JP2012172122A - Phenolic polymer, production method of the same and application of the same - Google Patents

Abstract

【選択図】なしTo provide a phenolic polymer having a flame retardancy equal to or higher than that of a conventional phenol aralkyl resin having a biphenyl skeleton and a high fluidity, a composition thereof, and a method for producing the same.
In the reaction with a phenol of formula (1), an aromatic compound of formula (2), an aldehyde of formula (3), and a condensate of m-xylene, formaldehyde and methanol, the phenol of the aromatic compound The molar ratio of aldehydes to phenol is 0.05 to 0.40, the molar ratio of aldehydes to phenols is 0 to 0.20, the oxygen content is 10 to 20 wt%, the viscosity at 25 ° C. is 10 to 200 mPa · s, the number average A phenolic polymer obtained by reacting a condensate of m-xylene, formaldehyde and methanol having a molecular weight of 200 to 400 at 5 to 25 wt% of the weight of phenols.

[Selection figure] None

Description

The present invention relates to a phenolic polymer, a process for producing the same, and a use thereof. More specifically, the present invention relates to a phenolic polymer suitable for semiconductor encapsulant use having low melt viscosity and high flame retardancy, its production method and its use.

When used as a curing agent for epoxy resins, phenol aralkyl resins have excellent physical properties such as heat resistance, moisture resistance, mechanical properties, etc., and low viscosity resins can be produced and workability is good. And is used as a resin for surface mounting, particularly as a semiconductor sealing resin.

In recent years, as semiconductor packages have become smaller and thinner and more complicated in shape, semiconductor sealing resins are increasingly required to have low viscosity. If the viscosity is low, its fluidity will improve and it will be possible to deal with packages with complex shapes, such as BGA, and it will be possible to increase the filling of the filler. This is also advantageous in terms of reliability.

In recent years, epoxy resin compositions with excellent flame retardancy that do not use halogenated flame retardants and antimony compounds have been moving to reduce or eliminate potentially harmful substances due to the importance of corporate activities in consideration of the global environment. The phenol aralkyl resin used in applications ranging from general-purpose packages to advanced packages is also required to have excellent flame retardancy without using halogen-based flame retardants and antimony compounds. (For example, patent document 1 etc.). Among them, a phenol aralkyl resin having a biphenyl skeleton is known to be highly flame retardant and is used extensively in advanced package applications. On the other hand, there is an increasing demand for higher fluidity (for example, patents). Reference 2). However, there is no case where the improvement of the high fluidity is achieved while having the flame retardance equal to or higher than that of the conventional phenol aralkyl resin having a biphenyl skeleton. On the other hand, there is a modification example of phenol aralkyl resin by m-xylene / formaldehyde condensate, and high fluidity is achieved while having the same or better flame retardance than unmodified one. Although the subject is not a biphenyl skeleton type phenol aralkyl resin and the flowability of the unmodified product can be improved, the flame retardancy is unsatisfactory because the unmodified product itself has poor self-extinguishing properties (Patent Document 3). .

JP 5-97965 JP2007-106928A JP2009-242480

  An object of the present invention is to provide a phenolic polymer having a flame retardancy equal to or higher than that of a conventional phenol aralkyl resin having a biphenyl skeleton and a high fluidity, a composition thereof, and a method for producing the same.

  The present invention includes phenols represented by the following general formula (1), aromatic compounds represented by the following general formula (2), aldehydes represented by the following general formula (3), and m-xylene / formaldehyde / methanol. In the reaction with the condensate, the molar ratio of the aromatic compound to the phenol is 0.05 to 0.40, the molar ratio of the aldehyde to the phenol is 0 to 0.20, the oxygen content is 10 to 20 wt%, 25 A phenolic system obtained by reacting under the condition that a condensate of m-xylene, formaldehyde and methanol having a viscosity at 10 ° C. of 10 to 200 mPa · s and a number average molecular weight of 200 to 400 is used in an amount of 5 to 25 wt% of the phenol weight. A polymer is provided.

式（１）中、Ｒ^１は水素原子、炭素数１〜６のアルキル基またはアリール基であり、式（２）中、Ｘはハロゲン、ＯＨ基又はＯＣＨ_３基、式（３）中、Ｒ^２は水素原子又はフェニル基である。

In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. In the formula (2), X is a halogen, OH group or OCH ₃ group, in the formula (3), R ² is a hydrogen atom or a phenyl group.

