JP2010235819A - Polyvalent hydroxy resin, epoxy resin, methods for producing them, epoxy resin composition, and cured material thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin which obtains a cured material excellent in flame retardancy, moisture resistance, low elasticity, or the like, is used for sealing an electronic components and is suitable for a circuit board material or the like, and to provide a polyvalent hydroxy resin and an epoxy resin composition. <P>SOLUTION: The styrene-modified polyvalent hydroxy resin is obtained by reacting 1 mole polyvalent hydroxy compound such as a phenol novolac resin with 0.1-4.0 moles styrenes in the presence of an acid catalyst and has 250-400 g/eq. hydroxyl equivalent. The epoxy resin is obtained by reacting the polyvalent hydroxy compound with epichlorohydrin and has 310-500 g/eq. epoxy equivalent. The epoxy resin composition contains the polyvalent hydroxy resin or the epoxy resin as an essential component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention provides an epoxy resin that is excellent in flame retardancy and also provides a cured product excellent in moisture resistance and low elasticity, a polyvalent hydroxy resin suitable as an intermediate thereof, a production method thereof, an epoxy resin composition used in these, and It relates to the cured product, and is suitably used for insulating materials in the electric and electronic fields such as semiconductor sealing materials and printed wiring boards.

  Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. The transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded. Similarly, for circuit board materials, in addition to improving low heat absorption, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance, it is desirable to develop materials with excellent low dielectric properties from the viewpoint of reducing dielectric loss. Yes. In order to meet these requirements, various new structures of epoxy resins and curing agents have been studied. Furthermore, recently, from the viewpoint of reducing environmental impact, there has been a movement to eliminate halogen-based flame retardants, and epoxy resins and curing agents with more excellent flame retardancy have been demanded.

  Therefore, various epoxy resins and epoxy resin curing agents have been studied from the above background. As an example of an epoxy resin curing agent, a naphthalene-based resin is known, and Patent Document 1 discloses an application of a naphthol aralkyl resin to a semiconductor sealing material. It is flame retardant, low moisture absorption, and low thermal expansion. It is described that it is excellent. Patent Document 2 proposes a curing agent having a biphenyl structure and describes that it is effective for improving flame retardancy. However, both naphthol aralkyl resins and biphenyl aralkyl resins have drawbacks that are inferior in curability, and there are cases where the effect of improving flame retardancy is not sufficient.

  On the other hand, an epoxy resin that satisfies these requirements is not yet known. For example, the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc. There is a problem in terms of moisture resistance. In addition, an o-cresol novolac type epoxy resin is known as an improved heat resistance, but the flame retardancy is insufficient.

  As a measure for improving flame retardancy without using a halogen flame retardant, a method of adding a phosphate ester flame retardant is disclosed. However, the method using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under a high temperature and humidity environment, and there is a problem that the reliability as an insulating material is lowered.

  Patent Documents 2 and 3 disclose an example in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as a material that improves flame retardancy without containing a phosphorus atom or a halogen atom. Patent Document 4 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used. However, these epoxy resins have insufficient performance in any of flame retardancy, moisture resistance or heat resistance. Patent Documents 7 and 8 disclose a naphthol-based aralkyl epoxy resin and a semiconductor sealing material containing the naphthol-based aralkyl epoxy resin, but nothing focuses on flame retardancy.

  On the other hand, as an example of an epoxy resin composition focused on improving moisture resistance and low stress properties, Patent Documents 5 and 6 disclose a monostyrenated phenol novolak resin and an epoxy resin composition using the epoxy resin. These do not focus on flame retardancy. In addition, since these use a monostyrenated phenol as a starting material, there is a problem that an extra step of producing a monostyrenated phenol as a raw material is included. Further, after the novolak reaction, it is necessary to remove the remaining high-boiling monostyrenated phenol monomer, and there is a problem that the resin is produced by a complicated process. Furthermore, when a novolak resin is used as a starting material from phenols that have been monostyrenated in advance, there is a problem in fluidity because the melt viscosity becomes high.

  Patent Document 7 discloses benzylated polyphenol and its epoxy resin, and describes that it is excellent in heat resistance, moisture resistance, crack resistance, etc., but it does not focus on flame retardancy. None of them focused on the relationship between functional group concentration and flame retardancy.

  Furthermore, Patent Document 8 discloses an epoxy resin curing agent containing an indene structure and describes that it is excellent in dielectric properties, heat resistance, etc., but was not focused on flame retardancy. Furthermore, since the indene structure with high rigidity is included, the heat resistance is excellent, but the performance is not sufficient in terms of adhesiveness.

