JP2012077120A - Curable resin composition, cured product of the same, phenol resin, epoxy resin, and semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simultaneously achieve high resistance to wet and soldering and high halogen-free flame retardancy for environmental harmony.SOLUTION: The phenolic resin (B) includes respective structural parts of a naphthylmethyloxy group- or anthracenylmethyloxy group-containing aromatic hydrocarbon group (ph1), a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2), and an alkylidene group or aromatic hydrocarbon structure-containing methylene group (X). Also, a phenol resin including structure, in which a plurality of aromatic hydrocarbon groups selected from the group consisting of the naphthylmethyloxy group- or anthracenylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) are bonded through the alkylidene group or aromatic hydrocarbon structure-containing methylene group (X), is used as a curing agent for epoxy resins.

Description

  The cured product obtained according to the present invention is excellent in heat resistance, moisture resistance, solder resistance, flame retardancy, dielectric properties, curability during curing reaction, and suitable for semiconductor encapsulant, printed circuit board, paint, casting application, etc. The present invention relates to a thermosetting resin composition that can be used for the above, a cured product thereof, a phenol resin, an epoxy resin, and a semiconductor sealing material using the thermosetting resin.

  Thermosetting resin compositions containing an epoxy resin and its curing agent as essential components are excellent in various physical properties such as high heat resistance, moisture resistance, and low viscosity. Electronic components such as semiconductor encapsulants and printed circuit boards, electronic Widely used in parts field, conductive adhesives such as conductive paste, other adhesives, matrix for composite materials, paints, photoresist materials, developer materials, etc.

  In recent years, there has been a demand for further improvements in performances typified by heat resistance and moisture and solder resistance in these various applications, especially in advanced materials. For example, in the field of semiconductor encapsulating materials, the transition to surface mount packages such as BGA and CSP, as well as support for lead-free solder, led to higher reflow processing temperatures, thus increasing moisture resistance and solder resistance. There is a demand for an electronic component encapsulating resin material that is excellent in performance.

  Furthermore, in recent years, from the viewpoint of environmental harmony, the movement of eliminating halogen-based flame retardants has further increased, and there has been a demand for epoxy resins and phenol resins (curing agents) that are highly halogen-free and exhibit high flame retardancy.

  Examples of the phenol resin and epoxy resin for electronic component encapsulating materials that meet the required characteristics include an epoxy resin or a curing agent (phenol resin) in which a benzyl ether structure is introduced by reacting a phenol resin and a benzylating agent such as benzyl chloride under alkaline conditions. (For example, see Patent Documents 1 and 2).

  However, the epoxy resin and the phenol resin described in Patent Document 1 or 2 have improved flame retardancy but have not reached a higher level than recently required, and are resistant to moisture and solder. Was not enough.

  Thus, in the field of electronic component-related materials, the present situation is that a thermosetting resin composition having both high flame retardance and moisture and solder resistance has not been obtained.

JP 2009-286944 A JP 2009-286949 A

  Therefore, the problem to be solved by the present invention is a thermosetting resin composition that realizes high humidity resistance and solder resistance required for recent electronic component-related materials and halogen-free and high flame resistance for environmental harmony. Another object of the present invention is to provide a cured product, a semiconductor sealing material using the thermosetting resin composition, and a phenolic resin and an epoxy resin that provide these performances.

  As a result of intensive studies in order to solve the above problems, the present inventors have introduced a naphthylmethyloxy group or an antonylmethyloxy group into an aromatic nucleus in a phenol resin or an epoxy resin, and a phenolic hydroxyl group (or, Glycidyloxy group) and naphthylmethyloxy group or antonylmethyloxy group are adjusted to a ratio of 10:90 to 99: 1 so that they have low viscosity, solder resistance and halogen-free and high flame resistance. As a result, the present invention has been completed.

  That is, the present invention is a thermosetting resin composition comprising an epoxy resin (A) and a phenolic resin (B) as essential components, wherein the phenolic resin (B) is a naphthylmethyloxy group or an antonylmethyl. It has an oxy group-containing aromatic hydrocarbon group (ph1), a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2), and an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X). And an aromatic hydrocarbon group selected from the group consisting of the naphthylmethyloxy group or anthonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2). A plurality of the phenolic resins having a structure bonded via the alkylidene group or the aromatic hydrocarbon structure-containing methylene group (X). The thermosetting resin composition according to symptoms (hereinafter, this thermosetting resin composition is abbreviated as "thermosetting resin composition (I)") it relates.

  Furthermore, this invention relates to the epoxy resin hardened | cured material characterized by making the said thermosetting resin composition (I) carry out hardening reaction.

  Furthermore, the present invention includes a naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2), and an alkylidene group or an aromatic hydrocarbon structure. It has each structural part of a methylene group (X), and the naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2 This relates to a phenol resin having in its molecular structure a structure in which a plurality of aromatic hydrocarbon groups selected from the group consisting of these groups are bonded via the alkylidene group or the aromatic hydrocarbon structure-containing methylene group (X).

  Furthermore, the present invention provides a thermosetting resin composition comprising an epoxy resin (A ′) and a curing agent (B ′) as essential components, wherein the epoxy resin (A ′) is a naphthylmethyloxy group or an antonyl. Each structural site has a methyloxy group-containing aromatic hydrocarbon group (ph1), a glycidyloxy group-containing aromatic hydrocarbon group (ep), and an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X). And an aromatic hydrocarbon group selected from the group consisting of the naphthylmethyloxy group or anthonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the glycidyloxy group-containing aromatic hydrocarbon (ep), A thermosetting resin composition, which is an epoxy resin having a structure bonded through the methylene group (X) containing the alkylidene group or aromatic hydrocarbon structure (Hereinafter, this thermosetting resin composition is abbreviated as "thermosetting resin composition (II)") it relates.

  Furthermore, in the present invention, in addition to the epoxy resin (A ′) and the curing agent (B ′) in the thermosetting resin composition (II), an inorganic filler is 70 to 95% by mass in the composition. It is related with the semiconductor sealing material characterized by containing by a ratio.

  Furthermore, the present invention relates to a cured product obtained by curing the thermosetting resin composition (II).

Furthermore, the present invention provides a naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), a glycidyloxy group-containing aromatic hydrocarbon group (ep),
And each structural site of an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X), and the naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and glycidyl Epoxy having a structure in which a plurality of aromatic hydrocarbon groups selected from the group consisting of oxy group-containing aromatic hydrocarbons (ep) are bonded via the alkylidene group or aromatic hydrocarbon structure-containing methylene group (X) It relates to resin.

  According to the present invention, the problems to be solved by the present invention are high moisture resistance and solder resistance required for recent electronic component-related materials, and thermosetting that realizes halogen-free and high flame resistance for environmental harmony. The resin composition, the cured product thereof, the semiconductor sealing material using the thermosetting resin composition, and the phenolic resin and epoxy resin that provide these performances can be provided.

1 is a GPC chart of the phenol resin (A-1) obtained in Example 1. FIG. FIG. 2 is a C ¹³ NMR chart of the phenol resin (A-1) obtained in Example 1. FIG. 3 is an MS spectrum of the phenol resin (A-1) obtained in Example 1. FIG. 4 is a GPC chart of the phenol resin (A-2) obtained in Example 2. FIG. 5 is a GPC chart of the epoxy resin (E-1) obtained in Example 3. 6 is a C ¹³ NMR chart of the epoxy resin (E-1) obtained in Example 3. FIG. FIG. 7 is an MS spectrum of the epoxy resin (E-1) obtained in Example 3. FIG. 8 is a GPC chart of the epoxy resin (E-2) obtained in Example 4.

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition (I) of the present invention is first a thermosetting resin composition containing an epoxy resin (A) and a phenolic resin (B) as essential components, and the phenolic resin (B). Is a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph), a naphthylmethyloxy group or an antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), and an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X And a group consisting of the naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2). A plurality of, preferably two, aromatic hydrocarbon groups selected from the above-mentioned alkylidene groups or aromatic hydrocarbon structure-containing methylene groups (X It is characterized in that a phenolic resin having a structure bonded through.