  The present invention provides an epoxy resin composition comprising the above-described phenolic polymer and an epoxy resin.

  The present invention provides a phenol represented by the general formula (1), an aromatic compound represented by the general formula (2), an aldehyde represented by the general formula (3), and a condensate of m-xylene / formaldehyde. In the reaction, the molar ratio of the aromatic compound to the phenols is 0.05 to 0.40, the molar ratio of the aldehydes to the phenols is 0 to 0.20, the oxygen content is 10 to 20 wt%, at 25 ° C. A phenolic polymer obtained by reacting a m-xylene / formaldehyde / methanol condensate having a viscosity of 10 to 200 mPa · s and a number average molecular weight of 200 to 400 under a condition that 5 to 25 wt% of the phenol weight is used. A manufacturing method is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the low melt viscosity phenolic polymer which has a high self-extinguishing property effective in a molding material, various binders, a coating material, a laminated material, etc. and its manufacturing method are provided.

  According to the present invention, a phenolic polymer that is particularly useful as an epoxy resin curing agent and can form an epoxy resin composition excellent in low melt viscosity and flame retardancy, especially when used for semiconductor encapsulation, And an epoxy resin composition thereof.

  The present invention includes phenols represented by the general formula (1), aromatic compounds represented by the general formula (2), aldehydes represented by the general formula (3), and m-xylene / formaldehyde / methanol. In the reaction with the condensate, the molar ratio of the aromatic compound to the phenol is 0.05 to 0.40, the molar ratio of the aldehyde to the phenol is 0 to 0.20, the oxygen content is 10 to 20 wt%, 25 A phenolic system obtained by reacting under the condition that a condensate of m-xylene, formaldehyde and methanol having a viscosity at 10 ° C. of 10 to 200 mPa · s and a number average molecular weight of 200 to 400 is used in an amount of 5 to 25 wt% of the phenol weight. A polymer is provided.

  The present invention includes phenols represented by the general formula (1), aromatic compounds represented by the general formula (2), aldehydes represented by the general formula (3), and m-xylene / formaldehyde / methanol. In the reaction with the condensate, the molar ratio of the aromatic compound to the phenol is 0.05 to 0.40, the molar ratio of the aldehyde to the phenol is 0 to 0.20, the oxygen content is 10 to 20 wt%, 25 A phenolic system obtained by reacting under the condition that a condensate of m-xylene, formaldehyde and methanol having a viscosity at 10 ° C. of 10 to 200 mPa · s and a number average molecular weight of 200 to 400 is used in an amount of 5 to 25 wt% of the phenol weight. A method for producing a polymer is provided.

  Examples of the phenols represented by the general formula (1) include phenol, o-, m-, p-cresol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- , 3,5-xylenol, o-, m-, p-ethylphenol, and the like, and one or more of them can be used, and phenol is particularly preferable.

  The condensate of m-xylene / formaldehyde / methanol used in the present invention is an oligomer mixture having a structure in which m-xylene is crosslinked with a methylene group and having a reactive functional group capable of crosslinking via the methylene group. is there. These can be obtained by condensing m-xylene, formaldehyde, and methanol in the presence of an acidic catalyst, and an index of reactivity is given by oxygen content (Japanese Patent Laid-Open No. 10-168147). The oxygen content of the condensate of m-xylene / formaldehyde / methanol, viscosity at 25 ° C., and number average molecular weight depend on the ratio of m-xylene, formaldehyde, and methanol as raw materials, but considering the balance between flame retardancy and fluidity The oxygen content is preferably 10 to 20 wt%, the viscosity at 25 ° C. is 10 to 200 mPa · s, and the number average molecular weight is preferably in the range of 200 to 400. This compound is commercially available and can be easily obtained. (For example, “Nikanol Y-50” “Nikanol Y-100” manufactured by Fudou Co., Ltd.).

  Examples of the aromatic compound represented by the general formula (2) include 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, 4,4′-bis (iodomethyl) biphenyl, 4 4,4′-bis (hydroxymethyl) biphenyl, 4,4′-bis (methoxymethyl) biphenyl, and the like. Of these aromatic compounds, 4,4'-bis (chloromethyl) biphenyl is preferably used from the viewpoint of availability.

