JP2018138679A - Epoxy resin, curable resin composition, cured product thereof and semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin which is excellent in flowability and provides a cured product excellent in heat resistance or flame retardancy; a curable resin composition comprising the same; a cured product thereof; and a sealing material.SOLUTION: There is provided an epoxy resin composed of a mixture of a glycidyl ether (z1) of a monoaralkylated product having one aralkyl group on an aromatic ring of a phenol compound (b1), a glycidyl ether (z2) of a diaralkylated product having two aralkyl groups on an aromatic ring of a phenol compound (b2), a polyglycidyl ether (x3) of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent, where the content ratio of (z1) is in the range of 0.01 to 15% by area ratio in a GPC measurement and the content ratio of (x2) is in the range of 0.01 to 15% by area ratio in a GPC measurement.SELECTED DRAWING: Figure 3

Description

The present invention is excellent in flowability and excellent in heat resistance and flame retardancy in cured Rue epoxy resin, a curable resin composition containing this, a cured product thereof, and a semiconductor encapsulating material.

  Epoxy resins and phenolic hydroxyl group-containing resins are used in adhesives, molding materials, paints, and other materials, and the resulting cured products are excellent in heat resistance and moisture resistance. Widely used in electrical and electronic fields such as insulating materials for plates.

  Among these various applications, in the field of semiconductor encapsulation materials, technological innovations such as transition to surface mount packages such as BGA and CSP, compatibility with lead-free solder, and elimination of halogen-based flame retardants are being promoted. Specifically, there is a need for a resin material that can further improve heat resistance, reduce the elastic modulus during heat, and achieve high flame retardancy even without halogen. Further, since the semiconductor sealing material is used by filling the resin material with a filler such as silica, in order to increase the filling rate, the resin material needs to have low viscosity and excellent fluidity in addition to the above-mentioned performances. Furthermore, in recent years, signal speeds and frequencies have been increasing in various electronic devices, and low dielectric constant properties that can cope with this have become one of the required performances.

  As a resin material for meeting these various required properties, for example, a benzylated phenol novolak resin obtained by reacting phenol biphenyl aralkyl resin and benzyl chloride at 140 ° C. for 3 hours, and this and epichlorohydrin are reacted. There are known epoxy resins obtained (see, for example, Patent Documents 1 and 2).

JP 2003-64164 A JP 2004-323580 A

  The phenol novolac resin and the epoxy resin described in Patent Documents 1 and 2 are low in melt viscosity and excellent in fluidity as compared with conventional resin materials, but the heat resistance in the cured product is not sufficient, both performances It was not something that had a good balance and high level.

Accordingly, an object of the present invention is to provide, excellent fluidity, and heat resistance and flame retardancy even better Rue epoxy resin in the cured product, the curable resin composition containing the same, cured product thereof, And providing a sealing material.

As a result of intensive studies to solve the above problems, the present inventors have found that a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound and a xylylene compound with an aralkylating agent, aralkyl on the aromatic nucleus of the phenol compound. and mono aralkylation body having one group, and each of the polyglycidyl ale the phenolic hydroxyl group-containing resins composed of a mixture containing a certain percentage of two and a diaralkyl of the body an aralkyl group on the aromatic nucleus of the phenolic compound The obtained epoxy resin was found to be excellent in fluidity and excellent in heat resistance and flame retardancy in a cured product, and the present invention was completed.

That is, the present invention, two phenol compound (b1) glycidyl ether mono aralkylation having one aralkyl group on the aromatic nucleus of (z1), the aromatic nucleus on the aralkyl group of the phenolic compound (b2) A mixture of a glycidyl ether (z2) of a diaralkylated product and a polyglycidyl ether (x3) of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent. It is an epoxy resin, and the content ratio of the glycidyl ether (z1) of the monoaralkylated product is in a range of 0.01% to 15% as an area ratio in GPC measurement, and the glycidyl ether of the diaralkylated product ( The content ratio of z2) is a range in which the area ratio in GPC measurement is 0.01% to 15%. It is to provide an epoxy resin characterized by.

  The present invention further provides a curable resin composition containing the epoxy resin and a curing agent.

  The present invention further provides a cured product obtained by curing reaction of the curable resin composition.

  The present invention further provides a semiconductor sealing material containing an inorganic filler in addition to the curable resin composition.

According to the present invention, excellent fluidity, and excellent heat resistance and flame retardancy in cured Rue epoxy resin, a curable resin composition containing any of these, the cured product, and a semiconductor sealing A stop material can be provided.

2 is a GPC chart of a phenolic hydroxyl group-containing resin (1) obtained in Synthesis Example 1. 6 is a GPC chart of a phenolic hydroxyl group-containing resin (2) obtained in Synthesis Example 2. 1 is a GPC chart of an epoxy resin (1) obtained in Example 1 .

  Hereinafter, the present invention will be described in detail.

  The epoxy resin of the present invention comprises a monoaralkylated glycidyl ether (z1) having one aralkyl group on the aromatic nucleus of the phenol compound (b1) and two aralkyl groups on the aromatic nucleus of the phenol compound (b2). A mixture of a glycidyl ether (z2) of a diaralkylated product and a polyglycidyl ether (x3) of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent. It is an epoxy resin, and the content ratio of the glycidyl ether (z1) of the monoaralkylated product is in a range of 0.01% to 15% as an area ratio in GPC measurement, and the glycidyl ether of the diaralkylated product ( The range in which the content of z2) is 0.01% to 15% in terms of area ratio in GPC measurement Characterized in that there. Here, the phenol compounds (b1), (b2) and (b3) may be the same or different.

