JP2009242658A - Polyhydroxy compound, epoxy resin, manufacturing method thereof, epoxy resin composition, and hardened product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin, a polyhydroxyl compound and a composition thereof, providing a hardened product excellent in flame retardant, humidity resistance, low elasticity and so on, and suitable for applications such as sealing for electronic components, and circuit substrate materials. <P>SOLUTION: An indene-modified polyhydroxy compound having a hydroxyl group equivalent of 200 to 400 g/eq., which is obtained by reacting 1 mol of a polyhydroxy compound such as a phenol aralkyl resin with 0.1 to 4.0 mol of indene in the presence of an acid catalyst, and an epoxy resin obtained by reacting the polyhydroxy compound with epichlorohydrin are provided. An epoxy resin composition comprises the polyhydroxy compound or the epoxy resin as an essential component. <P>COPYRIGHT: (C)2010,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 compound 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.

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 Japanese Patent Laid-Open No. 9-208673

  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, Patent Documents 5 and 6 disclose a styrenated phenol novolac resin and an epoxy resin composition using the epoxy resin. None of these focus on flame retardancy.

  Patent Document 7 discloses an indene-modified polyfunctional phenolic compound, and it is described that a cured product obtained by using this compound is excellent in low dielectric constant, etc., but attention has been paid to flame retardancy. In addition, there was nothing that focused on the relationship between functional group concentration and flame retardancy.

  The object of the present invention is to provide an epoxy resin having excellent performance in terms of moisture resistance, low elasticity, etc., as well as excellent flame resistance in applications such as lamination, molding, casting and adhesion, and excellent flame resistance Providing an epoxy resin composition useful for sealing electrical and electronic parts, circuit board materials, etc. that provide a cured product that has excellent properties such as moisture resistance and low elasticity, and also provides a cured product thereof There is to do.

（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、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（ｃ）又は式（ｄ）で表される架橋基であり、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は独立に、水素原子又は炭素数１〜６の炭化水素基を示し、Ｂはベンゼン環、ビフェニル環又はナフタレン環からなる基を示し、ｎは１〜２０の数を示す。

）で表され、水酸基当量が２００〜４００ｇ／ｅｑ．の範囲であることを特徴とする多価ヒドロキシ化合物である。 That is, the present invention provides the following general formula (1)

(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), p and q Represents a number of 0 to 2, but p + q is 1 or more, X is a bridging group represented by the following formula (c) or formula (d), and R ₂ , R ₃ , R ₄ and R ₅ are Independently, a hydrogen atom or a C1-C6 hydrocarbon group is shown, B shows the group which consists of a benzene ring, a biphenyl ring, or a naphthalene ring, n shows the number of 1-20.

) With a hydroxyl group equivalent of 200 to 400 g / eq. It is a polyhydric hydroxy compound characterized by being in the range.

  The polyvalent hydroxy compound preferably has a melt viscosity at 150 ° C. in the range of 0.02 to 2.0 Pa · s.

（式中、Ａ、Ｘ及びｎは、一般式（１）と同じ意味を有する。） Further, the present invention is characterized in that 0.1 mol to 4.0 mol of indene is reacted in the presence of an acid catalyst with respect to 1 mol of the hydroxy group of the polyvalent hydroxy compound represented by the following general formula (2). This is a method for producing a polyvalent hydroxy compound having a structure in which the substituent represented by the above formula (a) is substituted on the benzene ring or naphthalene ring of the polyvalent hydroxy compound.

(In the formula, A, 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。）
で表されるエポキシ当量が２５０〜５００ｇ／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).)
The epoxy equivalent represented by 250-500 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 0.02 to 2.0 Pa · s.

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

  Furthermore, the present invention is an epoxy resin composition comprising one or both of the above polyvalent hydroxy compound and the above epoxy resin as an essential component in an epoxy resin composition comprising an epoxy resin and a curing agent. Moreover, this invention is a flame-retardant epoxy resin hardened | cured material formed by hardening | curing said epoxy resin composition.

  When applied to an epoxy resin composition, the epoxy resin and the polyvalent hydroxy compound 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.

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

  In the PIN of the present invention, first, the hydroxyl equivalent can be arbitrarily adjusted by adding indene to the basic structure of the polyvalent hydroxy compound (2). In other words, in the cured epoxy resin, the hydroxypropyl group produced by the reaction between the epoxy group and the hydroxyl group is said to be easily burned, but by increasing the hydroxyl equivalent, the flammable component fat derived from the epoxy group The group carbon ratio is lowered, and high flame retardancy can be exhibited. Moreover, by adding indene 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 PIN of the present invention, by adding indene, the molecular weight increases, but the melt viscosity range suitable for a semiconductor encapsulant or the like can be maintained. 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 PIN of the present invention can be obtained by addition reaction of the polyvalent hydroxy compound (2) represented by the general formula (2) and indene. At this time, the ratio between the polyvalent hydroxy compound (2) and the indene is represented by a phenol component (A in the general formula (2) in consideration of the balance between flame retardancy and curability of the obtained cured product). The ratio of indene to 1 mol) is preferably in the range of 0.1 to 4.0 mol, more preferably in the range of 1.0 to 3.0 mol. From another point of view, the use ratio of indene with respect to 1 mol of the hydroxy group in the polyvalent hydroxy compound (2) is preferably in the range of 0.1 to 4.0 mol, more preferably 1.0 to 3.0 mol. It is a range. From another point of view, the use ratio of indene to 1 mol of polyvalent hydroxy compound (2) is preferably in the range of 0.1 to 4.0 mol, more preferably in the range of 1.0 to 3.0 mol.