  Examples of aldehydes represented by the general formula (3) include formaldehyde and benzaldehyde. These are used as necessary for the purpose of adjusting the performance of the curing agent for epoxy resin and may be used alone or in combination, but from the viewpoint of suppressing cold flow of the epoxy resin composition and imparting high fluidity, The use of benzaldehyde is preferred.

  The phenolic polymer shown above includes phenols represented by the general formula (1), aromatic compounds represented by the general formula (2), aldehydes represented by the general formula (3), and m- It can be obtained by reacting a condensate of xylene, formaldehyde and methanol.

  Reaction of phenols represented by the general formula (1), aromatic compounds represented by the general formula (2), aldehydes represented by the general formula (3), and a condensate of m-xylene / formaldehyde / methanol. In order to obtain a phenolic polymer having an appropriate molecular weight and excellent performance as a curing agent for epoxy resins, the molar ratio of aromatic compound to phenols is 0.05 to 0.40, preferably 0.8. 15 to 0.25, molar ratio of aldehydes to phenol is 0 to 0.20, preferably 0 to 0.10, m-xylene / formaldehyde / methanol condensate is 5 to 25 wt% of phenols, preferably It is good to make it react at 5 to 15 wt%.

  The above reaction can be obtained by reacting at a temperature of about 60 to 150 ° C. for about 1 to 10 hours in the presence or absence of a catalyst. That is, in the formula (2), when X is an OH group or an OCH3 group, it is necessary to carry out the reaction in the presence of an acid catalyst, and when X is a halogen in the formula (2), a slight amount of water is required. The reaction can be initiated by the presence of and can be accelerated by the hydrogen halide produced by the reaction.

  Catalysts usable in the above reaction include inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, zinc chloride, and second chloride. Lewis acid catalysts such as tin and ferric chloride can be used alone or in combination.

  When the product phenolic polymer is used for electronic material applications such as semiconductor encapsulation, it is not preferable that the acid remains. Therefore, by using hydrochloric acid as the acid catalyst, the condensation reaction mixture is chlorinated under reduced pressure. Hydrogen is preferred because it can be easily removed.

  By removing low-boiling components such as unreacted raw materials, reaction byproducts, and catalysts from the condensation reaction mixture obtained by the condensation reaction, the phenolic polymer that is a reaction product can be recovered. Such a reaction product has an ICI melt viscosity at 150 ° C. of 10 to 300 mPa · s, preferably 50 to 180 mPa · s. The separation operation under reduced pressure, which is performed for removing unreacted raw materials in the reaction product, is usually performed at a temperature of 130 ° C. or higher, so that the molten reaction product obtained by the operation is used as it is. By quenching and solidifying, it can be isolated as an amorphous solid having a softening point (JIS K2207) of about 50 to 80 ° C.

  The phenolic polymer, which is the reaction product thus obtained, generally has a low melt viscosity in the molding temperature range and excellent workability, and the cured product has excellent flame retardancy. Therefore, it can be used for molding materials, various binders, coating materials, laminated materials and the like. Therefore, it is useful as an epoxy resin curing agent, and when used as a curing agent in an epoxy resin-based semiconductor encapsulant, an epoxy resin composition having excellent fluidity is obtained, and a semiconductor device obtained by curing the epoxy resin composition is excellent in flame retardancy.

  Examples of the epoxy resin that can be used with the phenolic polymer in the epoxy resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and biphenyl type. Epoxy resin, phenol biphenyl aralkyl type epoxy resin, epoxidized aralkyl resin with xylylene bonds such as phenol and naphthol, glycidyl ether type epoxy resin such as dicyclopentadiene type epoxy resin, dihydroxynaphthalene type epoxy resin, triphenolmethane type epoxy resin Epoxy compounds having two or more epoxy groups in one molecule such as glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, etc. It is below. These epoxy resins may be used alone or in combination of two or more. In consideration of moisture resistance, low elastic modulus during heat and flame retardancy, bifunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, xylylene such as phenol and naphthol It is preferable to use a polyfunctional epoxy resin having many aromatic rings selected from epoxidized aralkyl resins by bonding.