JP 2005-344081 A JP-A-11-140166 JP 2000-129092 A JP 2004-57992 A JP-A-5-132544 Japanese Patent Laid-Open No. 5-140265 JP-A-8-120039 Japanese Patent Laid-Open No. 9-208673

  An object of the present invention is to provide a polyvalent hydroxy resin and an epoxy resin that have excellent performance in flame retardancy, moisture resistance, low elasticity, etc. in applications such as lamination, molding, casting, and adhesion. Providing an epoxy resin composition useful for sealing electrical and electronic parts, circuit board materials, etc., which has excellent flame retardancy, and gives a cured product excellent in moisture resistance, low elasticity, etc., and It is to provide the cured product.

  That is, the present invention is represented by the following general formula (1) and has a hydroxyl group equivalent of 250 to 400 g / eq. It is the polyhydric hydroxy resin characterized by being in the range.

（Ａは炭素数１〜８のアルキル基若しくは水酸基が置換してもよいベンゼン環又はナフタレン環からなる基を示し、Ｒ₁は下記式（ａ）で表される置換基を示し、Ｒ₂は水素原子又は炭素数１〜６の炭化水素基を示し、ｐ及びｑは０〜２の数を示すが、ｐ＋ｑは１以上である。Ｘは下記式（ｂ）又は式（ｃ）で表される架橋基であり、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は独立に、水素原子又は炭素数１〜６の炭化水素基を示し、ｎは１〜２０の数を示す。）

(A represents a group consisting of a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, R ₁ represents a substituent represented by the following formula (a), and R ₂ represents A hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and p and q represent a number of 0 to 2, but p + q is 1 or more, X is represented by the following formula (b) or formula (c). R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents a number of 1 to 20).

  The polyvalent hydroxy resin preferably has a melt viscosity at 150 ° C. in the range of 0.01 to 10.0 Pa · s.

（式中、Ａは炭素数１〜８のアルキル基若しくは水酸基が置換してもよいベンゼン環又はナフタレン環からなる基を示し、Ｘ及びｎは、一般式（１）と同じ意味を有する。） Moreover, this invention makes it react with 0.1-4.0 mol of styrene with presence of an acid catalyst with respect to 1 mol of hydroxy groups of the polyvalent hydroxy compound represented by following General formula (2). This is a method for producing a polyvalent hydroxy resin having a structure in which the substituent represented by the above formula (a) is substituted with a benzene ring or a naphthalene ring of a polyvalent hydroxy compound.

(In the formula, A represents an alkyl group having 1 to 8 carbon atoms or a group consisting of a benzene ring or a naphthalene ring which may be substituted by a hydroxyl group, and X and n have the same meaning as in the general formula (1).)

（Ａは炭素数１〜８のアルキル基若しくはグリシジルオキシ基が置換してもよいベンゼン環又はナフタレン環からなる基を示し、Ｇはグリシジル基を示す。Ｒ₁、ｐ、ｑ及びｎは一般式（１）と同じ意味を有する。）で表され、エポキシ当量が３１０〜５００ｇ／ｅｑ．の範囲であることを特徴とするエポキシ樹脂である。 Furthermore, the present invention provides the following general formula (3)

(A represents a group consisting of a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 8 carbon atoms or a glycidyloxy group, and G represents a glycidyl group. R ₁ , p, q and n represent general formulas. It has the same meaning as (1).) And has an epoxy equivalent of 310 to 500 g / eq. It is the epoxy resin characterized by being in the range.

  The epoxy resin preferably has a melt viscosity at 150 ° C. in the range of 0.01 to 10.0 Pa · s.

  Moreover, this invention is a manufacturing method of the epoxy resin characterized by making said polyhydric hydroxy resin and epichlorohydrin react.

  Furthermore, this invention is an epoxy resin composition which mix | blends one or both of said polyhydric hydroxy resin and said epoxy resin as an essential component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Moreover, this invention is an epoxy resin hardened | cured material formed by hardening | curing said epoxy resin composition.

  When applied to an epoxy resin composition, the epoxy resin and polyvalent hydroxy resin of the present invention give a cured product that is excellent in flame retardancy and also in moisture resistance and low elasticity, and seals electrical and electronic parts It can be suitably used for applications such as circuit board materials. In particular, the use of a flame retardant having excellent flame retardancy and environmental impact is made unnecessary or reduced.