  That is, since the phenol resin (B) has the resin structure as a basic skeleton, the cured product has excellent heat resistance and flame retardancy. In the present invention, such a phenolic resin (B) is the novel phenolic resin of the present invention. Further, among the phenolic resins (B), they contain a naphthylmethyloxy group or an antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), and a phenolic hydroxyl group and a naphthylmethyloxy group or anthonyl. Those having a ratio of methyloxy groups (the former: latter) in the ratio of 10:90 to 99: 1 can enhance the aromatic nuclei of the resin itself and maintain the fluidity of the resin itself, thereby encapsulating the semiconductor. Affinity with inorganic fillers such as silica for material applications, improved osmosis in circuit board applications, low thermal expansion coefficient when cured, high adhesion, moisture and solder resistance and flame resistance Are preferable from the viewpoint that they are remarkably good. Among them, the ratio of 60:40 to 90:10 and 65:35 to 80:15 is excellent in the affinity of the filler such as silica and the impregnation property into the glass substrate, and the effect of the present invention. It is preferable because it is remarkable.

  The thermosetting resin composition (I) in the present invention has a low viscosity despite containing a bulky condensed polycyclic skeleton and a low functional group concentration. Excellent solderability. Having a property of low functional group concentration is very useful for recent advanced electronic materials because it has a low moisture absorption, a low dielectric constant, and a low dielectric loss tangent when it is made into a cured product. It is.

  Thus, the phenolic resin (B) in the thermosetting resin composition (I) comprises an aromatic skeleton (ph1) having a naphthylmethyloxy group or an antonylmethyloxy group, and a phenolic hydroxyl group-containing aromatic hydrocarbon group. (Ph2) in the resin structure, and a plurality of structural sites selected from these are alkylidene groups or aromatic hydrocarbon structure-containing methylene groups (X) (hereinafter referred to as “methylene nodule groups (X ) ", Which has a resin structure knotted by.

  Here, examples of the naphthylmethyloxy group or anthonylmethyloxy group-containing aromatic hydrocarbon group (ph1) include those represented by the following structural formulas P1 to P13.

ここで、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。また、１つの芳香族骨格にフェノール性水酸基とナフチルメチルオキシ基又はアントラニルメチルオキシ基の両方を含有していてもよい。

Here, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. May be. One aromatic skeleton may contain both a phenolic hydroxyl group and a naphthylmethyloxy group or an anthranylmethyloxy group.

  In the present invention, among these, those having a phenol skeleton represented by the structural formula Ph1-1 are preferable in terms of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance. In addition, those having a methyl group in the phenol skeleton as represented by the structural formula Ph1-4 are preferable because the effects of improving heat resistance and moisture and solder resistance are remarkable. Moreover, when a naphthylmethyloxy group or an antonylmethyloxy group containing aromatic hydrocarbon group (ph1) is located at the molecular end, those represented by the following structural formulas Ph1-14 to Ph1-22 can be mentioned.

ここで、上掲した構造のうちナフタレン骨格の場合、メチレンエーテル基と他の構造部位との結合は、同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, in the case of the naphthalene skeleton among the structures listed above, the bond between the methylene ether group and the other structural site may be on the same nucleus or on different nuclei.

  In the present invention, among these, those having a phenol skeleton represented by the structural formula Ph1-14 are preferable in terms of low viscosity and excellent curability, heat resistance, and moisture resistance and solder resistance. Further, those having a methyl group in the phenol skeleton as represented by the structural formulas Ph1-15, Ph1-20, and Ph1-22 are preferable because the effects of improving heat resistance and moisture and solder resistance are remarkable.

  On the other hand, the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) specifically includes those represented by the following structural formulas P22 to P38. Phenol, naphthol, and substituents on these aromatic nuclei. An aromatic hydrocarbon group formed from a compound having an alkyl group is preferable from the viewpoint of excellent heat resistance and moisture and solder resistance.

ここで、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. May be.

  In the present invention, among these, Ph2-1 is preferable in terms of excellent curability, and Ph2-4 is preferable in terms of moisture resistance and solder resistance.

  Next, the methylene group nodule group (X) contained in the resin structure of the phenol resin (B) includes, for example, an methylene group, an ethylidene group, a 1-propylidene group, a 2,2-propylidene group, dimethylene as an alkylidene group. Group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, n-pentane-1,1,5,5-tetrayl group, and the like. Examples of the group-containing hydrocarbon structure-containing methylene group include those represented by the following structural formulas X1 to X8.

Among these, a methylene group and a structure represented by the structural formulas X1, X2, and X5 are preferable from the viewpoint of excellent flame retardancy in the cured product of the phenol resin (B).

  The phenolic resin (B) used in the present invention is selected from the group consisting of naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2). The aromatic hydrocarbon group has a resin structure in which a plurality, preferably two, of the aromatic hydrocarbon groups are bonded via a methylene group nodule group (X), and these bond forms can take any combination. The molecular structure of the phenol resin composed of each of such constituent parts is as follows: the naphthylmethyloxy group or the anthonymethyloxy group-containing aromatic hydrocarbon group (ph1) is “Ph1”, and the phenolic hydroxyl group-containing aromatic hydrocarbon group. When (ph2) is represented by “Ph2” and the methylene nodule group (X) is represented by “X”, the structural moiety represented by the following partial structural formulas B1 and B2

を繰り返し単位とするランダム共重合体、若しくはブロック共重合体、Ｂ２を繰り返し単位とする重合体ブロックの分子鎖中にＢ１が存在する重合体、或いは、下記構造式Ｂ３〜Ｂ８

A random copolymer having a repeating unit or a block copolymer, a polymer having B1 in the molecular chain of a polymer block having B2 as a repeating unit, or the following structural formulas B3 to B8

で表される構造部位を分岐点として樹脂構造中に有する重合体、或いは、これら自体を繰り返し単位とする重合体であって、その樹脂構造の末端に下記構造式Ｂ９又はＢ１０

A polymer having a structural site represented by the following formula in the resin structure as a branch point, or a polymer having these as repeating units, and having the following structural formula B9 or B10 at the end of the resin structure:

で表される構造を有するものが挙げられる。

What has the structure represented by these is mentioned.

  In this invention, since it has such a characteristic chemical structure, the aromatic content rate in molecular structure becomes high, and it can provide the heat resistance and flame retardance which were excellent in hardened | cured material. In particular, it constitutes a naphthylmethyloxy group or anthonylmethyloxy group-containing aromatic hydrocarbon group (ph1) or a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) which is the basic skeleton of the phenolic resin (B) of the present invention. It is preferable that the aromatic nucleus to be formed is composed of a phenyl group or an alkyl-substituted phenyl group because the effect of improving moisture resistance and solder resistance is increased. By comprising a phenyl group or an alkyl-substituted phenyl group, toughness is brought to the cured product, and the condensed polycyclic skeleton arranged as a side chain develops low viscosity, thus improving adhesion with low thermal expansion. In addition to drastically improving moisture resistance and solder resistance, flame resistance can be improved.

  Furthermore, the structural site bonded through the methylene group nodule group (X) may contain an alkoxy group-containing aromatic hydrocarbon group, and examples thereof include those represented by the following structural formulas A1 to A13. It is done.

In the present invention, when the phenolic resin (B) contains an alkoxy group-containing aromatic hydrocarbon group in the resin structure, the alkoxy group-containing aromatic hydrocarbon group is represented by the structural formula A8. What has a structure is preferable from the point which is excellent in the heat resistance and flame retardance of hardened | cured material, and can reduce a dielectric loss tangent remarkably.

  The phenolic resin (B) has a melt viscosity in the range of 0.1 to 50 dPa · s at 150 degrees (Celsius) as measured with an ICI viscometer, particularly 0 at 150 degrees (Celsius). .1 to 20 dPa · s is preferable in terms of excellent fluidity during molding and moisture and solder resistance. Furthermore, the phenolic resin (B) has a hydroxyl equivalent of 120 to 400 g / eq. The thing of this range is preferable from the point from which the heat resistance and flame retardance of hardened | cured material become still better. The hydroxyl group equivalent is 150 to 250 g / eq. Within this range, the balance between the moisture resistance solder resistance and flame resistance of the cured product and the curability of the composition is particularly excellent.

  Further, the naphthylmethyloxy group or anthonylmethyloxy group is present in a ratio of 10:90 to 99: 1 of the phenolic hydroxyl group and the naphthylmethyloxy group or anthonylmethyloxy group. From the viewpoint of improving the effect of improving moisture resistance and solder resistance and flame retardancy, it is preferable that the ratio of the filler such as silica is 60:40 to 90:10, and further 65:35 to 80:15. It is preferable because it is excellent in affinity and impregnation into a glass substrate and the effect of the present invention is remarkable.