  That is, the epoxy resin of the present invention is mainly composed of a polyglycidyl ether of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent, and the phenol resin (b1) A monoaralkylated glycidyl ether (z1) (hereinafter abbreviated as “monoaralkylated (z1)”) having one aralkyl group on the aromatic nucleus, and an aralkyl group on the aromatic nucleus of the phenol compound (b2) The glycidyl ether (z2) (hereinafter abbreviated as “diaralkylated product (z2)”) of a diaralkylated product having two of each is contained in a predetermined amount. Here, the phenol compounds (b1), (b2) and (b3) may be the same or different.

  Since the monoaralkylated product (z1) contained as an essential component of the epoxy resin of the present invention has a molecular structure containing a high concentration of aromatic rings while being a relatively low molecular weight compound, the heat resistance of the cured product is improved. There is an effect of improving the fluidity of the epoxy resin without lowering. Furthermore, such a structure having a high concentration of aromatic rings also has an effect of increasing the flame retardancy of the cured product. The content of the monoaralkylated product (z1) in the epoxy resin of the present invention is in the range of 0.01% to 15% in terms of area ratio in GPC measurement. Fluidity decreases. On the other hand, if it exceeds 15%, the heat resistance of the cured product decreases. From the viewpoint of the balance between the fluidity and the heat resistance, it is preferably contained in the range of 1.0% to 10.0% by area ratio in GPC measurement, particularly in the range of 2.0% to 8.0%. It is preferable to contain.

  Further, the diaralkylated product (z2 is another essential component of the epoxy resin of the present invention (z2 is the same as the monoaralkylated product (z1)), and improves the fluidity of the epoxy resin without lowering the heat resistance of the cured product. Furthermore, since the molecular orientation is higher than that of a general novolac resin and the aromatic ring structure has a high concentration, in addition to the curing, the flame retardancy of the cured product is enhanced, The effect of reducing the elastic modulus during heating is also produced.The content of the diaralkylated product (z2) in the epoxy resin of the present invention is in the range of 0.01% to 15% in terms of area ratio in GPC measurement, If it is less than 0.01%, the fluidity of the epoxy resin is reduced, whereas if it exceeds 15%, the heat resistance of the cured product is reduced.From the viewpoint of this performance balance, the area ratio in GPC measurement In preferably contains in the range 1.0 to 5.0%, and preferably in the range in particular 1.0 to 3.0%.

The phenolic compounds (b1) and (b2), which are the raw materials for the epoxy resin of the present invention, have a phenolic hydroxyl group and have at least one in the case of (b1) on the aromatic nucleus, (b2 ) Has at least two hydrogen atoms as long as the monoaralkylated product (x1) and the diaralkylated product (x2) can be produced. Especially, since it is excellent in the reactivity and the said monoaralkylated body (x1) and the said diaralkylated body (x2) are easy to produce | generate, a C1-C4 alkyl group or alkoxy on the aromatic nucleus of phenol or phenol Phenol compound having one alkyl group or alkoxy group having 1 to 4 carbon atoms on the aromatic nucleus of phenol is preferable because it is a phenol compound having one group, and a cured product having more excellent heat resistance is obtained. It is more preferable that The phenolic compounds (b1) and (b2) may be the same or different, but are preferably the same from the viewpoint of production efficiency.

  In this case, the monoaralkylated product (z1) specifically has the following structural formula (4).

[In Formula (4), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. Each of Ar ³ is independently a phenyl group, a naphthyl group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups on the aromatic nucleus thereof. And G represents a glycidyl group. ]
It is a compound represented by these. In addition, the diaralkylated product (z2) is specifically represented by the following structural formula (5).

[In Formula (5), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. Each of Ar ³ is independently a phenyl group, a naphthyl group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups on the aromatic nucleus thereof. And G represents a glycidyl group. ]
It is a compound represented by these.

  Among the phenol compounds having one alkyl group or alkoxy group having 1 to 4 carbon atoms on the aromatic nucleus of the phenol, the monoaralkylated product (z1) and the diaralkylated product (z2) are excellent in reactivity. Is more preferable, and is more preferably a phenol compound having one alkyl group or alkoxy group having 1 to 4 carbon atoms in the ortho-position or para-position of the phenolic hydroxyl group, and further has higher heat resistance. Since a cured product is obtained, ortho-cresol or para-cresol is particularly preferable.

  As described above, the epoxy resin of the present invention contains, as a main component, polyglycidyl ether of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent. Contains various resin components. Specifically, it is a polyglycidyl ether of a phenol resin in which part or all of the aromatic nucleus of the phenol resin, which is a polycondensate of the phenol compound (b3) and the xylylene compound, is aralkylated, particularly a phenol compound ( Those having an aralkyl group on the aromatic nucleus of b3) are preferably obtained. Specifically, such a compound has the following structural formula (6).

[In Formula (6), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Ar ³ is each independently a phenylene group, a naphthylene group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups on the aromatic nucleus. Ar ⁴ is independently a phenylene group, a biphenylene group, a naphthylene group, or a structure having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups on these aromatic nuclei. G is a glycidyl group, p is independently 1 or 2, and q is an integer of 0-20. ]
The polyfunctional compound (W) which has a structure represented by these is mentioned.

  Here, the polycondensation reaction between the phenol compound (b3) and the xylylene compound and the reaction between the obtained polycondensate and the aralkylating agent are mainly performed at the ortho-position or para-position of the phenolic hydroxyl group. Progress as. Therefore, when the phenol compound (b3) is a phenol compound having one alkyl group or alkoxy group having 1 to 4 carbon atoms in the ortho position or para position of the phenolic hydroxyl group, the phenol compound (b3) and the xylylene compound Among the aromatic nuclei contained in the polycondensate, a compound in which two aromatic nuclei at the end of the molecular chain are aralkylated, that is, a precursor of the polyfunctional compound (W) represented by the structural formula (6) Phenol is produced in high yield.