¹ H-NMR spectrum of polyvalent hydroxy resin Infrared absorption spectrum of polyvalent hydroxy resin. GPC chart of polyvalent hydroxy resin FD-MS chart of polyvalent hydroxy resin ¹ H-NMR spectrum of epoxy resin Infrared absorption spectrum of epoxy resin. Epoxy resin GPC chart

  First, the polyvalent hydroxy resin (hereinafter abbreviated as PSN) of the present invention will be described. The PSN of the present invention is represented by the general formula (1), which is a polyvalent hydroxy compound represented by the general formula (2) (also referred to as a polyvalent hydroxy compound (2) when distinguished from PSN) and styrenes. Can be obtained by reacting.

  In the PSN of the present invention, first, the hydroxyl group equivalent can be arbitrarily adjusted by adding styrenes to the basic structure of the polyvalent hydroxy compound (2). Here, the addition of styrenes refers to the replacement of hydrogen on the benzene ring or naphthalene ring of the polyvalent hydroxy compound (2) with the substituent represented by the formula (a) (also referred to as a styryl group). In other words, in the epoxy resin cured product, the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to burn easily, but by increasing the hydroxyl equivalent, aliphatic carbon of the flammable component derived from the epoxy group The rate is low and a high degree of flame retardancy can be expressed. Moreover, by adding styrene rich in aromaticity, the aromaticity is further improved, and it is effective in improving moisture resistance in addition to flame retardancy.

  Therefore, a highly flame-retardant epoxy resin composition, especially an epoxy resin composition for semiconductor encapsulation is obtained using these. That is, in addition to high flame retardancy in these compositions, physical properties excellent in moisture resistance and low elasticity are expressed, and a highly reliable semiconductor device can be obtained using this material.

  Next, in the PSN of the present invention, the addition of styrenes increases the molecular weight, but can maintain a melt viscosity range suitable for a semiconductor encapsulant and the like. When this is used as a semiconductor sealing material, it is possible to increase the filling of silica or the like. As a result, various physical properties are improved, for example, improved flame retardancy, further lower water absorption and thermal expansion coefficient. A material having excellent reliability can be obtained due to reduction or the like.

  The PSN of the present invention can be obtained by addition reaction of the polyvalent hydroxy compound (2) represented by the general formula (2) and styrenes. At this time, the proportion of the polyvalent hydroxy compound (2) and the styrenes is represented by a phenol component (A in the general formula (2), considering the balance between flame retardancy and curability of the obtained cured product. The ratio of the styrenes used per mole is preferably in the range of 0.1 to 4.0 moles, more preferably in the range of 0.5 to 3.0 moles.

  In this reaction, styrenes are added to the aromatic ring having an OH group in the polyvalent hydroxy compound (2) to substitute the styryl group represented by the above formula (a). Further, the addition position of styrenes is mainly the vacant ortho and / or para position of the polyvalent hydroxy compound.

  Further, in the method for producing PSN of the present invention, if the proportion of styrene used is excessive with respect to the phenol component, the proportion of addition reaction of styrene increases and the molecular weight can be easily increased.

  The hydroxyl equivalent of the PSN of the present invention obtained in this way is 250 to 400 g / eq. More preferably, it is 270-350 g / eq. Range. If the hydroxyl equivalent is lower than this range, it is difficult to obtain a high level of flame retardancy, and if it is higher than this range, a high level of flame retardancy is obtained, but the curability is inferior and it tends to be difficult to use in the same application. .

  Moreover, general-purpose phenol resin, phenol aralkyl resin, naphthol aralkyl resin, etc. are mentioned as polyhydric hydroxy compound (2) used as the manufacturing raw material of PSN of this invention. In order to obtain higher flame retardancy, moisture resistance and adhesion, it is preferable to use a polyvalent hydroxy compound having an aralkyl structure. That is, in the general formula (2), a polyvalent hydroxy compound having a structure in which X is represented by the formula (c) is preferable.

  The PSN of the present invention preferably has a melt viscosity at 150 ° C. in the range of 0.01 to 10.0 Pa · s. From the viewpoint of workability, the melt viscosity is preferably as low as possible within the above range.

  Furthermore, the softening point may be 40 to 150 ° C, preferably 50 to 100 ° C. Here, the softening point refers to a softening point measured based on the ring and ball method of JIS-K-2207. When lower than this, when this is mix | blended with an epoxy resin, the heat resistance of hardened | cured material will fall, and when higher than this, the fluidity | liquidity at the time of shaping | molding will fall.