  The above-described phenolic resin (B) can be produced by the method described in detail below as the production method.

  That is, the method for producing the phenolic resin (B) is a method in which a novolak resin is reacted with a naphthyl methylating agent or an antonyl methylating agent (a2) (method 1), or a phenol compound (Ph1 ′) is converted to carbonyl. A method (Method 2) in which a novolak-type phenol resin is produced by reacting with the compound (X ′) and then reacted with a naphthyl methylating agent or an antonyl methylating agent (a2).

  In the novolak resin used in Method 1, the above-described phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) is bonded to the phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) via the methylene group nodule group (X). And those having the alkoxy group-containing aromatic hydrocarbon group via the methylene group nodule group (X). Among these, a phenol novolak resin, which has good reactivity with a naphthyl methylating agent or an antonyl methylating agent (a2), and can provide a phenolic resin excellent in moisture resistance, solder resistance and flame retardancy, Cresol novolak resins and naphthol novolak resins are preferred.

  Examples of the phenol compound (Ph1 ′) that can be used in Method 2 include unsubstituted phenol compounds such as phenol, resorcinol, hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, and t-butylphenol. Monosubstituted phenolic compounds such as, xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol and other disubstituted phenolic compounds, mesitol, 2,3,5-trimethylphenol, 2,3, Examples thereof include trisubstituted phenolic compounds such as 6-trimethylphenol, and phenolic compounds such as 1-naphthol, 2-naphthol, and methylnaphthol.

  Among these, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint that the cured product has flame retardancy, moisture and solder resistance, and the composition has excellent fluidity.

  The carbonyl compound (X ′) is specifically, and then the carbonyl group-containing compound (a3) is specifically an aliphatic aldehyde such as formaldehyde, acetaldehyde or propionaldehyde, or a dialdehyde such as glyoxal. , Benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldehyde, aromatic aldehydes such as naphthylaldehyde, and ketone compounds such as benzophenone, fluorenone, and indanone.

  Among these, formaldehyde, benzaldehyde, 4-biphenylaldehyde, and naphthylaldehyde are preferable because the cured product obtained has excellent flame retardancy.

  Here, the reaction between the phenol compound (Ph1 ′) and the carbonyl compound (X ′) is performed by using 0.01 to 1.0 mol of the carbonyl compound (X ′) as a catalyst with respect to 1 mol of the phenol compound (Ph1 ′). Obtained by heating in the presence. If it is more than this, the viscosity of the resin after reacting with the naphthylmethylating agent or the anthonymethylating agent will be high, and the moldability and impregnation will be hindered, and the effects of the present invention cannot be fully exhibited. The polymerization catalyst used here is not particularly limited, but is preferably an acid catalyst. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic substances such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. Examples thereof include Lewis acids such as acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by mass with respect to the total mass of the charged raw materials.

  In carrying out this reaction, an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials. Moreover, as reaction temperature, it is 40-250 degree | times (Celsius) normally, and the range of 100-200 degree | times (Centigrade) is more preferable. The reaction time is usually 1 to 20 hours.

  Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. What is necessary is just to perform a neutralization process and a water washing process according to a conventional method. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used. After neutralizing or washing with water, under reduced pressure heating, unreacted raw materials, organic solvents and by-products mainly containing phenolic compound (Ph1 ′) are distilled off to concentrate the product, and the target polyhydric hydroxy A compound can be obtained. The unreacted raw material recovered here can be reused. It is more preferable to introduce a microfiltration step into the processing operation after the reaction is completed because inorganic salts and foreign substances can be purified and removed.

  On the other hand, the naphthylmethylating agent or antonylmethylating agent (a2) used in Method 1 or Method 2 is 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, (9-anthrylmethyl) chloride, 1-methoxymethyl. Examples include naphthalene, 1-naphthylmethanol, 2-methoxymethylnaphthalene, 2-naphthylmethanol 9- (methoxymethyl) anthracene, and 9-anthracenemethanol.

  Reaction of novolak resin and naphthyl methylating agent or antonyl methylating agent (a2) in Method 1 or Aralkyl type phenol resin and naphthyl methylating agent or antonyl methylating agent (a2) in Method 2 It is necessary to use an alkali catalyst for the reaction. Examples of the alkali catalyst used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic alkalis with metal sodium, metal lithium, sodium carbonate, and potassium carbonate. The amount used is preferably in the range of 1.0 to 2.0 times the number of moles of the naphthyl methylating agent or anthony methylating agent (a2). The reaction temperature is 20 degrees Celsius to 150 degrees Celsius, preferably 40 degrees Celsius to 120 degrees Celsius.

  In carrying out this reaction, an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. However, when 1-naphthylmethyl chloride, 2-naphthylmethyl chloride, or (9-anthrylmethyl) chloride is used, it is preferable not to use an alcoholic organic solvent because side reactions occur. The amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials.

  Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water as necessary until the pH value of the reaction mixture becomes 5 to 9, preferably 6 to 8. What is necessary is just to perform a neutralization process and a water washing process according to a conventional method. As the neutralizing agent, an acidic substance such as acetic acid, phosphoric acid or sodium phosphate can be used as the neutralizing agent. After neutralization or washing with water, under reduced pressure heating, the unreacted naphthyl methylating agent, anthony methylating agent, organic solvent and by-products are distilled off to concentrate the product, and the phenol resin of the present invention is removed. Obtainable. In addition, it is more preferable to introduce a microfiltration step in the treatment operation after the end of the reaction because inorganic salts and foreign matters can be purified and removed.

  When the phenolic resin (B) is subsequently epoxidized, the neutralization or washing treatment may not be performed.

  In the thermosetting resin composition (I) of the present invention, the phenolic resin (B) may be used alone, but other epoxy resin curing agents (b) may be used as long as the effects of the present invention are not impaired. May be used. Specifically, the other curing agent can be used in combination in such a range that the phenolic resin (B) is 30% by mass or more, preferably 40% by mass or more with respect to the total mass of the curing agent.

  The other epoxy resin curing agent (b) that can be used in combination with the phenolic resin (B) of the present invention is not particularly limited, and examples thereof include amine compounds, amide compounds, acid anhydride compounds, Examples include phenolic compounds other than the above-described phenolic resin (B) and polyphenolic compounds of aminotriazine-modified phenolic resins (polyhydric phenolic compounds in which phenolic nuclei are linked with melamine, benzoguanamine, or the like).

  Here, as phenolic compounds other than the phenolic resin (B), phenol novolak resin, cresol novolak resin, phenol novolak resin, cresol novolak resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol A novolak resin such as a co-condensed novolac resin; a phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the novolak resin through a methylene group; A methoxy aromatic structure-containing phenol resin such as a phenol resin having a resin structure;

The following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるフェノールアラルキル樹脂、
下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Phenol aralkyl resin represented by
The following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるナフトールアラルキル樹脂、下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Naphthol aralkyl resin represented by the following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル変性フェノール樹脂、
下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl-modified phenolic resin represented by
The following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル変性ナフトール樹脂等のアラルキル型フェノール樹脂；
前記アラルキル型フェノール樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記アラルキル型フェノール樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂；
下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Aralkyl type phenolic resins such as biphenyl-modified naphthol resins represented by:
A phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group, and a phenol having a resin structure in which the methoxyphenyl skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group. resin;
The following structural formula

（式中、Ｘは、フェニル基、ビフェニル基を表し、ｎは繰り返し単位であり、０以上の整数である。）で表される芳香族メチレンを結節基とするノボラック樹脂；トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ジシクロペンタジエンフェノール付加型フェノール樹脂等が挙げられる。

(Wherein X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more). A novolak resin having a nodule group represented by an aromatic methylene represented by: trimethylolmethane resin; Tetraphenylol ethane resin, dicyclopentadiene phenol addition type phenol resin, etc. are mentioned.

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are particularly preferred from the viewpoint of the flame retardant effect. Specifically, phenol novolac resins, cresol novolak resins, novolak resins having aromatic methylene as a nodule, phenol Aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, methoxy aromatic structure-containing phenol resin, aminotriazine-modified phenol resin Is preferable because of its excellent flame retardancy.