  The polyfunctional compound (W) has a structure in which two aromatic nuclei at the end of the molecular chain are aralkylated, so that the increase in viscosity due to aralkylation can be suppressed to a low level. Combined with the heat resistance of the product, it also has excellent flame retardancy. In addition, since the compound having such a controlled structure has high molecular orientation and excellent reactivity, the thermal elastic modulus and dielectric constant of the cured product can be kept low.

  As described above, the phenol compounds (b1), (b2), and (b3) used in the present invention are excellent in reactivity and are phenols that are precursors of the monoaralkylated product (z1) and the diaralkylated product (z2). Since it is easy to produce | generate, it is more preferable that it is a phenol compound which has one C1-C4 alkyl group or alkoxy group in the ortho-position or para-position of phenolic hydroxyl group, or a hardened | cured material. Phenol, ortho-cresol, or para-cresol is particularly preferable because it is an epoxy resin that excels in heat resistance and flame retardancy. In addition to this, since the precursor phenol of the polyfunctional compound (W) represented by the structural formula (6) is easily generated, the phenol compound (b3) is phenol, ortho-cresol or para-cresol. Is particularly preferred.

  Further, among the polyfunctional compound (W), diglycidyl ether of a compound in which two aromatic rings of the dimer of the phenol compound (b3) are each aralkylated, specifically, in the structural formula (6) The bifunctional compound (w1) in which the value of n is 0 is excellent in the balance between the aromatic ring structure concentration and the functional group concentration in the molecular structure, so that the heat resistance and flame retardancy of the cured product is improved, and the heat It is preferable because the effect of reducing the elastic modulus and dielectric constant is high. Further, since the bifunctional compound (w1) is a relatively low molecular weight compound, the heat resistance of the cured product can be improved without increasing the viscosity of the resin. The content ratio of the bifunctional compound (w1) in the epoxy resin of the present invention is excellent in heat resistance and flame retardancy, and a cured product having low thermal elastic modulus and dielectric constant can be obtained. A range of 5 to 30% is preferable.

The content of the monoaralkylated product (z1), the diaralkylated product (z2), and the bifunctional compound (w1) in the epoxy resin of the present invention is calculated by GPC measurement under the following conditions. It is an abundance ratio of the peak area of each structure to the total peak area of the epoxy resin of the present invention.
<GPC measurement conditions>
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  The above-described epoxy resin of the present invention can be produced, for example, by the following method. That is, the phenol compound (b3) and the xylylene compound are reacted in the presence of a polymerization catalyst to obtain a polycondensation reaction product (step 1), and then the obtained polycondensation reaction product and the phenol compound (b1) (b2) And an aralkylating agent are reacted under conditions of an organic solvent and an acid catalyst to obtain a phenol resin (step 2), and this is reacted with an epihalohydrin in the presence of a basic catalyst (step 3). I can do it. Here, the phenol compounds (b1), (b2) and (b3) may be the same or different. Moreover, as the polycondensation reaction product, a commercially available product may be used as it is.

  First, the step 1 will be described. Specific examples of the xylylene compound to be reacted with the phenol compound (b3) in the process include di (chloromethyl) benzene, di (bromomethyl) benzene, di (chloromethyl) biphenyl, di (chloromethyl) naphthalene, di (chloromethyl). ) Biphenyl ether, di (methoxymethyl) benzene, di (methoxymethyl) biphenyl, di (methoxymethyl) biphenyl ether, di (methoxymethyl) naphthalene, etc. Among these, reactivity with phenolic compounds and obtained Di (chloromethyl) benzene, di (chloromethyl) biphenyl, di (methoxymethyl) benzene, and di (methoxymethyl) biphenyl are preferred because the cured product has an excellent balance of fluidity, heat resistance, and flame retardancy. The substitution position of the chloromethyl group and methoxymethyl group in these compounds may be any of ortho, meta and para, but generally preferred is the para or meta position, and di (chloromethyl) biphenyl or di (methoxy) is preferred. In the case of methyl) biphenyl, 4,4′-bis (chloromethyl) biphenyl and 4,4′-bis (methoxymethyl) biphenyl can be mentioned. A mixed system of meta and para positions may also be used. The reaction ratio between the phenol compound (b3) and the xylylene compound is usually in the range of 0.01 to 0.9 mol of the xylylene compound with respect to 1 mol of the phenol compound (b3). More preferably, since a dimer of the phenol compound (b3) is easily formed, the xylylene compound is in a range of 0.01 to 0.8 mol with respect to 1 mol of the phenol compound (b3), and 0.01 to A range of 0.7 mol is particularly preferred.

  The polymerization catalyst used in the reaction of Step 1 is not particularly limited, but an acid catalyst is preferable. For example, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic substances such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid are used. Examples include Lewis acids such as acids, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. At this time, it is preferable that the usage-amount of a polymerization catalyst is the range of 0.1-5 mass% with respect to the total mass of a reaction raw material. In the case of di (chloromethyl) biphenyl and di (chloromethylbenzene), the reaction proceeds due to the presence of a small amount of water without using an acid catalyst.

  Step 1 is usually performed at a temperature of 100 to 200 ° C. for 1 to 20 hours. Moreover, you may perform the said process 1 in an organic solvent as needed. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When using these organic solvents, it is preferable to use in the range of 10-500 mass% with respect to the total mass of a reaction raw material.

  In the step 1, various antioxidants and reducing agents may be used for the purpose of suppressing the coloration of the resulting polycondensation reaction product. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, salts thereof, and zinc.

  After completion of the reaction in Step 1, 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 in accordance with a conventional method. Specifically, when an acid catalyst is used as a polymerization catalyst, a basic substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline can be used as a neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or after making basic once, the pH value may be adjusted to 3 to 7 with oxalic acid or the like.