  In general formulas (1), (2) and (3), it is understood that common symbols have the same meaning except A. In these formulas, A independently represents a group comprising a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 8 carbon atoms or a hydroxyl group. However, in the general formula (3), A is different in that a hydroxyl group is not substituted and a glycidyloxy group is substituted. In the general formula (2), A is different in that it does not have a substituent represented by the formula (a). In general formula (3), G represents a glycidyl group. In the general formulas (1), (2) and (3), when A is substituted with an alkyl group, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. When the hydroxyl group is substituted, the number is preferably 1. That is, the total number of hydroxyl groups substituted by A is preferably 1 or 2. In the general formula (2), A has 1 or more, preferably 3 or more, hydrogens that can be substituted with the substituent represented by the formula (a).

R ₁ is a styrenyl group represented by the above formula (a). p and q represent a number of 0 to 2, but p + q is 1 or more. More preferably, p + q is 2 or more, and more preferably 2.6-4. It is preferred that an average of 0.2 to 2 styryl groups be substituted for one A, and 1.3 to 2 is particularly preferred. In the formula (a), R ₂ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen. This R ₂ is determined by the styrenes used as reaction raw materials. Here, q is an average value when n is a number other than 1. The average of p and q means the average value of all p and q.

X is a crosslinking group represented by the formula (b) or the formula (c), preferably a crosslinking group represented by the formula (c). R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Although n shows the number of 1-20, Preferably, it is the range of 1.5-3.0 as an average. Furthermore, it is preferable that the component in which n = 2 or more is 30% or more in the area percentage value of the gel permeation chromatography chart. In addition, when n is a different mixture, n is a number average.

  Next, the manufacturing method of PSN of this invention is demonstrated. As the polyvalent hydroxy compound (2) used in the method for producing PSN of the present invention, a general-purpose phenol resin can be mentioned. Specifically, there are those in which the linking group X in the general formula (2) is derived from aldehydes or ketones, for example, those represented by the general formula (5).

ここで、Ｒ₇は水素原子、炭素数１〜８の炭化水素基又は水酸基を示し、Ｒ₃及びＲ₄は独立に、水素原子又は炭素数１〜６の炭化水素基を示す。ｎは１〜２０の数を示す。

Here, R ₇ represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a hydroxyl group, and R ₃ and R ₄ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n shows the number of 1-20.

  Moreover, a phenol aralkyl resin is also mentioned similarly. Specifically, the linking group X in the general formula (2) is derived from xylylene glycols, xylylene glycol dimethyl ethers, xylylene dichlorides, divinylbenzenes, diisopropenylbenzenes, etc. It is represented by (6).

ここで、Ｒ₇は水素原子、炭素数１〜８の炭化水素基又は水酸基を示し、Ｒ₅及びＲ₆は独立に、水素原子又は炭素数１〜６の炭化水素基を示す。ｎは１〜２０の数を示す。

Here, R ₇ represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a hydroxyl group, and R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n shows the number of 1-20.

  Furthermore, a naphthol aralkyl resin is mentioned similarly. Specifically, A in the general formula (2) represents a naphthalene ring, and the linking group X is derived from xylylene glycols, xylylene glycol dimethyl ethers, xylylene dichlorides, etc., for example, the general formula (7) It is represented by

ここで、一般式（７）において、Ｒ₅、Ｒ₆、Ｒ₇及びｎは一般式（６）と同じ意味を有する。

Here, in the general formula (7), R ₅ , R ₆ , R ₇ and n have the same meaning as in the general formula (6).

  Examples of phenols or naphthols used to obtain these polyvalent hydroxy compounds (2) include phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, and tertiary butylphenol. , Allylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol 1,7-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, and the like. These phenols or naphthols may be used alone or in combination of two or more.

  Styrenes used in the reaction are styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms or a hydroxyl group. The styrenes may contain small amounts of other reaction components. When other reactive components include unsaturated bond-containing components such as α-methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene, the resulting polyvalent hydroxy resin has aromatic groups. A substituted compound on the ring will be included. The phenol resin obtained by the method for producing a polyvalent hydroxy resin of the present invention may contain a polyvalent hydroxy resin having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention can include an epoxy resin having such a substituent.