  Next, examples of the epoxy resin (A) used in the thermosetting resin composition (I) of the present invention include diglycidyloxynaphthalene, 1,1-bis (2,7-diglycidyloxynaphthyl) methane, -(2,7-diglycidyloxynaphthyl) -1- (2'-glycidyloxynaphthyl) methane and other naphthalene type epoxy resins; bisphenol A type epoxy resins, bisphenol F type epoxy resins and other bisphenol type epoxy resins; Type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, biphenyl novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxide A novolac epoxy resin such as a resin; an epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the novolac epoxy resin through a methylene group; and a methoxyphenyl skeleton having a methylene group on the aromatic nucleus of the novolac epoxy resin. Epoxy resin having a resin structure bonded through the following structural formula B1

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるフェノールアラルキル型エポキシ樹脂、下記構造式Ｂ２

(In the formula, n is a repeating unit and is an integer of 0 or more.)
A phenol aralkyl type epoxy resin represented by the following structural formula B2

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるナフトールアラルキル型エポキシ樹脂、下記構造式Ｂ３

(In the formula, n is a repeating unit and is an integer of 0 or more.)
A naphthol aralkyl epoxy resin represented by the following structural formula B3

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル型エポキシ樹脂、下記構造式Ｂ４

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl type epoxy resin represented by the following structural formula B4

（式中、Ｘは、フェニル基、ビフェニル基を表し、ｎは繰り返し単位であり、０以上の整数である。）
で表される芳香族メチレンを結節基とするノボラック型エポキシ樹脂；前記アラルキル型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記アラルキル型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂；その他テトラメチルビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等が挙げられる。またこれらのエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。

(In the formula, X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more.)
A novolak-type epoxy resin having an aromatic methylene as a nodule group; an epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl-type epoxy resin via a methylene group; and the fragrance of the aralkyl-type epoxy resin Epoxy resin with a resin structure in which a methoxyphenyl skeleton is bonded to the nucleus via a methylene group; other tetramethylbiphenyl type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy Examples thereof include resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

Among these, naphthalene type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, alkoxy group-containing novolac type epoxy resins, and alkoxy group-containing aralkyl type epoxy resins have excellent flame retardancy and dielectric properties. It is particularly preferable from the viewpoint.

  As a compounding quantity of the epoxy resin (A) and the phenol-based resin (B) in the thermosetting resin composition (I) of the present invention, the epoxy resin (A) has a favorable cured product characteristic. The amount by which the active group in the curing agent containing the phenol resin (B) is 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups is preferable.

  Moreover, a hardening accelerator can also be used together suitably with the thermosetting resin composition (I) of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance and solder resistance, and so on, for phosphorus compounds, triphenylphosphine, and for tertiary amines, 1,8- Diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

Another thermosetting resin composition (II) of the present invention is a thermosetting resin composition containing an epoxy resin (A ′) and a curing agent (B ′) as essential components, the epoxy resin (A ′) Is a naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), a glycidyloxy group-containing aromatic hydrocarbon group (ep),
Each having a structural portion of an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X) (hereinafter abbreviated as “methylene group nodule group (X)”), and the naphthylmethyloxy Group or an aromatic hydrocarbon group selected from the group consisting of an antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and a glycidyloxy group-containing aromatic hydrocarbon (ep), It has the structure couple | bonded through this, It is characterized by the above-mentioned.

  That is, the epoxy resin (A ′) in the thermosetting resin composition (II) is obtained by epoxidizing the phenolic resin (B) constituting the thermosetting resin composition (I) with epihalohydrin. And having a basic skeleton in common with the phenolic resin (B). Therefore, as in the case of the phenolic resin (B), the aromatic nuclei of the resin itself can be enhanced, and the moisture resistance, solder resistance and flame retardancy are remarkably good. In the present invention, such an epoxy resin (A ′) is the novel epoxy resin of the present invention.

  In addition, the ratio of naphthylmethyloxy group or anthonylmethyloxy group is such that the ratio of glycidyloxy group to naphthylmethyloxy group or anthonylmethyloxy group (the former: latter) is 10:90 to 99: 1. In addition, the aromatic nucleus of the resin itself can be enhanced and the fluidity of the resin itself can be maintained, and the affinity for inorganic fillers such as silica is improved for semiconductor sealing materials, and the permeability is improved for circuit board applications. In addition, it is preferable because it has a low thermal expansion coefficient when cured and has excellent adhesion. Further, the ratio of 60:40 to 90:10 and 65:35 to 80:15 is excellent in the affinity of the filler such as silica and the impregnation property into the glass substrate, and the effect of the present invention is remarkable. This is preferable.

  Thus, the epoxy resin (A ′) in the thermosetting resin composition (II) is composed of the naphthylmethyloxy group or anthonymethyloxy group-containing aromatic hydrocarbon group (ph1) and the glycidyloxy group-containing aromatic carbonization. It has a hydrogen group (ep) in the resin structure, and has a resin structure in which a plurality of these structural sites are knotted by a methylene-based knot group (X).

Here, examples of the naphthylmethyloxy group or anthonymethyloxy group-containing aromatic hydrocarbon group (ph1) include those represented by the structural formulas P1 to P13.

  On the other hand, specific examples of the glycidyl group-containing aromatic skeleton (ep) include those represented by the following structural formulas Ep1-1 to Ep1-17, such as phenol, naphthol, and substitutions on these aromatic nuclei. An aromatic hydrocarbon group formed from a compound having an alkyl group as a group is preferable from the viewpoint of excellent heat resistance and moisture and solder resistance.

ここで、「Ｇｒ」は、グリシジルオキシ基を表し、また、上掲した構造のうちナフタレン骨格上に他の構造部位との結合位置を二つ以上有するものは、それらの結合位置は同一核上であってもよいし、或いは、それぞれ異核上にあってもよい。

Here, “Gr” represents a glycidyloxy group, and among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton have their bonding positions on the same nucleus. They may be on different nuclei.

  In the present invention, among these, Ep1-1 is preferable from the viewpoint of excellent curability, and Ep1-4 is preferable from the viewpoint of moisture resistance and solder resistance.

  Next, in the resin structure of the epoxy resin (A ′), the methylene group nodule group (X) is represented by X1 to X5 as in the phenolic resin (B) in the thermosetting resin composition (I). The thing of the structure represented is mentioned.

  The epoxy resin (A ′) used in the thermosetting resin composition (II) of the present invention is a naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and a glycidyloxy group-containing aromatic hydrocarbon. A plurality of aromatic hydrocarbon groups selected from the group consisting of groups (ep) have a resin structure bonded via a methylene group nodule group (X), and these bond forms are in any combination Can be taken. The molecular structure of the epoxy resin composed of each of such components is such that the naphthylmethyloxy group or anthonymethyloxy group-containing aromatic hydrocarbon group (ph1) is “Ph1”, and the glycidyloxy group-containing aromatic skeleton (ep ) Is represented by “Ep1” and the methylene group nodule group (X) is represented by “X”, the structural sites represented by the following partial structural formulas E1 and E2

を繰り返し単位とするランダム共重合体、若しくはブロック共重合体、Ｅ２を繰り返し単位とする重合体ブロックの分子鎖中にＥ１が存在する重合体、或いは、
下記構造式Ｅ３〜Ｅ８

A random copolymer having a repeating unit or a block copolymer, a polymer having E1 in the molecular chain of a polymer block having a repeating unit of E2, or
Following structural formulas E3-E8

で表される構造部位を分岐点として樹脂構造中に有する重合体、或いは、これら自体を繰り返し単位とする重合体であって、その樹脂構造の末端に下記構造式Ｅ９又はＥ１０

A polymer having a structural site represented by the following formula in the resin structure as a branch point, or a polymer having these as repeating units, and having the following structural formula E9 or E10 at the end of the resin structure

で表される構造を有するものが挙げられる。

What has the structure represented by these is mentioned.