  In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As such a 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 compound, a quaternary ammonium salt, an imidazole, a phosphine compound, a phosphonium A salt etc. can be mentioned. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 , 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, tri (p -Phosphine compounds such as methylphenyl) phosphine and tri (nonylphenyl) phosphine, triphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoic acid borate and the like. Honiumu salt can be mentioned. Of these, phosphine compounds and phosphonium salts are preferred from the viewpoint of low water absorption and reliability.

  In the epoxy resin composition of the present invention, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance if necessary. Other curing agents can be used in combination. Examples of such other curing agents include phenol novolac resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, and triphenolmethane type novolac resins.

  When using the said epoxy resin composition for semiconductor sealing, addition of an inorganic filler is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesia, barium sulfate, etc. Silica, crystalline silica, and barium sulfate are preferred. 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.

  Examples of coupling agents include mercaptosilane-based, vinylsilane-based, aminosilane-based, and epoxysilane-based silane coupling agents and titanium coupling agents. Examples of mold release agents include carnauba wax, paraffin wax, and coloring. Examples of the agent include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

  The compounding ratio of the phenolic polymer of the present invention and the epoxy resin is such that the equivalent ratio of hydroxyl group / epoxy group is 0.5 to 1.5, particularly 0.8 to 1.2, considering heat resistance, mechanical properties and the like. It is preferable that it exists in the range. Further, even when used in combination with another curing agent, it is preferable that the equivalent ratio of hydroxyl group / epoxy group is the above-mentioned ratio. 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. Furthermore, in an epoxy resin composition for semiconductor encapsulation, although it varies depending on the type of inorganic filler, considering the solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., it is inorganic. It is preferable to blend the filler in a proportion that occupies 60 to 93% by weight of the entire composition.

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

  The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.

[Example 1]
488.5 g (5.196 mol) of phenol, 220.0 g (0.909 mol) of 4,4′-bis (chloromethyl) biphenyl and Nicanol Y-100 (manufactured by Fudou Co., Ltd., number average molecular weight 270) When 7g was charged into a four-necked flask with an outlet at the bottom and the temperature was raised, the system became a slurry state at 50 ° C, and evenly melted at 70 ° C, and generation of hydrogen chloride started. After holding for 1 hour, the temperature was raised, the temperature was kept at 95 ° C. for 2 hours, and then heat treatment was added at 150 ° C. for 1 hour. Hydrogen chloride produced in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 4,4′-bis (chloromethyl) biphenyl and nicanol did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the pressure was reduced to remove hydrogen chloride remaining in the system and unreacted phenol out of the system. Finally, the residual phenol was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. This reaction product was extracted while maintaining at 150 ° C. to obtain 394.1 g of a pale yellowish brown and transparent phenol polymer (1).
The softening point of this phenol polymer (1) based on JIS K 2207 was 67 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 60 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 195 g / eq.

[Example 2]
839.3 g (8.928 mol) of phenol, 350.0 g (1.446 mol) of 4,4′-bis (chloromethyl) biphenyl, 33.1 g (0.312 mol) of benzaldehyde and Nicanol Y-100 (Fudo ( Co., Ltd., number average molecular weight 270) 60.1 g was charged into a four-necked flask with a discharge outlet at the bottom, and when the temperature was raised, the system became a slurry at 50 ° C and melted uniformly at 70 ° C Then, the generation of hydrogen chloride started, and after maintaining at 70 ° C. for 1 hour, the temperature was raised, the temperature was maintained at 95 ° C. for 2 hours, and heat treatment was further applied at 150 ° C. for 1 hour. Hydrogen chloride produced in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 4,4′-bis (chloromethyl) biphenyl, benzaldehyde, and nicanol did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the pressure was reduced to remove hydrogen chloride remaining in the system and unreacted phenol out of the system. Finally, the residual phenol was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. The reaction product was extracted while maintaining at 150 ° C. to obtain 643.2 g of a pale yellowish brown and transparent phenol polymer (2).
The softening point of this phenol polymer (2) based on JIS K 2207 was 68 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 60 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylated back titration method was 188 g / eq.