  After neutralization or washing with water, the target polycondensation reaction product is obtained by concentrating the product by distilling off unreacted raw materials, organic solvents and by-products under reduced pressure heating conditions. I can do it. At this time, since the phenol compound (b3) used as a raw material can be a raw material in the reaction with the aralkylating agent in the subsequent step (2), it is not necessary to remove all from the system as an unreacted product.

  The polycondensation reaction product obtained in step 1 is a preferred range in which the monoaralkylated product (z1), the diaralkylated product (z2), and the bifunctional product (w1) are contained in the resulting epoxy resin. Therefore, the softening point measured according to JIS K7234 is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower.

  Subsequent step 2 is a step of adding phenol compounds (b1) and (b2) to the obtained polycondensation reaction product as necessary, and reacting these mixture with the aralkylating agent. Examples of the aralkylating agent used here include phenylmethanol compounds, phenylmethyl halide compounds, naphthylmethanol compounds, naphthylmethyl halide compounds, and styrene compounds. Specifically, benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butyl Benzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substituted isomers, α-methylbenzyl chloride, α, α-dimethyl Benzyl chloride, benzyl methyl ether, o-methyl benzyl methyl ether, m-methyl benzyl methyl ether, p-methyl benzyl methyl ether, p-ethyl benzyl methyl ether and their nuclear substitution isomerism , Benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether and their nuclear substitution isomers, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methyl Benzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, ptert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol and their nuclear substituted isomers, α-methylbenzyl alcohol, α, α-dimethyl Examples include benzyl alcohol, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene and the like. These may be used alone or in combination of two or more.

  Among these, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, which is excellent in reactivity and easily forms a precursor phenol of the monoaralkylated product (z1) or the diaralkylated product (z2). Benzyl alcohol compounds such as p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, ptert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol or naphthylmethanol compounds are preferred, and benzyl alcohol compounds are preferred. Particularly preferred.

  In step 2, the phenolic compounds (b1) and (b2) to be reacted with the aralkylating agent may be the same or different, and the unreacted phenol in the polycondensation reaction product obtained in step 1 is newly added. You may react by adding. The reaction rate of the polycondensation reaction product obtained in Step 1 above, unreacted phenol in the polycondensation reaction product, phenol compounds (b1) (b2) and the aralkylating agent is as follows: unreacted phenol in the polycondensation reaction product Although it depends on the amount of the compound and the average number of nuclei of the polycondensate, the phenol compound part in the polycondensation reaction product of the phenol compound (b3) and the xylylene compound used in Step 1, the polycondensation reaction product It is preferable to use the aralkylating agent in a range of 0.55 to 0.80 mol with respect to a total of 1 mol of unreacted phenol and phenolic compounds (b1) and (b2).

  Examples of the acid catalyst used in Step 2 include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid etc. are mentioned. Among them, an organic acid is preferable because it has high catalytic ability and promotes generation of a precursor phenol of the monoaralkylated product (z1) or the diaralkylated product (z2). At this time, it is preferable that the usage-amount of a polymerization catalyst is the range of 0.1-5 mass% with respect to the total mass of a reaction raw material.

  The reaction in the step 2 is preferably performed under a high temperature condition of 100 to 200 ° C. in order to promote the formation of the precursor phenol of the monoaralkylated product (z1) or the diaralkylated product (z2), More preferably. The reaction time in step 2 varies depending on the production scale, but the longer the retention time at 100 ° C. or higher, preferably 130 ° C. or higher, the longer the monoaralkylated product (z1) or the diaralkylated product (z2). Precursor phenol is easily generated. Specifically, the holding time at 100 ° C. or higher, preferably 130 ° C. or higher, is preferably 4 hours or longer.

  By carrying out the reaction in the step 2 in an organic solvent, the production of the precursor phenol of the monoaralkylated product (z1) or the diaralkylated product (z2) can be promoted. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . The amount of these organic solvents used is preferably in the range of 10 to 500% by mass with respect to the total mass of the reaction raw materials because the reaction is effectively promoted.

  After completion of step 2, the reaction solution may be used as it is in step 3, or the reaction product may be neutralized or washed with water and then used in step 3. The method for neutralizing or washing the reaction product is the same as that described in Step 1 above. In the above-described production method, from the viewpoint of efficiency, the aralkylation of the phenol compounds (b1) and (b2) and the aralkylation of the polycondensation reaction product of the phenol compound (b3) and the xylylene compound are performed in the same manner. However, as a method of obtaining the target epoxy resin precursor phenol, a monoaralkylated product prepared separately on a resin obtained by aralkylation of a polycondensation reaction product of a phenol compound (b3) and a xylylene compound (Z1) and the precursor phenol of the diaralkylated product (z2) may be mixed and adjusted to the range specified in the present invention.

  Since the phenol resin obtained in step 2 can easily adjust the content ratios of the monoaralkylated product (z1) and the diaralkylated product (z2) in the obtained epoxy resin to the preferred ranges described above, In the area ratio in GPC measurement, the phenol compound which is the precursor of the monoaralkylated product (z1) is in the range of 0.01% to 15%, and the phenolic compound which is the precursor of the diaralkylated product (z2) is 0.00. It is preferable to contain in 01 to 15% of range.

  Furthermore, it becomes easy to adjust the content of the monoaralkylated product (z1), the diaralkylated product (z2), and the bifunctional product (w1) in the obtained epoxy resin to the above-described preferable ranges. From the range of 0.01% to 15% of the phenol compound that is the precursor of the monoaralkylated product (z1) in the area ratio in GPC measurement, the phenolic compound that is the precursor of the diaralkylated product (z2) It is preferable to contain the phenol compound which is a precursor of the said bifunctional body (w1) in the range of 0.01%-15% in the range of 5%-30%.

  In addition, the hydroxyl equivalent of the phenol resin obtained in step 2 is preferably in the range of 170 to 300 g / equivalent because it becomes easy to adjust the epoxy equivalent of the obtained epoxy resin to the range of steps described later. .