  In the method of the present invention in which styrenes are reacted with the polyvalent hydroxy compound (2), the amount of styrene used is preferably in the range of 0.1 to 4 mol with respect to 1 mol of the phenol component of the polyvalent hydroxy compound. More preferably, it is the range of 1.3-3 mol. And it is preferable that p and q in General formula (1) become the range of 1.3-3 on average. When the amount is less than this range, the properties of the starting polyvalent hydroxy compound are not improved. When the amount is more than this range, the functional group density tends to be too low and the curability tends to decrease. In the present invention, the hydroxyl group equivalent of PSN is 250 g / eq to 400 g / eq. It is possible to adjust to. As a result, the epoxy resin composition exhibits excellent physical properties such as flame retardancy, moisture resistance, and low elasticity, and gives a composition excellent in flame retardancy and reliability in applications such as semiconductor sealing materials. Therefore, the use ratio of styrenes is changed by the hydroxyl equivalent of the polyvalent hydroxy compound itself. That is, those having a small hydroxyl equivalent, such as phenol novolac resins, have a relatively large proportion of styrene, and those having a relatively small proportion of alkyl-substituted phenol novolacs, phenol aralkyl resins, naphthol aralkyl resins, etc. May be.

  This reaction can be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clays, silica-alumina, solid acids such as zeolite, and the like.

  Moreover, this reaction is normally performed at 10-250 degreeC for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the solvent.

  As a specific method for carrying out this reaction, all raw materials are charged in a lump and reacted at a predetermined temperature as it is, or a polyvalent hydroxy compound and a catalyst are charged and maintained at a predetermined temperature while maintaining styrenes. A method of reacting while dropping is generally used. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours. If a solvent is used after the reaction, the catalyst component can be removed if necessary, and then the solvent can be distilled off to obtain the resin of the present invention. If the solvent is not used, it can be discharged directly when heated. The object can be obtained.

Next, the epoxy resin of the present invention will be described.
The epoxy resin (abbreviated as PSNE) of the present invention is represented by the general formula (3). The polyvalent hydroxy resin (PSN) is represented by the general formula (1). PSNE can be obtained by epoxidizing PSN.

In the general formula (3), symbols and formulas common to the general formula (1) have the same meanings unless otherwise specified. G represents a glycidyl group, which is generated by the reaction of the hydroxyl group of the general formula (1). R ₁ is a substituent represented by the formula (a).

X is a bridging group represented by formula (b) or formula (c), but R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. . X crosslinks A, but the substitution position of X is not particularly limited.
The PSNE of the present invention is advantageously produced by reacting the PSN represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction.

  In addition to the reaction of reacting PSN with epichlorohydrin, PSN and allyl halide can be reacted to form an allyl ether compound and then reacted with peroxide. The reaction of reacting the PSN with epichlorohydrin can be performed in the same manner as a normal epoxidation reaction.

  For example, after the PSN is dissolved in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the temperature is 20 to 150 ° C., preferably 30 to 80 ° C. The method of making it react for time is mentioned. The amount of alkali metal hydroxide used in this case is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per mol of the PSN hydroxyl group. Epichlorohydrin is used in excess with respect to 1 mol of the hydroxyl group in PSN, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, with respect to 1 mol of the hydroxyl group in PSN. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the target epoxy is removed by distilling off the solvent. A resin can be obtained.

The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types.
1) The composition which mix | blended the said PSNE as a part or all of an epoxy resin.
2) The composition which mix | blended the said PSN as a part or all of a hardening | curing agent.
3) The composition which mix | blended said PSNE and PSN as part or all of an epoxy resin and a hardening | curing agent.

  In the case of the above compositions 2) and 3), the blending amount of PSN is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. If it is less than this, the effect of improving flame retardancy and moisture resistance is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

  When PSN is used as the total amount of the curing agent, the blending amount of PSN is usually blended in consideration of the equivalent balance of the OH group of PSN and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.

  A curing agent other than PSN can be used in combination as the curing agent. The blending amount of the other curing agent is determined so that the blending amount of PSN is normally 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. . When the blending amount of PSN is less than this, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small, and when it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

  As the curing agent other than PSN, all those generally known as curing agents for epoxy resins can be used, and examples thereof include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Among these, polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Below, the specific example of a hardening | curing agent is shown.

  Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.

  Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, Examples include polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, and bischloromethylnaphthalene.

Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and reethylenetetramine.
One or more of these curing agents can be mixed and used in the composition.

  The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, tetrabromobisphenol A, hydroquinone, resorcin, or tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resins such as phenol, cresol and naphthol, and aralkyl resins such as phenol, cresol and naphthol There are glycidyl etherified compounds of the active compound. These epoxy resins can be used alone or in combination of two or more.