[Example 3]
Epoxy resin represented by the following general formula (4) (Nippon Kayaku Co., Ltd. NC-3000P, phenol biphenyl aralkyl type, epoxy equivalent 272 g / eq), phenolic polymer (1) obtained in Example 1, molten Silica and phosphorus-based curing accelerator tetraphenylphosphonium tetra-p-methylphenylborate (Hokuko Sangyo Co., Ltd., TPP-MK) were blended in the proportions shown in Table 2 and mixed well, and then 2 at 85 ± 3 ° C. The molding composition was obtained by kneading with this roll for 3 minutes, cooling and grinding. This molding composition was molded at 175 ° C. for 2 minutes at a pressure of 100 kgf / cm 2 using a transfer molding machine, and then post-cured at 180 ° C. for 6 hours to obtain test pieces for measuring the glass transition temperature and for the flame retardancy test. .

（式中、Ｇはグリシジル基、ｎは１〜１０の数）

(In the formula, G is a glycidyl group, n is a number of 1 to 10)

[Example 4]
In Example 3, a molding composition was prepared in the same manner except that the phenolic polymer (2) obtained in Example 2 was used instead of the phenolic polymer (1) obtained in Example 1. Test pieces for glass transition temperature measurement and flame retardancy test were obtained.

[Comparative Example 1]
Phenol biphenyl aralkyl resin (manufactured by Air Water Co., Ltd., HE200C-10) represented by the following general formula (5) was used as the phenol polymer (3).
The softening point of this phenol polymer (2) based on JIS K 2207 was 70 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 100 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 205 g / eq.

（式中、ｎは１〜８の数）

(Where n is a number from 1 to 8)

[Comparative Example 2]
168.8 g (1.796 mol) of phenol, 77.0 g (0.440 mol) of 1,4-di (chloromethyl) benzene and 30.4 g of Nicanol Y-100 (manufactured by Fudou Co., Ltd., number average molecular weight 270) Is added to a four-necked flask with an outlet at the bottom, and when the temperature is raised, the system becomes a slurry state at 50 ° C., dissolves uniformly at 70 ° C., generation of HCl begins, and at 70 ° C. for 1 hour After being held, the temperature was raised, the temperature was kept at 95 ° C. for 2 hours, and then heat treatment was added at 150 ° C. for 1 hour. HCl generated in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 1,4-di (chloromethyl) benzene and nicanol did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the pressure was reduced to remove HCl remaining in the system and unreacted phenol out of the system. Finally, the residual phenol was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. The reaction product was withdrawn while maintaining at 150 ° C. to obtain 152.1 g of a pale yellowish brown and transparent phenol polymer (4).
The softening point of this phenol polymer (4) based on JIS K 2207 was 64 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 50 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 175 g / Eq.

[Comparative Example 3]
In Comparative Example 3, a molding composition was prepared in the same manner except that the phenolic polymer (3) of Comparative Example 1 was used in place of the phenolic polymer (1) obtained in Example 1, and the glass transition was obtained therefrom. Test pieces for temperature measurement and flame retardancy test were obtained.

[Comparative Example 4]
In Comparative Example 4, a molding composition was prepared in the same manner except that the phenolic polymer (4) obtained in Comparative Example 2 was used instead of the phenolic polymer (1) obtained in Example 1. Test pieces for glass transition temperature measurement and flame retardancy test were obtained.

The physical properties of these molding materials were measured by the following method.
(1) Melt viscosity of composition 2.5 g of the epoxy resin composition was used as a tablet, and measured with a high and low flow tester (temperature: 175 ° C., orifice diameter: 1 mm, length: 1 mm).
(2) Glass transition temperature The linear expansion coefficient of the test piece was measured by TMA at a heating rate of 10 ° C./min, and the inflection point of the linear expansion coefficient was taken as the glass transition temperature.
(3) Flame retardance Using a sample having a thickness of 1.6 mm × width 10 mm × length 135 mm, the afterflame time was measured and evaluated in accordance with UL-94.
These evaluation results are shown in Table 2.