  In this invention, since it has such a characteristic chemical structure, the aromatic content rate in molecular structure becomes high, and it can provide the heat resistance and flame retardance which were excellent in hardened | cured material. In particular, a naphthylmethyloxy group or anthonylmethyloxy group-containing aromatic hydrocarbon group (ph1) or a glycidyloxy group-containing aromatic hydrocarbon group (ep), which is the basic skeleton of the epoxy resin (A ′) of the present invention, is constituted. It is preferable that the aromatic nucleus to be composed of a phenyl group or an alkyl-substituted phenyl group has a large effect of improving moisture resistance and solder resistance. By comprising a phenyl group or an alkyl-substituted phenyl group, toughness is brought to the cured product, and the condensed polycyclic skeleton arranged as a side chain develops low viscosity, thus improving adhesion with low thermal expansion. In addition to drastically improving moisture resistance and solder resistance, flame resistance can be improved.

  Furthermore, the structural site bonded through the methylene group nodule group (X) may contain an alkoxy group-containing aromatic hydrocarbon group, and examples thereof include those represented by the following structural formulas A1 to A13. It is done.

  In the present invention, when the epoxy resin (A ′) contains an alkoxy group-containing aromatic hydrocarbon group in the resin structure, the alkoxy group-containing aromatic hydrocarbon group is represented by the structural formula A8. Those having a structure are excellent in the heat resistance and flame retardancy of the cured epoxy resin and can significantly reduce the dielectric loss tangent.

The epoxy resin (A ′) has an epoxy equivalent of 173 to 700 g / eq. The thing of this range is preferable from the point from which the heat resistance and flame retardance of hardened | cured material become still better.
Furthermore, the melt viscosity at 150 degrees (Celsius) measured with an ICI viscometer is in the range of 0.1 to 100 dPa · s, particularly 0.1 to 10 dPa · s. It is preferable in that it has excellent moisture resistance and solder resistance. Here, when it has the conditions of the said epoxy equivalent and melt viscosity, it becomes a novel epoxy resin of this invention. The epoxy equivalent is 180 to 500 g / eq, particularly 200 to 400 g / eq. Within this range, the balance between the moisture resistance solder resistance and flame resistance of the cured product and the curability of the composition is particularly excellent.

  The aforementioned epoxy resin (A ′) can be produced by the method described in detail below. That is, the manufacturing method of an epoxy resin (A ') manufactures the target epoxy resin by manufacturing the phenol-type resin (B) in a thermosetting resin composition (I), and making this react with an epihalohydrin. be able to. For example, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenolic resin (B), and 0.9 to 2.0 mol of basic catalyst is further added to 1 mol of phenolic hydroxyl group. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degree | times (Celsius), adding or adding gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. Under the present circumstances, the impurity induced | guided | derived by reaction with epichlorohydrin, water, an organic solvent, etc. may be contained, such as glycidol. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  In the thermosetting resin composition (II) of the present invention, the epoxy resin (A ′) can be used alone, but it is used in combination with other epoxy resins (a ′) as long as the effects of the present invention are not impaired. Can be used. When used in combination, the proportion of the epoxy resin (A ′) of the present invention in the entire epoxy resin is preferably 30% by mass or more, particularly preferably 40% by mass or more.

As the other epoxy resin (a ′) that can be used in combination with the epoxy resin (A ′) of the present invention, various epoxy resins can be used. For example, diglycidyloxynaphthalene,
1,1-bis (2,7-diglycidyloxynaphthyl) methane, 1- (2,7-diglycidyloxynaphthyl) -1- (2′-glycidyloxynaphthyl) methane and other naphthalene type epoxy resins; bisphenol A Type epoxy resin, bisphenol type epoxy resin such as bisphenol F type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol-phenol Novolac type epoxy resins such as co-condensed novolac type epoxy resin and naphthol-cresol co-condensed novolac type epoxy resin; methoxynaphthalene skeleton via methylene group in aromatic nucleus of the novolac type epoxy resin An epoxy resin having a resin structure bonded to each other, an epoxy resin having a resin structure in which a methoxyphenyl skeleton is bonded to an aromatic nucleus of the novolak epoxy resin through a methylene group;

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるフェノールアラルキル型エポキシ樹脂、
下記構造式Ｂ２

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Phenol aralkyl type epoxy resin represented by
Following structural formula B2

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるナフトールアラルキル型エポキシ樹脂、
下記構造式Ｂ３

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Naphthol aralkyl epoxy resin represented by
Structural formula B3

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル型エポキシ樹脂、
下記構造式Ｂ４

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl type epoxy resin represented by
Following structural formula B4

（式中、Ｘは、フェニル基、ビフェニル基を表し、ｎは繰り返し単位であり、０以上の整数である。）
で表される芳香族メチレンを結節基とするノボラック型エポキシ樹脂；前記アラルキル型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記アラルキル型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂；その他テトラメチルビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等が挙げられる。またこれらのエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。

(In the formula, X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more.)
A novolak-type epoxy resin having an aromatic methylene as a nodule group; an epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl-type epoxy resin via a methylene group; and the fragrance of the aralkyl-type epoxy resin Epoxy resin with a resin structure in which a methoxyphenyl skeleton is bonded to the nucleus via a methylene group; other tetramethylbiphenyl type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy Examples thereof include resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Among these, in particular, naphthalene type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, alkoxy group containing novolak type epoxy resin, alkoxy group containing aralkyl type epoxy resin are flame retardant and dielectric. This is particularly preferable from the viewpoint of excellent characteristics.

Next, as the curing agent (B ′) used in the thermosetting resin composition (II) of the present invention, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. Can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin A novolak resin such as a naphthol novolak resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, or the like; A phenol resin containing a methoxy aromatic structure such as a phenol resin having a methoxyphenyl skeleton bonded to the aromatic nucleus of the resin via a methylene group;

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるフェノールアラルキル樹脂、
下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Phenol aralkyl resin represented by
The following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるナフトールアラルキル樹脂、下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Naphthol aralkyl resin represented by the following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル変性フェノール樹脂、
下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl-modified phenolic resin represented by
The following structural formula

（式中、ｎは繰り返し単位であり、０以上の整数である。）
で表されるビフェニル変性ナフトール樹脂等のアラルキル型フェノール樹脂；
前記アラルキル型フェノール樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記アラルキル型フェノール樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂；下記構造式

(In the formula, n is a repeating unit and is an integer of 0 or more.)
Aralkyl type phenolic resins such as biphenyl-modified naphthol resins represented by:
A phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group, and a phenol having a resin structure in which the methoxyphenyl skeleton is bonded to an aromatic nucleus of the aralkyl type phenol resin via a methylene group. Resin; following structural formula

（式中、Ｘは、フェニル基、ビフェニル基を表し、ｎは繰り返し単位であり、０以上の整数である。）で表される芳香族メチレンを結節基とするノボラック樹脂；トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ジシクロペンタジエンフェノール付加型フェノール樹脂、アミノトリアジン変性フェノール樹脂（メラミンやベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。

(Wherein X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more). A novolak resin having a nodule group represented by an aromatic methylene represented by: trimethylolmethane resin; Examples thereof include polyphenol compounds such as tetraphenylolethane resin, dicyclopentadiene phenol addition type phenol resin, aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are particularly preferred from the viewpoint of the flame retardant effect. Specifically, phenol novolac resins, cresol novolak resins, novolak resins having aromatic methylene as a nodule, phenol Aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, methoxy aromatic structure-containing phenol resin, aminotriazine-modified phenol resin Is preferable because of its excellent flame retardancy.

  From the viewpoint of excellent fluidity, dihydroxyphenols such as resorcin, catechol and hydroquinone, bisphenols such as bisphenol F and bisphenol A, and dihydroxynaphthalenes such as 2,7-dihydroxynaphthalene and 1,6-dihydroxynaphthalene are used. It is preferable to use together.

  However, in the present invention, the phenolic resin (B) used in the thermosetting resin composition (I) described above is particularly preferable since the effect of improving the heat resistance and moisture resistance and solder resistance becomes remarkable. It is preferable. Further, the phenol resin may have the above Ph1-14, Ph1-15 as a naphthylmethyloxy group or anthonymethyloxy group-containing aromatic hydrocarbon group (ph1) having a naphthylmethyloxy group or an antonylmethyloxy group in an aromatic nucleus. Ph1-20, Ph1-22, and the Ph2-1 as a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2) having no naphthylmethyloxy group or antonylmethyloxy group in the aromatic nucleus, It is preferable that it is represented by Ph2-4 and is represented by X1, X2 or X5 as the methylene-based nodule group (X) from the viewpoint of excellent moisture resistance and solder resistance.