  In step 3, the reaction product obtained in step 2 is reacted with epihalohydrin to obtain the target epoxy resin.

  Specifically, in such step 3, epihalohydrin is added at a ratio of 2 to 10 times (molar basis) with respect to the number of moles of the phenolic hydroxyl group contained in the phenol resin obtained in step 2, The reaction is carried out at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 0.9 to 2.0 times (molar basis) of the basic catalyst to the number of moles of the phenolic hydroxyl group. A method 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 epihalohydrin are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be further separated to remove water, and the epihalohydrin is continuously returned to the reaction mixture.

  In addition, in the first batch of epoxy compound production, all of the epihalohydrins used for charging are new in industrial production, but the subsequent batches are consumed in 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. 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.

  Examples of the basic catalyst used in Step 3 include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides as in Step 1. In particular, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred from the viewpoint of excellent catalytic activity of the epoxidation reaction. 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.

  In addition, the reaction rate can be increased by performing step 3 in an organic solvent. The organic solvent used here is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, methanol, ethanol, 1-propyl alcohol, and isopropyl alcohol. Alcohol solvents such as 1-butanol, secondary butanol and tertiary butanol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, acetonitrile And aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  After completion of step 3, the reaction product is washed with water, and then unreacted epihalohydrin and the combined organic solvent are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy compound with less hydrolyzable halogen, unreacted epihalohydrin and the organic solvent used in combination are distilled off before the water washing step, and the resulting crude product is toluene, methyl isobutyl ketone, It can be redissolved in an organic solvent such as methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added for further reaction. 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 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the crude epoxy product used. After the completion of the post-reaction, the produced salt is removed by a method such as filtration or washing with water, and further, a target epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. it can. Step 3 is a method for efficiently obtaining the epoxy resin of the present invention. A polycondensation product obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent and converting it to glycidyl ether is used. Separately prepared glycidyl ether, monoaralkylated glycidyl ether (z1) having one aralkyl group on the aromatic nucleus of phenol compound (b1), two aralkyl groups on the aromatic nucleus of phenol compound (b2) It is also possible to prepare the epoxy resin of the present invention by mixing a predetermined amount of the glycalyl ether (z2) of the diaralkylated product.

  The epoxy resin thus obtained is excellent in curability, and has a high heat resistance and flame retardancy, and a cured product having a low thermal elastic modulus can be obtained. Therefore, the epoxy equivalent is 230 to 360 g / equivalent. A range is preferable.

  Moreover, the epoxy resin of the present invention is characterized by excellent fluidity, low thermal elastic modulus in the cured product, and excellent heat resistance and flame retardancy. Specifically, since it is excellent in fluidity and can be suitably used for semiconductor encapsulant applications, the softening point is preferably in the range of 40 to 130 ° C, and the melt viscosity at 150 ° C is 0. The range is preferably from 0.05 to 500 dPa · s.

The curable resin composition of the present invention, prior SL (abbreviated hereinafter "curable resin composition (2)" and.) Those containing an epoxy resin and a curing agent Ru der.

In the curable resin composition (2), examples of the curing agent for the epoxy resin include various known curing agents such as an amine compound, an amide compound, an acid anhydride compound, and a phenol compound. It is done. 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 Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensation Novolac resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group) , Aminotriazine-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novo Examples thereof include polyhydric phenol compounds such as rack resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

  The blending ratio of the epoxy resin and the curing agent is a resin composition excellent in curability, and since a cured product excellent in heat resistance, flame retardancy and thermal low elasticity is obtained, an epoxy group in the epoxy resin, It is preferable that the equivalent ratio (epoxy group / active hydrogen atom) to the active hydrogen atom in the curing agent is 1 / 0.5 to 1 / 1.5.

  Moreover, the said curable resin composition (2) may contain other epoxy resins other than the epoxy resin of this invention in addition to the epoxy resin of this invention, and the said hardening | curing agent.

  Other epoxy resins used here are specifically 2,7-diglycidyloxynaphthalene, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, α-naphthol / β-naphthol co-condensation type novolak. Polyglycidyl ether, naphthol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. Biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, etc .; phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolak type epoxy Di-resin, epoxidized product of condensate of phenolic compound and aromatic aldehyde having phenolic hydroxyl group, novolac type epoxy resin such as biphenyl novolac type epoxy resin; triphenylmethane type epoxy resin; tetraphenylethane type epoxy resin; Examples thereof include cyclopentadiene-phenol addition reaction type epoxy resin; phenol aralkyl type epoxy resin; and phosphorus atom-containing epoxy resin.

  Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxidized phenol resin obtained by reacting phenol, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, bisphenol A type epoxy resin and HCA and quinone An epoxy resin obtained by modification with a phenol resin obtained by reacting with a resin.

  When these other epoxy resins are used, the fluidity exhibited by the present invention is excellent, and since the thermal elastic modulus in the cured product is low, the effects of excellent heat resistance and flame retardancy are sufficiently exhibited. It is preferable to use the epoxy resin of the present invention in a range of 50% by mass or more in all the epoxy resin components.

  Moreover, when these other epoxy resins are used, the blending ratio of the curable resin composition (2) becomes a resin composition having excellent curability, and a cured product having excellent heat resistance, flame retardancy, and low thermal elasticity is obtained. Therefore, the equivalent ratio (epoxy group / active hydrogen atom) of epoxy groups in all epoxy components and active hydrogen atoms in the curing agent is a ratio of 1 / 0.5 to 1 / 1.5. It is preferable.

  The curable resin composition of this invention can also use together a hardening accelerator suitably 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 sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that 2-ethyl-4-methylimidazole is used for imidazole compounds, and triphenylphosphine is used for phosphorus compounds. For fins and tertiary amines, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, and an organic metal salt flame retardant. These may be used alone or in combination.