In Table 1, Examples 1 and 2 have the basic structure of the phenol biphenyl aralkyl resin of Comparative Example 1, but its melt viscosity is as low as 60% of Comparative Example 1, and the condensation of m-xylene, formaldehyde and methanol provided by the present invention. It can be seen that the modification treatment with the product is an effective means for increasing the fluidity of the phenol biphenyl aralkyl resin having a biphenyl structure. In particular, in Example 2, in addition to the modification treatment of the present invention, a modification treatment with benzaldehyde is added, so that the softening point is improved by 5 ° C. compared to Example 1. It is possible to provide a more practical epoxy resin composition that is less prone to flow.
In Table 2, as shown in Examples 3 to 4, it is confirmed that the high fluidity of the resins of Examples 1 and 2 in Table 1 is maintained even when the epoxy resin composition is used. On the other hand, according to the flame retardancy evaluation, the afterflame times of the cured products of Examples 3 to 4 were almost equivalent to Fmax and Ftotal of the cured product of Comparative Example 3 using the phenol biphenyl aralkyl resin of Comparative Example 1 as a curing agent. . On the other hand, as shown in Comparative Example 2 in Table 1 and Comparative Example 4 in Table 2, a modified product of m-xylene / formaldehyde / methanol condensate having a phenol aralkyl resin as a basic structure is provided with a curing agent and Although high fluidity equivalent to that of the epoxy resin composition is exhibited, it can be seen that the afterflame time of the cured product is twice or more that of Examples 3 to 4 and is inferior in self-digestibility.
From the above, the modification treatment with the condensate of m-xylene, formaldehyde, and methanol performed on the phenol biphenyl aralkyl resin having the biphenyl structure provided by the present invention is highly flame retardant possessed by the unmodified phenol biphenyl aralkyl resin. High fluidity can be imparted while maintaining the above characteristics, and it is possible to achieve both high fluidity and high flame retardance, which was difficult with conventional approaches.

  The hardening | curing agent and composition which this invention provides are suitable for the semiconductor sealing material use as which high fluidity and high flame retardance are calculated | required.

Claims (15)

A phenol represented by the following general formula (1), an aromatic compound represented by the following general formula (2), an aldehyde represented by the following general formula (3), and a condensate of m-xylene, formaldehyde and methanol. In the reaction, the molar ratio of aromatic compound to phenols is 0.05 to 0.40, the molar ratio of aldehydes to phenols is 0 to 0.20, the oxygen content is 10 to 20 wt%, and the viscosity at 25 ° C. A phenolic polymer obtained by reacting under the condition that a condensate of m-xylene, formaldehyde, and methanol having a number average molecular weight of 200 to 400 is used in an amount of 10 to 200 mPa · s and 5 to 25 wt% of the phenol weight.

(In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. In the formula (2), X is a halogen, OH group or OCH ₃ group, in the formula (3). R ² is a hydrogen atom or a phenyl group.)   The phenolic polymer according to claim 1, wherein the molar ratio of aldehydes to phenols is 0. The phenolic polymer according to claim 1 or 2, wherein the ICI melt viscosity at 150 ° C is 10 to 300 mPa · s.   The phenolic polymer according to any one of claims 1 to 3, wherein the phenol is phenol. A phenol represented by the general formula (1), an aromatic compound represented by the general formula (2), an aldehyde represented by the general formula (3), and a condensate of m-xylene / formaldehyde / methanol. In the reaction, the molar ratio of aromatic compound to phenols is 0.05 to 0.40, the molar ratio of aldehydes to phenols is 0 to 0.20, the oxygen content is 10 to 20 wt%, and the viscosity at 25 ° C. A method for producing a phenol polymer obtained by reacting a condensate of m-xylene / formaldehyde having a number average molecular weight of 200 to 400 with a weight of 10 to 200 mPa · s and 5 to 25 wt% of the phenol weight. The method for producing a phenolic polymer according to claim 5, wherein the molar ratio of aldehydes to phenols is 0. The phenolic polymer according to claim 5 or 6, wherein the ICI melt viscosity at 150 ° C is 10 to 300 mPa · s.   The method for producing a phenolic polymer according to any one of claims 5 to 7, wherein the phenol is phenol. The hardening | curing agent for epoxy resins which consists of a phenol type polymer in any one of Claims 1-4. The epoxy resin composition containing the hardening | curing agent for epoxy resins which consists of a phenolic polymer in any one of Claims 1-4, and an epoxy resin. Furthermore, the epoxy resin composition of Claim 10 containing an inorganic filler. Furthermore, the epoxy resin composition of Claim 10 or 11 containing a hardening accelerator. The epoxy resin composition according to claim 10, which is for semiconductor encapsulation. 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.