  The blending amount of the epoxy resin (A ′) and the curing agent (B ′) in the thermosetting resin composition (II) of the present invention is not particularly limited, but the properties of the resulting cured product are good. From the point which is, the quantity from which the active group in a hardening | curing agent becomes 0.7-1.5 equivalent is preferable with respect to a total of 1 equivalent of the epoxy group in the epoxy resin containing an epoxy resin.

  Moreover, a hardening accelerator can also be used together suitably with the thermosetting resin composition (II) of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance and solder resistance, and so on, for phosphorus compounds, triphenylphosphine, and for tertiary amines, 1,8- Diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

  In the thermosetting resin compositions (I) and (II) of the present invention described in detail above, the phenolic resin (B) in the thermosetting resin composition (I) or the thermosetting resin composition (II). Since the epoxy resin (A ′) has an excellent effect of imparting flame retardancy, the flame retardancy of the cured product is good even if a conventionally used flame retardant is not blended. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. A non-halogen flame retardant (C) may be added.

  The thermosetting resin compositions (I) and (II) containing the non-halogen flame retardant (C) are substantially free of halogen atoms. For example, 5000 ppm derived from epihalohydrin contained in an epoxy resin. Halogen atoms due to the following trace amounts of impurities may be included.

  Examples of the non-halogen flame retardant (C) include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. It is not limited at all, and it may be used alone, or a plurality of flame retardants of the same system may be used, or flame retardants of different systems may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa 10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected according to the type of the phosphorus-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, a curing agent, In 100 parts by mass of the thermosetting resin composition containing all of the non-halogen flame retardant and other fillers and additives, 0.1 to 2.0 mass when red phosphorus is used as the non-halogen flame retardant It is preferable to mix | blend in the range of 0.1 part, and when using an organophosphorus compound, it is preferable to mix | blend similarly in the range of 0.1-10.0 mass part, Especially the range of 0.5-6.0 mass part is preferable. It is preferable to mix with.

  Also, when using the phosphorus flame retardant, hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. are used in combination with the phosphorus flame retardant. Also good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) cocondensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde, (iii) ) A mixture of the co-condensate of (ii) above and a phenol resin such as a phenol formaldehyde condensate, (iv) The above (ii), (iii) modified with paulownia oil, isomerized linseed oil, etc. And the like.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 0.1-5 mass parts.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition in which all of the curing agent, non-halogen flame retardant and other fillers and additives are blended. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 0.5 to 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of organometallic salt-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the thermosetting resin composition containing all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives, it is blended in the range of 0.005 to 10 parts by mass. Is preferred.

  An inorganic filler can be blended with the thermosetting resin compositions (I) and (II) of the present invention as required. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. 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 filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by mass or more with respect to the total amount of the thermosetting resin compositions (I) and (II). Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier, can be added to the thermosetting resin composition (I) or (II) of the present invention as necessary.

  The thermosetting resin composition (I) or (II) of the present invention can be obtained by uniformly mixing the above-described components. Moreover, the thermosetting resin composition of this invention can be easily made into hardened | cured material by the method similar to the method known conventionally. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Examples of uses in which the thermosetting resin composition (I) or (II) of the present invention is used include semiconductor sealing materials, resin compositions used for laminated boards and electronic circuit boards, resin casting materials, adhesives, Examples thereof include interlayer insulating materials for build-up substrates, coating materials such as insulating paints, etc. Among them, they can be suitably used for semiconductor sealing materials.

  In order to produce the thermosetting resin composition (I) or (II) prepared for the semiconductor encapsulant, the above-mentioned components including the filler are used in an extruder, a kneader, a roll, etc. It is sufficient to obtain a melt-mixing type thermosetting resin composition by thoroughly mixing until it becomes uniform. At that time, silica is usually used as the filler, and the filler is preferably used in a range of 30 to 95% by mass per 100 parts by mass of the thermosetting resin composition. 70 parts by mass or more is particularly preferable in order to improve the property, moisture resistance and solder crack resistance, and decrease the linear expansion coefficient, and 80 parts by mass or more is more effective in order to significantly increase these effects. Can be increased. As semiconductor package molding, the composition is molded by casting or molding using a transfer molding machine, injection molding machine or the like, and further heated at 50 to 200 degrees (Celsius) for 2 to 10 hours. There is a method for obtaining a semiconductor device.

  In order to adjust the thermosetting resin composition (I) or (II) of the present invention to a composition for a printed circuit board, for example, a resin composition for a prepreg can be formed by varnishing using an organic solvent. preferable. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or less, such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 A prepreg that is a cured product can be obtained by heating at ˜170 degrees Celsius. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this thermosetting resin composition (I) or (II), the prepreg obtained as mentioned above is laminated | stacked by a conventional method, and copper foil is laminated | stacked suitably. Thus, a copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 degrees Celsius for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

  When the thermosetting resin composition (I) or (II) of the present invention is used as a resist ink, for example, a cationic polymerization catalyst is used as a curing agent for the thermosetting resin composition (II), and further a pigment. , Talc, and filler are added to obtain a resist ink composition, which is then applied to a printed circuit board by a screen printing method and then a resist ink cured product.

  When the thermosetting resin composition (I) or (II) of the present invention is used as a conductive paste, for example, fine conductive particles are dispersed in the thermosetting resin composition and used for an anisotropic conductive film. Examples thereof include a method of forming a composition, a paste resin composition for circuit connection that is liquid at room temperature, and a method of using an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for build-up substrates from the thermosetting resin composition (I) or (II) of the present invention, for example, a circuit is formed by using the curable resin composition appropriately blended with rubber, filler, etc. The coated wiring board is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. Moreover, the roughened surface is formed by heat-pressing the copper foil with resin obtained by semi-curing the resin composition on the copper foil on the wiring board on which the circuit is formed at 170 to 250 degrees Celsius. It is also possible to produce a build-up substrate by omitting the plating process.

  The method for obtaining the cured product of the present invention may be based on a general curing method for a thermosetting resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. However, the composition obtained by the above method may be heated in a temperature range of about 20 to 250 degrees (Celsius). As the molding method, a general method of a thermosetting resin composition is used, and in particular, conditions specific to the thermosetting resin composition (I) or (II) of the present invention are not necessary.

  Therefore, in the present invention, it is possible to obtain an epoxy resin material that is safe in an environment where high flame retardancy can be expressed without using a halogen-based flame retardant. In addition, its excellent dielectric characteristics can realize high-speed operation speed of high-frequency devices. In addition, the phenolic resin (B) or epoxy resin (A ′) can be easily and efficiently manufactured by the manufacturing method of the present invention, and molecular design according to the target level of performance described above is possible. It becomes.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. In addition, the melt viscosity in 150 degree | times (Celsius), GPC measurement, NMR, and MS spectrum were measured on condition of the following.
1) Melt viscosity at 150 ° C (according to ASTM D4287) 2) Softening point measurement method: JIS K7234
3) GPC:
・ Device: HLC-8220 GPC manufactured by Tosoh Corporation, Column: TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL manufactured by Tosoh Corporation
・ Solvent: Tetrahydrofuran ・ Flow rate: 1 ml / min
・ Detector: RI
4) NMR: NMR GSX270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 [Synthesis of phenol resin (A-1)]
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was purged with nitrogen gas, and 103.0 g of phenol novolac resin (softening point 70 degrees Celsius) (hydroxy group 1.00 equivalent) ), 65.3 g (0.37 mol) of 1-chloromethylnaphthalene and 200.0 g of methyl isobutyl ketone, and stirred at room temperature while blowing nitrogen. After raising the temperature to 60 degrees (Celsius), 33.5 g (0.41 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 1 hour. After completion of the addition, the temperature was raised, and the reaction was carried out at 70 degrees (Celsius) for 2 hours, at 95 degrees (Celsius) for 2 hours, and further for 5 hours while refluxing. After completion of the reaction, the temperature was set to 80 ° C., and the organic layer was repeatedly washed with 100 g of water four times, and then methyl isobutyl ketone was removed under heating and reduced pressure to obtain a phenol resin (A-1). The resulting phenol resin has a softening point of 90 degrees (Celsius) (B & R method), a melt viscosity (measurement method: ICI viscometer, measurement temperature: 150 degrees (Celsius)) of 3.0 dPa · s, and a hydroxyl group equivalent of 245 g. / Eq. Met.
The GPC chart of the obtained phenol resin is shown in FIG. 1, the C ¹³ NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. The presence of a methylnaphthyloxy group was confirmed by the above analysis. The ratio of phenolic hydroxyl group to naphthylmethyloxy group or antonylmethyloxy group was 63:37.