  The phosphorus flame retardant can be either inorganic or organic. Examples of the inorganic compound include phosphorous such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium acids and phosphoric acid amides.

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like, and the surface treatment method is, for example, (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, oxidation A method of coating with an inorganic compound such as bismuth, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenol resins; (Iii) Double coating with a thermosetting resin such as a phenol resin on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide. And the like.

  The organic phosphorus compounds 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-dihydro Examples thereof include cyclic organic phosphorus compounds such as oxynaphthyl) -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 depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the phenolic hydroxyl group-containing resin or In 100 parts by mass of curable resin composition containing all of epoxy resin, curing agent, and other additives and fillers, 0.1 to 2.0 mass when red phosphorus is used as a 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.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. 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, melam sulfate (Ii) co-condensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenol resin such as a phenol formaldehyde condensate, (iv) a mixture of (ii) and (iii) further modified with paulownia oil, isomerized linseed oil, etc. .

  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 curable resin composition, and the desired degree of flame retardancy. For example, the curable resin composition It is preferable to mix | blend in the range of 0.05-10 mass parts in 100 mass parts of things, and it is preferable to mix | blend especially 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 blending amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. It is preferable to mix | blend in the range of 0.05-20 mass parts in 100 mass parts of curable resin compositions which mix | blended all the containing resin or an epoxy resin, a hardening | curing agent, and other additives, fillers, etc. 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.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  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.

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

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

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the curable resin composition It is preferable to mix | blend in the range of 0.5-50 mass parts in 100 mass parts of things, and it is preferable to mix | blend especially in the range of 5-30 mass parts.

  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. And the like.

  The amount of the organic metal salt flame retardant is appropriately selected according to the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 to 10 parts by mass in 100 parts by mass of the curable resin composition.

  In addition, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be added to the curable resin composition of the present invention as necessary.

  An inorganic filler can be mix | blended with the curable resin composition of this invention as needed. Since the curable resin composition of the present invention has the characteristics of excellent fluidity, it is possible to increase the blending amount of the inorganic filler, and such a curable resin composition is particularly suitable for semiconductor sealing material applications. Can be used.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either a crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable resin composition, a spherical one is mainly used. It is preferable to use it. Furthermore, in order to 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 in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

  In addition, when using the curable resin composition of this invention for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  When adjusting the curable resin composition of this invention to the varnish for printed wiring boards, it is preferable to mix | blend an organic solvent. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The amount used can be appropriately selected depending on the application. For example, in printed wiring board applications, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, and the non-volatile content of 40 to 80% by mass. It is preferable to use in the ratio which becomes. On the other hand, in build-up adhesive film applications, as organic solvents, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, It is preferable to use carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the nonvolatile content is 30 to 60% by mass. It is preferable to use in proportions.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components . D epoxy resin, a curing agent, further curable resin composition comprising an additive such as a curing accelerator if necessary, can be easily cured by the same method known in the art. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  The curable resin composition of the present invention can be used for various electronic material applications because the cured product has excellent heat resistance and flame retardancy and has a low thermal elastic modulus and dielectric constant. Especially, it can use suitably for a semiconductor sealing material application taking advantage of the high fluidity.

The semiconductor encapsulation material, for example, d epoxy resin of the present invention, a curing agent, and a blend of such fillers, extruders, kneaders, adjusted by a method of mixing well until uniform using a roll or the like I can do it. Examples of the filler used here include the inorganic filler described above. As described above, the filler is preferably used in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition. Of these, flame retardancy, moisture resistance, and solder crack resistance are improved, and the linear expansion coefficient can be reduced. Therefore, it is preferably used in the range of 70 to 95 parts by mass, particularly in the range of 80 to 95 parts by mass. preferable.

  A method for molding a semiconductor package using the obtained semiconductor sealing material is, for example, molding the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, etc., and a temperature of 50 to 200 ° C. The method of heating for 2 to 10 hours under conditions is mentioned, By such a method, the semiconductor device which is a molding can be obtained.

  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, 1) softening point, 2) melt viscosity, 3) GPC, 4) 13C-NMR, and 5) MS were measured under the following conditions.

1) Softening point measurement method: JIS K7234

2) Melt viscosity measurement method: Measured with an ICI viscometer in accordance with ASTM D4287.

3) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Synthesis Example 1 Production of phenolic hydroxyl group-containing resin (1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 211 g (1) biphenylaralkyl resin tree HE-200C-10 manufactured by Air Water 0.0 equivalent), phenol 23.5 g (0.25 mol), benzyl alcohol 40.5 g (0.375 mol), p-toluenesulfonic acid 2.8 g, and xylene 235 g were charged, and the temperature was raised from room temperature to 140 ° C. with stirring. The temperature was raised to 150 ° C. for 4 hours at 140 ° C. and further reacted for 3 hours. After completion of the reaction, the temperature was lowered to 80 ° C., and neutralized by adding 1.2% of 49% sodium hydroxide, followed by drying under heating and reduced pressure to obtain 240 parts by mass of a phenolic hydroxyl group-containing resin (1). The resulting phenolic hydroxyl group-containing resin (1) has a softening point of 60 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.9 dPa · s, and a hydroxyl group equivalent of 236 g. / Equivalent. A GPC chart of the phenolic hydroxyl group-containing resin (1) is shown in FIG. The monoaralkylated product (x1) content in the phenolic hydroxyl group-containing resin (1) calculated from the GPC chart is 2.8%, the diaralkylated product (x2) content is 1.2%, and the bifunctional compound. The content rate of (y1) was 13.0%.