  In the case of the compositions 1) and 3), another epoxy resin may be blended in addition to PSNE as an epoxy resin component in the epoxy resin composition. As the epoxy resin in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak and other trivalent or higher phenols, phenol-based aralkyl resins, biphenyl aralkyl resins, naphthol-based aralkyl resins Alternatively, there are glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more. And in the case of the composition which has PSNE of this invention as an essential component, the compounding quantity of PSNE is 5-100% in the whole epoxy resin, Preferably it is good to be the range of 60-100%.

  In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. You may mix | blend suitably. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

  In addition, the epoxy resin composition of the present invention can contain additives such as inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like. Examples of inorganic fillers include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a stopper is 70% by weight or more, and more preferably 80% by weight or more.

  Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.

Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenyl Tetraphenyl such as ruphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, tetrasubstituted phosphonium / tetrasubstituted borate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. There is boron salt. The addition amount is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. Flame retardants such as antimony, low stress agents such as silicone oil, lubricants such as calcium stearate, etc. can be used.

  The epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, and the like, and then the solvent is removed. It can be. Moreover, it can be set as a laminated body by apply | coating on sheet-like materials, such as copper foil, stainless steel foil, a polyimide film, and a polyester film depending on the case.

  If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, and this cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy, and the like. Become. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding or transfer molding. The temperature at this time is usually in the range of 120 to 220 ° C.

Hereinafter, the present invention will be described more specifically with reference to examples.
Here, the viscosity was measured using a B-type viscometer, and the softening point was measured by the ring and ball method according to JIS-K-2207. The gel permeation chromatography (GPC) measurement conditions were as follows: apparatus; MODEL 151 (manufactured by Waters), column; TSK-GEL 2000 × 3 and TSK-GEL 400 × 1 (both manufactured by Tosoh Corporation), Solvent; tetrahydrofuran; flow rate; 1 ml / min; temperature; 38 ° C; detector; RI; polystyrene standard solution was used for the calibration curve.

(Synthesis of polyvalent hydroxy resin)
Example 1
Into a 1 L 4-neck flask, phenol novolac (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C., GPC as a polyvalent hydroxy compound component 105 g of n = 1 component (38%) and n = 2 or more component (62%)) and 0.13 g of p-toluenesulfonic acid as an acid catalyst were charged and heated to 150 ° C. Next, with stirring at 150 ° C., 156 g (1.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Furthermore, after reacting at 150 ° C. for 1 hour, it was dissolved in 500 g of MIBK and washed 5 times at 80 ° C. Subsequently, after MIBK was distilled off under reduced pressure, 255 g of a polyvalent hydroxy resin was obtained. Its softening point is 75 ° C., melt viscosity at 150 ° C. is 0.16 Pa · s, and hydroxyl equivalent is 261 g / eq. The average of p and q was 1.5. This compound is referred to as PSN-A. FIG. 1 shows the ¹ H-NMR spectrum of PSN-A, FIG. 2 shows the infrared absorption spectrum, FIG. 3 shows the GPC chart, and FIG. 4 shows the FD-MS chart.

Example 2
As a polyvalent hydroxy compound component, 100 g of bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) manufactured by Honshu Chemical Co., Ltd. as an acid catalyst 0.13 g of p-toluenesulfonic acid was charged and heated to 150 ° C. Next, with stirring at 150 ° C., 156 g (1.5 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 251 g of a polyvalent hydroxy resin was obtained. The softening point is 50 ° C., the melt viscosity at 150 ° C. is 0.020 Pa · s, and the hydroxyl equivalent is 256 g / eq. The average of p and q was 1.5. This compound is referred to as PSN-B.

Example 3
As a polyvalent hydroxy compound component, 175 g of phenol aralkyl resin (Maywa Kasei Co., Ltd .; MEH-7800SS, hydroxyl equivalent 175 g / eq., Softening point 66 ° C., melt viscosity 0.050 Pa · s at 150 ° C.), acid catalyst P-toluenesulfonic acid 0.16g was prepared and heated to 150 ° C. Next, while stirring at 150 ° C., 135 g (1.3 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Then, after processing similar to Example 1, 305 g of polyvalent hydroxy resin was obtained. Its softening point is 82 ° C., melt viscosity at 150 ° C. is 0.45 Pa · s, and hydroxyl equivalent is 310 g / eq. The average of p and q was 1.3. This compound is referred to as PSN-C.