Example 2 [Synthesis of phenol resin (A-2)]
In Example 1, 103.0 g of phenol novolak resin (softening point 70 degrees (Celsius)) was added to 104.0 g of phenol novolak resin (softening point 80 degrees (Celsius)), 19.4 g (0.11 mol) of 1-chloromethylnaphthalene. ), A phenol resin (A-2) was obtained in the same manner except that 9.9 g (0.12 mol) of a 49% aqueous sodium hydroxide solution was used. The obtained phenol resin has a softening point of 89 degrees Celsius (B & R method), melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 degrees Celsius) is 4.4 dPa · s, and a hydroxyl group equivalent is 133 g. / Eq. Met.
The GPC chart of the obtained phenol resin is shown in FIG. The ratio of phenolic hydroxyl group to naphthylmethyloxy group or antonylmethyloxy group was 89:11.

Comparative Example 1 [Synthesis of phenol resin (A-3): phenol resin described in Patent Document 1]
To a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 520 parts (5.0 mol) of phenol novolac resin (Phenolite TD-2131 manufactured by DIC Corporation), 209 parts of benzyl chloride ( 1.65 mol), 1094 parts of methyl isobutyl ketone and 7 parts of tetraethylammonium chloride were charged and stirred at room temperature while blowing nitrogen. 149 parts (1.82 mol) of a 49% aqueous sodium hydroxide solution was added at 70 degrees (Celsius) over 1 hour. After completion of the addition, the mixture was further stirred at 100 degrees (Celsius) for 3 hours. After completion of the reaction, 10 parts of first sodium phosphate was added to neutralize, and the aqueous layer was discarded. Further, the organic layer was repeatedly washed with 300 parts of water three times, and then methyl isobutyl ketone was removed under reduced pressure by heating to obtain 626 parts of compound (A-5). The softening point of the obtained compound (A-3) is 66 degrees (Celsius) (B & R method), the melt viscosity (measurement method: ICI viscometer, measurement temperature: 150 degrees (Celsius)) is 0.7 dPa · s, The hydroxyl equivalent is 189 g / eq. Met.

Example 3 [Epoxidation of phenol resin (A-1) Epoxy resin (E-1)]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas while 245 g (1 equivalent of hydroxyl group) of the phenol resin (A-1) obtained in Example 1 and 463 g of epichlorohydrin (5. 0 mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 degrees (Celsius), the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 degrees (Celsius) for 2 hours, and then washing with water (150 g) was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 271 g of an epoxy resin (E-1). The resulting epoxy resin has a softening point of 76 degrees Celsius (B & R method), a melt viscosity (measurement method: ICI viscometer, measurement temperature: 150 degrees Celsius) is 2.3 dPa · s, and an epoxy equivalent is 335 g. / Eq. Met.

FIG. 5 shows a GPC chart of the obtained phenol resin, FIG. 6 shows a C ¹³ NMR chart, and FIG. 7 shows an MS spectrum. The presence of a methylnaphthyloxy group was confirmed by the above analysis. The ratio of glycidyloxy group to naphthylmethyloxy group or antonylmethyloxy group was 63:37.

Example 4 [Epoxidation of phenol resin (A-2) Epoxy resin (E-2)]
In Example 3, 170 g of epoxidized product (E-2) was obtained in the same manner except that 133 g of phenol resin (A-2) (1 equivalent of hydroxyl group) was used instead of phenol resin (A-1). The resulting epoxy resin had a softening point of 63 degrees (Celsius) (B & R method), a melt viscosity (measurement method: ICI viscometer, measurement temperature: 150 degrees (Celsius)) of 1.9 dPa · s, and an epoxy equivalent of 210 g. / Eq. Met. A GPC chart of the obtained epoxy resin is shown in FIG. The ratio of glycidyloxy group to naphthylmethyloxy group or antonylmethyloxy group was 89:11.

Comparative Example 2 [Synthesis of Epoxy Resin (E-3)]
In Example 3, epoxidation was performed in the same manner except that 189 g of phenol resin (A-5) (1 equivalent of hydroxyl group) was used instead of phenol resin (A-1). The resulting epoxy resin (E-3) has a softening point of 43 degrees (Celsius) (B & R method) and a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 degrees (Celsius)) of 0.5 dPa · s. The epoxy equivalent was 269 g / eq.

Synthesis Example 1 [Synthesis of Epoxy Resin (E-4)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 432.4 g (4.00 mol) of o-cresol and 158.2 g (1.00 mol) of 2-methoxynaphthalene 179.3 g of formaldehyde aqueous solution (formaldehyde 2.45 mol) was added, 9.0 g of oxalic acid was added, the temperature was raised to 100 degrees (Celsius), and the reaction was carried out at 100 degrees (Celsius) for 3 hours. Subsequently, 73.2 g (formaldehyde 1.00 mol) of 41 mass% formaldehyde aqueous solution was dripped over 1 hour, collecting water with a fractionating tube. After completion of the dropwise addition, the temperature was raised to 150 degrees (Celsius) in 1 hour, and further reacted at 150 degrees (Celsius) for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Subsequently, after washing with water until the washing water showed neutrality, unreacted o-cresol, 2-methoxynaphthalene and methyl isobutyl ketone were removed from the organic layer under heating and reduced pressure to obtain a phenol resin. The obtained phenol resin has a hydroxyl group equivalent of 164 g / eq. Met.

  Next, 164 g (1 equivalent of hydroxyl group) of the obtained phenol resin, 463 g of epichlorohydrin (5.0 mol), and n-butanol were applied to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer while purging with nitrogen gas. 139 g and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 degrees (Celsius), the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 degrees (Celsius) for 2 hours, and then washing with water (150 g) was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (E-4). The resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 degrees Celsius) of 0.8 dPa · s, and an epoxy equivalent of 250 g / eq. Met.

  Examples 5 to 13 and Comparative Examples 1 to 3

As the epoxy resin, the above (E-1) to (E-4) and “YX-4000H” (tetramethylbiphenol type epoxy resin, epoxy equivalent: 195 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku Co., Ltd. “NC-3000” (biphenyl novolac type epoxy resin, epoxy equivalent: 274 g / eq) manufactured by Nippon Kayaku Co., Ltd. “NC-2000L” (phenol aralkyl type epoxy resin, epoxy equivalent: 236 g / eq), DIC Corporation “N-655-EXP-S” (orthocresol novolac type epoxy resin, epoxy equivalent: 200 g / eq), (A-1) to (A-3) as phenol resins, and “TD-” manufactured by DIC Corporation 2131 "(phenol novolac resin, hydroxyl group equivalent: 104 g / eq), Mitsui Chemicals, Inc. “XLC-3L” (phenol aralkyl resin, hydroxyl equivalent: 172 g / eq), “MEH-7851SS” (biphenyl novolac resin, hydroxyl equivalent: 200 g / eq) manufactured by Meiwa Kasei Co., Ltd., triphenylphosphine ( TPP), as a flame retardant, magnesium hydroxide (“Echo Mug Z-10” manufactured by Air Water Co., Ltd.), aluminum hydroxide (“CL-303” manufactured by Sumitomo Chemical Co., Ltd.),
Spherical silica (“FB-560” manufactured by Electrochemical Co., Ltd.) as an inorganic filler, γ-glycidoxytriethoxyxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, carnauba wax ( "PEARL WAX No. 1-P" manufactured by Celerica Noda Co., Ltd.), blended with carbon black in the composition shown in Tables 1-2, and melted at 90 degrees Celsius for 5 minutes using two rolls The desired composition was prepared by kneading. The obtained composition was crushed with a transfer molding machine in a disk shape of φ50 mm × 3 (t) mm at a pressure of 70 kg / cm 2, a ram speed of 5 cm / sec, a temperature of 175 degrees (Celsius), and a time of 180 seconds. Or a rectangular shape having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was further cured at 180 degrees (Celsius) for 5 hours. The physical properties of the cured product are as follows. Using the cured product obtained by the transfer molding, a test piece is prepared by the following method, and the heat resistance, linear expansion coefficient, adhesion, moisture resistance, solder resistance, and flame resistance are determined by the following method. The measurement results are shown in Tables 1-2. In addition, as for the adhesiveness, when performing the transfer molding, a copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., thickness 35 μm, using the Shine surface of GTS-MP treated as the adhesive surface with the resin composition) on one side of the mold is used. Then, a test piece was prepared from what was formed into a rectangle having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm and further cured at 180 degrees (Celsius) for 5 hours.