Synthesis Example 2 Production of phenolic hydroxyl group-containing resin (2) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 211 g (1) biphenylaralkyl resin tree HE-200C-10 manufactured by Air Water. 0.0 equivalent), 108 g (1.0 mol) of ο-cresol, 64.8 g (0.6 mol) of benzyl alcohol, 3.8 g of paratoluenesulfonic acid, and 319 g of xylene, and the temperature was raised from room temperature to 140 ° C. with stirring. The temperature was raised to 150 ° C. for 4 hours at 140 ° C. and further reacted for 3 hours. After completion of the reaction, the temperature was lowered to 80 ° C., and neutralized by adding 1.6 g of 49% sodium hydroxide, followed by drying under heating and reduced pressure to obtain 260 parts by mass of a phenolic hydroxyl group-containing resin ( 2 ). The resulting phenolic hydroxyl group-containing resin ( 2 ) has a softening point of 50 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.5 dPa · s, and a hydroxyl group equivalent of 233 g. / Equivalent. A GPC chart of the phenolic hydroxyl group-containing resin ( 2 ) is shown in FIG. The content of monoaralkylated product (x1) in phenolic hydroxyl group-containing resin (2) calculated from the GPC chart is 7.7%, the content of diaralkylated product (x2) is 1.7%, and bifunctional The content of (y1) was 10.6%.

Example 1 Production of Epoxy Resin (1) 233 g of phenolic hydroxyl group-containing resin ( 2 ) obtained in Synthesis Example 2 while purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge (1.0 equivalent of hydroxyl group) ), Epichlorohydrin (555 g, 6.0 mol) and n-butanol (167 g) were charged, and 2 g of tetraethylbenzylammonium chloride was charged and dissolved while stirring. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide 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. To the resulting crude epoxy resin, 590 g of methyl isobutyl ketone and 177 g of n-butanol were added and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. 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 microfiltration, the solvent was distilled off under reduced pressure to obtain 221 g of epoxy resin (1). The resulting epoxy resin (1) has a softening point of 46 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.8 dPa · s, and an epoxy equivalent of 328 g / equivalent. there were. A GPC chart of the epoxy resin (1) is shown in FIG. The content of the component corresponding to the monoaralkylated product (z1) in the epoxy resin (1) calculated from the GPC chart is 6.3%, and the content of the component corresponding to the diaralkylated product (z2) is 1 The content of the component corresponding to the bifunctional compound (w1) was 13.2%.

Comparative Production Example 1 Production of phenolic hydroxyl group-containing resin (1 ′) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 96.7 g (1.03 mol) of phenol, 4,4 '-Dichloromethylbiphenyl (103.3 g, 0.41 mol) and water (0.5 g) were charged and the temperature was raised. After the system became homogeneous and generation of HCl began, the temperature was maintained at 100 ° C for 3 hours, Heat treatment was applied at 150 ° C. for 1 hour. HCl generated in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 4,4′-bis (chloromethyl) biphenyl did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the reaction mixture was decompressed to remove unreacted phenol out of the system, and finally subjected to a decompression treatment at about 4000 Pa to 150 ° C., whereby residual phenol was not detected by gas chromatography. The obtained phenol biphenyl aralkyl resin had a hydroxyl group equivalent of 213 g / eq. Subsequently, while maintaining this phenol biphenyl aralkyl resin at 140 ° C., 34.0 g (0.27 mol) of benzyl chloride and 0.5 g of water were added dropwise over 1 hour, and the mixture was further maintained for 2 hours. HCl generated in the reaction was volatilized out of the system as it was and trapped with alkaline water. In this way, 186 g of the target phenol polymer was obtained. The hydroxyl group equivalent determined by the acetylation back titration method was 231 g / eq. The contents of monoaralkylated product (x1) and diaralkylated product (x2) in the phenolic hydroxyl group-containing resin ( 1 ′ ) calculated from the GPC chart were not detected.

Comparative Production Example 2 Production of Epoxy Resin (1 ′) Into a 2-liter four-necked flask equipped with a stirrer, thermometer, Dean-Stark trap and condenser, 231 g of phenol biphenyl aralkyl resin obtained in Comparative Production Example 1 and epichlorohydrin 555 g (6 mol) was added and dissolved. It was heated to 55 ° C., and 82 g (1 mol) of 49% NaOH aqueous solution was added dropwise over 4 hours under reduced pressure. At that time, the liquid distilled azeotropically was separated into water and epichlorohydrin with a Dean-Stark trap, and the reaction was carried out while returning only epichlorohydrin to the reaction system. After completion of the dropwise addition, the mixture was further stirred for 1 hour at that temperature, and then heated to 120 ° C. to recover unreacted epichlorohydrin by distillation. Next, 600 g of methyl isobutyl ketone and 200 g of water were added to the obtained crude resin solution, and inorganic salts were removed by washing with water. 1-Butanol 100g and 5% NaOH aqueous solution 100g were added to this solution, and it stirred at 85 degreeC for 3 hours. Thereafter, the mixture was allowed to stand for liquid separation, the lower layer was removed, and washing with water was repeated twice. Subsequently, azeotropic dehydration and filtration were performed, and then methylisobutylketone was removed to obtain 321 g of the desired epoxy resin (A). The epoxy equivalent of this resin was 311 g / eq, the melt viscosity was 1.2 dPa · s, and the hydrolyzable chlorine was 40 wtppm.

Examples 2 and 3 and Comparative Example 1
<Adjustment of curable resin composition (2A)>
Epoxy resin (1), epoxy resin (1 ′), phenol novolac type phenol resin (“TD-2131” hydroxyl equivalent of 104 g / eq manufactured by DIC Corporation), phenol aralkyl resin (“XLC-3L” hydroxyl group manufactured by Mitsui Chemicals, Inc.) Equivalent 172 g / eq), triphenylphosphine as a curing accelerator, fused silica, silane coupling agent, carnauba wax, and carbon black as an inorganic filler were blended in the composition shown in Table 1 below, and two rolls were used. The mixture was melt kneaded at 90 ° C. for 5 minutes to obtain a curable resin composition (2A).