Example 4
As a polyvalent hydroxy compound component, 210 g of 1-naphthol aralkyl resin (manufactured by Toto Kasei Co., Ltd .; SN-475, hydroxyl group equivalent 210 g / eq., Softening point 77 ° C., melt viscosity 0.050 Pa · s at 150 ° C.), As an acid catalyst, 0.17 g of p-toluenesulfonic acid was charged and heated to 150 ° C. Next, while stirring at 150 ° C., 135 g (1.3 mol) of styrene as styrenes was dropped over 3 hours to be reacted. Then, after processing similar to Example 1, 340 g of polyvalent hydroxy resin was obtained. Its softening point is 88 ° C., melt viscosity at 150 ° C. is 0.41 Pa · s, and hydroxyl equivalent is 345 g / eq. The average of p and q was 1.3. This compound is referred to as PSN-D.

Here, the average of p and q means the average number of R ₁ substituted with one A because p and q are substantially equivalent. Note that almost all of the styrene used in the reaction reacts.

Synthesis example 1
105 g of phenol novolak (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C.) as the polyvalent hydroxy compound component, p as the acid catalyst -Toluenesulfonic acid 0.10g was prepared and it heated up at 150 degreeC. Next, while stirring at 150 ° C., 73 g (0.7 mol) of styrene as styrenes was dropped over 2 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 172 g of a polyvalent hydroxy resin was obtained. Its softening point is 72 ° C., melt viscosity at 150 ° C. is 0.11 Pa · s, and hydroxyl equivalent is 178 g / eq. The average of p and q was 0.7.

Synthesis example 2
200 g of bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) manufactured by Honshu Chemical Co., Ltd. as a polyvalent hydroxy compound component was charged at 175 ° C. The temperature was raised to. After melting, 0.13 g of p-toluenesulfonic acid was charged with stirring, and 116 g (1.0 mol) of indene was added dropwise at 150 ° C. over about 3 hours. Then, after processing similar to Example 1, 413 g of polyvalent hydroxy resin was obtained. Its softening point is 78 ° C., melt viscosity at 150 ° C. is 0.06 Pa · s, and hydroxyl equivalent is 216 g / eq. The average of p and q was 1.0.

(Synthesis of epoxy resin)
Example 5
In a four-necked separable flask, 150 g of PSN-A obtained in Example 1, 306 g of epichlorohydrin and 46 g of diethylene glycol dimethyl ether were stirred and dissolved. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 47.9 g of 48% aqueous sodium hydroxide solution was dropped over 4 hours, and water and epichlorohydrin distilled under reflux were separated in the dropping tank in a separation tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 172 g of an epoxy resin (PSNE-A). The epoxy equivalent of the obtained resin was 329 g / eq. The softening point was 62 ° C. and the melt viscosity at 150 ° C. was 0.18 Pa · s. ¹ H-NMR spectrum of PSNE-A 5, shows an infrared absorption spectrum in Figure 7 to Figure 6, GPC chart.

Example 6
Using 150 g of PSN-B obtained in Example 2, the reaction was carried out in the same manner as in Example 5 to obtain 171 g of an epoxy resin (PSNE-B). The epoxy equivalent of the obtained resin was 322 g / eq. The melt viscosity at 150 ° C. was 0.03 Pa · s.

Example 7
Using 150 g of PSN-C obtained in Example 3, the reaction was carried out in the same manner as in Example 5 to obtain 165 g of epoxy resin (PSNE-C). The epoxy equivalent of the obtained resin was 378 g / eq. The softening point was 71 ° C. and the melt viscosity at 150 ° C. was 0.57 Pa · s.

Example 8
Using 150 g of PSN-D obtained in Example 4, the reaction was carried out in the same manner as in Example 5 to obtain 162 g of an epoxy resin (PSNE-E). The epoxy equivalent of the obtained resin was 411 g / eq. The softening point was 84 ° C. and the melt viscosity at 150 ° C. was 0.62 Pa · s.

Synthesis example 3
The resin obtained in Synthesis Example 1 was reacted in the same manner as in Example 5 to obtain 171 g of an epoxy resin. The epoxy equivalent of the obtained resin was 246 g / eq. The softening point was 57 ° C. and the melt viscosity at 150 ° C. was 0.14 Pa · s.

Synthesis example 4
The resin obtained in Synthesis Example 2 was used in the same manner as in Example 5 to obtain 169 g of epoxy resin. The epoxy equivalent of the obtained resin was 278 g / eq. The softening point was 58 ° C. and the melt viscosity at 150 ° C. was 0.05 Pa · s.

Examples 9-13 and Comparative Examples 1-4
An o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) was used as an epoxy resin component, and PSN-A and PSN-B obtained in Examples 1, 2, 3, and 4 were used as curing agents. In addition to the resins obtained in PSN-C, PSN-D and Synthesis Examples 1 and 2, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 82 ° C.) or phenol aralkyl resin ( Curing agent B: Meiwa Kasei Co., Ltd., MEH-7800SS, OH equivalent 175, softening point 67 ° C.) was used. Silica (average particle diameter of 18 μm) as a filler and triphenylphosphine as a curing accelerator were kneaded with the formulations shown in Tables 1 and 3 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements.