<Curing property>
0.15 g of the thermosetting resin composition is placed on a cure plate (manufactured by Thermo Electric) heated to 175 degrees Celsius, and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.
<Heat resistance>
Glass transition temperature: Measured using a viscoelasticity measuring device (solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., double-currency lever method; frequency 1 Hz, temperature rising rate 3 degrees (Celsius) / min).
<Linear expansion coefficient>
The cured product was used as a test piece having a width of about 5 mm and a length of about 5 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: “SS-6100” manufactured by Seiko Instruments Inc.). (Measurement weight: 30 mN, heating rate: 2 times at 3 degrees (Celsius) / minute, measurement temperature range: -50 degrees (Celsius) to 250 degrees (Celsius)) 50 degrees (Celsius) in the second measurement The linear expansion coefficient was evaluated.
<Adhesion>
The cured product was used as a test piece having a width of 10 mm, and the peel strength was measured at a speed of 50 mm / min.
<Moisture resistance and solder resistance>
The φ50 mm × 3 (t) mm disk-shaped test piece was left in an atmosphere of 85 degrees (Celsius) / 85% RH for 168 hours to perform moisture absorption treatment, and then this was soldered at 260 degrees (Celsius). When immersed in a bath for 10 seconds, the occurrence of cracks was examined.
○: No cracking ×: Cracking <flame retardant>
Using a test piece for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm, a combustion test was performed using five test pieces having a thickness of 1.6 mm in accordance with the UL-94 test method.
* 1: Total burning time of 5 specimens (seconds)
* 2: Maximum burning time (seconds) in one flame contact

表中の略号は以下の通りである。
ＮＣ−２０００Ｌ：フェノールアラルキル型エポキシ樹脂（日本化薬株式会社製「ＮＣ−２０００Ｌ」、エポキシ当量：２３６ｇ／ｅｑ）
ＮＣ−３０００：ビフェニルノボラック型エポキシ樹脂（日本化薬株式会社製「ＮＣ−３０００」、エポキシ当量：２７４ｇ／ｅｑ）
ＹＸ−４０００Ｈ：テトラメチルビフェノール型エポキシ樹脂（ジャパンエポキシレジン株式会社製「ＹＸ−４０００Ｈ」、エポキシ当量：１９５ｇ／ｅｑ）
Ｎ−６５５−ＥＸＰ−Ｓ：クレゾールノボラック型エポキシ樹脂（「エピクロンＮ−６５５−ＥＸＰ−Ｓ」、エポキシ当量：２００ｇ／ｅｑ）
ＭＥＨ−７８５１ＳＳ：ビフェニルノボラック樹脂（明和化成株式会社製「ＭＥＨ−７８５１ＳＳ」、水酸基当量：２００ｇ／ｅｑ）
ＸＬＣ−３Ｌ：フェノールアラルキル樹脂（三井化学株式会社製「ＸＬＣ−３Ｌ」、水酸基当量１７２ｇ／ｅｑ）
ＴＤ−２１３１：フェノールノボラック型フェノール樹脂（ＤＩＣ(株)製「ＴＤ−２１３１」、水酸基当量：１０４ｇ／ｅｑ）
ＴＰＰ：トリフェニルホスフィン

Abbreviations in the table are as follows.
NC-2000L: phenol aralkyl type epoxy resin (“NC-2000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 236 g / eq)
NC-3000: biphenyl novolac type epoxy resin (“NC-3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 274 g / eq)
YX-4000H: Tetramethylbiphenol type epoxy resin ("YX-4000H" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 195 g / eq)
N-655-EXP-S: Cresol novolac type epoxy resin (“Epiclon N-655-EXP-S”, epoxy equivalent: 200 g / eq)
MEH-7851SS: Biphenyl novolak resin (“MEH-7851SS” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 200 g / eq)
XLC-3L: Phenol aralkyl resin (“XLC-3L” manufactured by Mitsui Chemicals, hydroxyl equivalent 172 g / eq)
TD-2131: phenol novolac type phenolic resin (“TD-2131” manufactured by DIC Corporation, hydroxyl group equivalent: 104 g / eq)
TPP: Triphenylphosphine

Claims (12)

A thermosetting resin composition comprising an epoxy resin (A) and a phenolic resin (B) as essential components, wherein the phenolic resin (B) is an aromatic carbon containing a naphthylmethyloxy group or an antonylmethyloxy group Each of the naphthylmethyl has a structural part of a hydrogen group (ph1), a phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2), and an alkylidene group or an aromatic hydrocarbon structure-containing methylene group (X). A plurality of aromatic hydrocarbon groups selected from the group consisting of an oxy group or an antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon (ph2) are the alkylidene group or Thermosetting resin characterized by being a phenolic resin having a structure bonded via an aromatic hydrocarbon structure-containing methylene group (X) Fat composition. The thermosetting resin composition according to claim 1, wherein the phenol resin (B) has a melt viscosity at 150 ° C. of 0.1 to 100 dPa · s as measured with an ICI viscometer. In addition to the epoxy resin (A) and the phenolic resin (B) according to claim 1 or 2, an inorganic filler is further contained at a ratio of 70 to 95% by mass in the composition. Stop material. A cured product obtained by curing reaction of the thermosetting resin composition according to claim 1. Naphthylmethyloxy or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), phenolic hydroxyl group-containing aromatic hydrocarbon group (ph2), alkylidene group or aromatic hydrocarbon structure-containing methylene group (X) Each having a structural site, and selected from the group consisting of the naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the phenolic hydroxyl group-containing aromatic hydrocarbon (ph2). A phenol resin having a structure in which a plurality of aromatic hydrocarbon groups are bonded via the alkylidene group or the aromatic hydrocarbon structure-containing methylene group (X). 6. The phenol resin according to claim 5, which has a melt viscosity of 0.1 to 100 dPa · s at 150 ° C. measured with an ICI viscometer. A thermosetting resin composition comprising an epoxy resin (A ′) and a curing agent (B ′) as essential components, wherein the epoxy resin (A ′) is an aromatic containing a naphthylmethyloxy group or an antonylmethyloxy group Each of the hydrocarbon group (ph1), the glycidyloxy group-containing aromatic hydrocarbon group (ep), and the alkylidene group or the aromatic hydrocarbon structure-containing methylene group (X), and the naphthyl An aromatic hydrocarbon group selected from the group consisting of a methyloxy group or an antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and a glycidyloxy group-containing aromatic hydrocarbon (ep) is the alkylidene group or aromatic group. A thermosetting resin composition, which is an epoxy resin having a structure bonded via a hydrocarbon structure-containing methylene group (X). The thermosetting resin composition according to claim 7, wherein the epoxy resin (A ′) has a melt viscosity of 0.1 to 100 dPa · s at 150 ° C. measured with an ICI viscometer. A semiconductor sealing material comprising an inorganic filler in a proportion of 70 to 95% by mass in the composition in addition to the epoxy resin and the curing agent according to claim 7 or 8. A cured product obtained by curing reaction of the thermosetting resin composition according to claim 7 or 8. Of naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1), glycidyloxy group-containing aromatic hydrocarbon group (ep), and alkylidene group or aromatic hydrocarbon structure-containing methylene group (X) Each structural site is selected and selected from the group consisting of the naphthylmethyloxy group or antonylmethyloxy group-containing aromatic hydrocarbon group (ph1) and the glycidyloxy group-containing aromatic hydrocarbon (ep). An epoxy resin having a structure in which an aromatic hydrocarbon group is bonded via the alkylidene group or the aromatic hydrocarbon structure-containing methylene group (X). The epoxy resin according to claim 11, wherein the epoxy resin has a melt viscosity at 150 ° C. of 0.1 to 100 dPa · s measured with an ICI viscometer.

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