 mm x 2 mm x 2 mm). The metal plate and shear adhesive strength were measured at room temperature.

(2) Flexural modulus A strip of sample shape 80 mm × 10 mm × 4 mm was allowed to stand in a 260 ° C. atmosphere for 10 minutes, and then the flexural modulus at 260 ° C. was measured according to JIS K6911.

(3) Measurement of glass transition temperature (Tg) Using a strip of sample shape 5 mm × 5 mm × 2 mm, the linear expansion coefficient was measured by TMA, and the inflection point of the linear expansion coefficient was defined as Tg (temperature increase rate 5 ° C. / Min).

(4) Flammability test Using a sample having a thickness of 1.6 mm, a width of 10 mm, and a length of 135 mm, the afterflame time was measured in accordance with the UL-94 standard, and the flame retardancy was evaluated.

  The hardened | cured material obtained from the epoxy resin composition of Examples 3-4 containing the aromatic hydrocarbon resin of this invention is obtained from the epoxy resin composition of Comparative Examples 1-2 which does not contain the aromatic hydrocarbon resin. It can be seen that all of the cured products show excellent values in adhesiveness, low elastic modulus at heat, and flame retardancy. These are excellent, for example, as an epoxy resin composition for semiconductor encapsulation, and have high practical value.

2 is a GPC chart of an aromatic hydrocarbon resin obtained in Example 1. FIG.

Claims (15)

An aromatic hydrocarbon resin represented by the following formula (1), having a softening point of 50 to 150 ° C. according to the ring and ball method (JIS K2207) and an ICI melt viscosity at 150 ° C. of 0.5 to 200 poise.

(In the formula, A is a divalent aromatic group generated from a compound represented by the following formula (3), and B is a monovalent or 2 generated from an aromatic hydrocarbon having at least one replaceable hydrogen. the valence of the aromatic group, n is in an integer of 0 or more. the following equation ^{(3), R 2, R} 3 are each alkyl groups having 1 to 6 carbon atoms, q, r are each (It is an integer of 0 to 4, and q R ² and r R ³ may be the same or different.)

The aromatic hydrocarbon resin according to claim 1, wherein the monovalent or divalent aromatic group B is a group derived from an aromatic hydrocarbon which may be substituted with an alkyl group having 1 to 6 carbon atoms. The aromatic hydrocarbon resin according to claim 2 , wherein the aromatic hydrocarbon is a condensed polycyclic aromatic hydrocarbon. Reacting a compound represented by the following formula (4) at a ratio of 0.1 to 0.9 mol in the presence of an acid catalyst with respect to 1 mol of an aromatic hydrocarbon having at least one replaceable hydrogen. The method for producing an aromatic hydrocarbon resin according to claim 1 .

(In the formula, A is the same as A in formula (1). X is a halogen, a hydroxyl group or an alkoxy group.) The aromatic hydrocarbon resin according to claim 4 , wherein the aromatic hydrocarbon having at least one replaceable hydrogen is an aromatic hydrocarbon which may be substituted with an alkyl group having 1 to 6 carbon atoms. Method. The method for producing an aromatic hydrocarbon resin according to claim 5 , wherein the aromatic hydrocarbon is a condensed polycyclic aromatic hydrocarbon.   The method for producing an aromatic hydrocarbon resin according to any one of claims 4 to 6, wherein trifluoromethanesulfonic acid is used as the acid catalyst.   The modifier for epoxy resins which consists of an aromatic hydrocarbon resin in any one of Claims 1-3. The hardening | curing agent composition for epoxy resins formed by mix | blending the modifier for epoxy resins of Claim 8 in the ratio of 2-100 weight part with respect to 100 weight part of hardening | curing agents for epoxy resins. The epoxy resin, together with a curing agent, the epoxy resin modifier according to claim 8, epoxy resin composition obtained by blending in a proportion of 2 to 100 parts by weight based on the curing agent to 100 parts by weight. The epoxy resin composition according to claim 10, further comprising an inorganic filler. Further the epoxy resin composition according to claim 10 or 11 comprising a curing accelerator.   The epoxy resin composition according to any one of claims 10 to 12, which is used for a semiconductor sealing material.   The epoxy resin hardened | cured material formed by hardening | curing the epoxy resin composition in any one of Claims 10-13. A semiconductor device formed by sealing a semiconductor element using the epoxy resin composition according to claim 13.

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