  The glass transition point (Tg) and linear expansion coefficient (CTE) were measured at a rate of temperature increase of 10 ° C./min using a thermomechanical measurement device. The water absorption rate was defined as the rate of change in weight after absorbing moisture for 100 hours at 85 ° C. and 85% RH using a circular test piece having a diameter of 50 mm and a thickness of 3 mm. The adhesive strength was obtained by forming a molded product of 25 mm × 12.5 mm × 0.5 mm between two copper plates at 175 ° C. with a compression molding machine, post-curing at 180 ° C. for 12 hours, and then adjusting the tensile shear strength. Evaluated by seeking. Flame retardance was measured by molding a 1/16 inch thick test piece, evaluated according to the UL94V-0 standard, and expressed as the total burning time of 5 test pieces. The results are shown in Table 2.

Examples 14-19 and Comparative Examples 5-6
As an epoxy resin component, PSNE-A, PSNE-B, PSNE-C, PSNE-D obtained in Examples 5, 6, 7 and 8; resins obtained in Synthesis Examples 3 and 4; and o-cresol novolak type Using an epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.), PSN-A synthesized in Example 1 as a curing agent component, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent) 103, softening point 82 ° C.) or phenol aralkyl resin (curing agent B; manufactured by Meiwa Kasei Co., Ltd., MEH-7800SS, OH equivalent 175, softening point 67 ° C.). Furthermore, spherical silica (average particle size 18 μm) was used as a filler, triphenylphosphine was used as a curing accelerator, and an epoxy resin composition was obtained with the formulation shown in Table 3. The numerical value in a table | surface shows the weight part in a mixing | blending.

  This epoxy resin composition was molded at 175 ° C., and further post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 4.

Claims (10)

The following general formula (1)

(Here, A represents an alkyl group having 1 to 8 carbon atoms or a group consisting of a benzene ring or a naphthalene ring which may be substituted by a hydroxyl group, R ₁ represents a substituent represented by the following formula (a), R ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, p and q are the number of 0 to 2, is p + q is 1 or more .X the following formula (b) or formula (c) And R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents a number from 1 to 20.)

The hydroxyl group equivalent is 250 to 400 g / eq. A polyvalent hydroxy resin characterized by being in the range.   The polyvalent hydroxy resin according to claim 1, wherein the melt viscosity at 150 ° C. is in the range of 0.01 to 10.0 Pa · s. Represented by the formula (a) by reacting 0.1 to 4.0 moles of styrene in the presence of an acid catalyst with respect to 1 mole of the hydroxy group of the polyvalent hydroxy compound represented by the following general formula (2). A method for producing a polyvalent hydroxy resin, comprising substituting a benzene ring or a naphthalene ring of a polyvalent hydroxy compound with a substituted group.

(Here, A represents an alkyl group having 1 to 8 carbon atoms or a group consisting of a benzene ring or a naphthalene ring which may be substituted by a hydroxyl group, and X represents a bridging group represented by formula (b) or formula (c)). R ₂ , R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents a number from 1 to 20.)   The epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, The polyhydric hydroxy resin of Claim 1 or 2 becomes an essential component as a part or all of a hardening | curing agent.   A cured epoxy resin obtained by curing the epoxy resin composition according to claim 4. The following general formula (3)

(Here, A represents a group consisting of a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 8 carbon atoms or a glycidyloxy group, G represents a glycidyl group, and R ₁ represents the following formula (a): R ₂ represents a hydrocarbon group having 1 to 6 carbon atoms, p and q represent a number of 0 to 2, and p + q is 1 or more, X represents the following formula (b Or R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and n represents 1 to 20 Indicates the number of

The epoxy equivalent is 310-500 g / eq. Epoxy resin characterized by being in the range.   The epoxy resin according to claim 6, wherein the melt viscosity at 150 ° C. is in the range of 0.01 to 10.0 Pa · s.   A method for producing an epoxy resin, comprising reacting the polyvalent hydroxy resin according to claim 1 with epichlorohydrin to convert the hydroxy group of the polyvalent hydroxy resin into a glycidyl ether group.   In the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, the epoxy resin composition formed by mix | blending the epoxy resin of Claim 6 or 7 as an essential component.   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 9.

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