In addition, the detail of each component used by adjustment of curable resin composition is as follows.
Fused silica: “FB-560” manufactured by Electrochemical Co., Ltd.
Silane coupling agent: γ-glycidoxytriethoxyxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)
Carnauba wax: “PEARL WAX No. 1-P” manufactured by Serra Rica Noda Co., Ltd.

<Creation of test piece (A)>
The pulverized curable resin composition (2A) was pulverized using a transfer molding machine under conditions of a pressure of 70 kg / cm ² , a ram speed of 5 cm / second, a temperature of 175 ° C., and a time of 180 seconds. The test piece (A) was obtained by molding into a rectangle having a length of 127 mm and a thickness of 1.6 mm.

<Evaluation of flame retardancy>
A combustion test based on the UL-94 test method was performed using five test pieces (A).
* 1: Total burning time of 5 specimens (seconds)
* 2: Maximum burning time (seconds) in one flame contact
The evaluation results are shown in Table 1 .

Examples 3 and 4 and Comparative Example 2
<Adjustment of curable resin composition (2B)>
Epoxy resin (1), epoxy resin (1 ′), phenol novolac type phenol resin (“TD-2131” manufactured by DIC Corporation, hydroxyl equivalent: 104 g / eq), phenol aralkyl resin (“XLC-3L” manufactured by Mitsui Chemicals, Inc.) A hydroxyl group equivalent of 172 g / eq) and triphenylphosphine as a curing accelerator were blended in the compositions shown in Table 4 below, and melt kneaded at 120 ° C. for 1 hour to obtain a curable resin composition (2B).

<Creation of test piece (B)>
A pulverized product of the resulting curable resin composition (2B) was transferred to a width of 12.7 mm under the conditions of a pressure of 50 kg / cm ² , a ram speed of 5 cm / second, a temperature of 150 ° C., and a time of 300 seconds. The test piece (B) was obtained by forming into a rectangle having a length of 127 mm and a thickness of 2.4 mm.

<Evaluation of heat resistance>
About a sample cut out to a size of 5 mm × 54 mm × 2.4 mm from the test piece (B), a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Rectangular Tension Method; frequency 1 Hz, heating rate) 3 ° C./min), and the temperature at which the change in the elastic modulus was maximized (the tan δ change rate was the largest) was measured as the glass transition temperature. The evaluation results are shown in Table 2 .

<Measurement of thermal elastic modulus>
For a sample cut out to a size of 5 mm × 54 mm × 2.4 mm from the test piece (B), a viscoelasticity measuring device (DMA: “Solid Viscoelasticity Measuring Device RSAII” manufactured by Rheometric, rectangular tension method; frequency 1 Hz, ascending The storage elastic modulus of the obtained chart was measured using a temperature rate of 3 ° C./min. The evaluation results are shown in Table 4.

<Evaluation of dielectric constant>
After the specimen (B) is stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after being completely dried by an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, in accordance with JIS-C-6481. The dielectric constant at 1 GHz of the test piece was measured. The evaluation results are shown in Table 4.

Claims (8)

A monoaralkylated glycidyl ether (z1) having one aralkyl group on the aromatic nucleus of the phenolic compound (b1), and a diaralkylated glycidyl ether having two aralkyl groups on the aromatic nucleus of the phenolic compound (b2) An epoxy resin comprising a mixture of (z2) and a polyglycidyl ether (x3) of a phenol resin obtained by reacting a polycondensation reaction product of a phenol compound (b3) and a xylylene compound with an aralkylating agent,
The content ratio of the glycidyl ether (z1) of the monoaralkylated product is in a range of 0.01% to 15% in terms of area ratio in GPC measurement, and the content of the glycidyl ether (z2) of the diaralkylated product is An epoxy resin having an area ratio in a GPC measurement of 0.01% to 15%. The monoaralkylated glycidyl ether (z1) is represented by the following structural formula (4):
[In Formula (4), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. Each of Ar ³ is independently a phenyl group, a naphthyl group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups on the aromatic nucleus thereof. And G represents a glycidyl group. ]
The glycidyl ether (z2) of the diaralkylated compound is represented by the following structural formula (5):
[In Formula (5), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. Each of Ar ³ is independently a phenyl group, a naphthyl group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups on the aromatic nucleus thereof. And G represents a glycidyl group. ]
In claim 1, wherein the epoxy resin is a compound represented. In a polyglycidyl ether (x3) of a phenol resin obtained by reacting a polycondensation reaction product of the phenol compound (a3) and a xylylene compound with an aralkylating agent, the following structural formula (6)
[In Formula (6), R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Ar ³ is each independently a phenylene group, a naphthylene group, or a structural site having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups on the aromatic nucleus. Ar ⁴ is independently a phenylene group, a biphenylene group, a naphthylene group, or a structure having one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups on these aromatic nuclei. G is a glycidyl group, p is independently 1 or 2, and q is an integer of 0-20. ]
The epoxy resin of Claim 2 containing the polyfunctional compound (W) represented by these. Content in the total epoxy resin of the formula bifunctional body the value of n is 0 in (6) (w1) is, according to claim 3, wherein a range of 5% to 30% by area ratio in GPC measurement Epoxy resin. The epoxy resin according to any one of claims 1 to 4 , wherein a softening point is in a range of 40 ° C to 130 ° C and a melt viscosity at 150 ° C is in a range of 0.05 to 500 dPa · s. A curable resin composition comprising the epoxy resin according to any one of claims 1 to 5 and a curing agent. Cured product characterized by comprising a curable resin composition according to claim 6 Symbol mounting by curing reaction. In addition to the curable resin composition according to claim 6 Symbol mounting, semiconductor sealing material, characterized in that it further comprises an inorganic filler.