  In this reaction, indene attacks the aromatic ring having an OH group in the polyvalent hydroxy compound (2) to replace the indenyl group represented by the above formula (a). The indene is added mainly at the vacant ortho and / or para position of the polyvalent hydroxy compound.

  Further, in the PIN of the present invention, when the proportion of indene used is excessive with respect to the phenol component, the proportion of indene addition reaction increases, and the molecular weight can be easily increased.

  The hydroxyl equivalent of the PIN of the present invention thus obtained is 200 to 400 g / eq. And more preferably 200 to 300 g / eq. Range. If the hydroxyl equivalent is lower than this range, it is difficult to obtain high flame retardancy. .

  Examples of the polyvalent hydroxy compound (2) serving as the basic structure of the PIN of the present invention include general-purpose phenol resins, phenol aralkyl resins, biphenyl aralkyl resins, and naphthol aralkyl resins. In order to obtain higher flame retardancy, 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 (d) is preferable.

  The melt viscosity at 150 ° C. of the PIN of the present invention is preferably in the range of 0.02 to 2.0 Pa · s. From the viewpoint of workability, the melt viscosity is preferably as low as possible within the above range.

  Further, the softening point is preferably 40 to 150 ° C, and preferably in the range of 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 falls, 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 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 3 carbon atoms. When the hydroxyl group is substituted, the number is preferably 1. R ₁ represents an indenyl group represented by the above formula (a). p and q represent a number of 0 to 2, but p + q is 1 or more. Preferably, an average of 0.2 to 2 indenyl groups are substituted for one A. X is a crosslinking group represented by the formula (c) or the formula (d), preferably a crosslinking group represented by the formula (d). R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and n represents 1 to 1 The number of 20 is shown. Preferably, it is in the range of 1.5 to 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.

  Next, a method for manufacturing the PIN of the present invention will be described. As the polyvalent hydroxy compound (2) used in the method for producing the PIN 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、Ｒ₂及びＲ₃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は通常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 ₂ and R ₃ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n shows the number of 1-20 normally.

  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、Ｒ₄及びＲ₅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は通常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 ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n shows the number of 1-20 normally.

  Furthermore, a biphenyl aralkyl resin is mentioned similarly. Specifically, the linking group X in the general formula (2) is derived from dihydroxymethylbiphenyls, dimethoxymethylbiphenyls, dichloromethylbiphenyls, etc., for example, represented by the general formula (7).

一般式（７）において、Ｒ₄、Ｒ₅、Ｒ₇及びｎは一般式（６）と同じ意味を有する。

In the general formula (7), R ₄ , R ₅ , R ₇ and n have the same meaning as in the general formula (6).

一般式（８）において、Ｒ₄、Ｒ₅、Ｒ₇及びｎは一般式（６）と同じ意味を有する。 Furthermore, a naphthalene aralkyl resin is mentioned similarly. Specifically, the linking group X in the general formula (2) is derived from dihydroxymethylnaphthalenes, dimethoxymethylnaphthalenes, dichloromethylnaphthalenes, etc., for example, represented by the general formula (8).

In the general formula (8), R ₄ , R ₅ , R ₇ and n have the same meaning as in the general formula (6).

  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 (9) It is represented by

ここで、一般式（９）において、Ｒ₄、Ｒ₅、Ｒ₇及びｎは一般式（６）と同じ意味を有する。

Here, in the general formula (9), R ₄ , R ₅ , 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.

  The indene used for the reaction contains a polyvalent hydroxy compound obtained when it contains an unsaturated bond-containing component such as styrene, α-methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, and vinylnaphthalene as other reaction components. These include compounds in which the groups resulting therefrom are substituted on the aromatic ring. The phenol resin obtained by the method for producing a polyvalent hydroxy compound of the present invention may contain a polyvalent hydroxy compound 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 indene is reacted with polyvalent hydroxy compound (2), the amount of indene 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. 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 equivalent of PIN is 200 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 indene 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 high indene usage ratio, and are relatively high in alkyl-substituted phenol novolacs, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, etc. The usage rate may be small.

  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 clay, silica-alumina, zeolite and other solid acids.

  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 together 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 indene is added. The method of making it react, making it dripping is common. 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 PINE) of the present invention is represented by the general formula (3). The polyvalent hydroxy compound (PIN) is represented by the general formula (1). PINE can be obtained by epoxidizing PIN.

In general formula (3), R ₁ represents a hydrogen atom, an alkoxy group having 1 to 8 carbon atoms, glycidyloxy group, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Here, examples of the alkoxy group include a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, an allyloxy group, a propargyl ether group, a putoxy group, a phenoxy group, and a benzyloxy group. The halogen atom includes a fluorine atom, a chlorine atom, Examples include bromine atoms. The hydrocarbon groups include methyl, ethyl, vinyl, ethyne, n-propyl, isopropyl, allyl, propargyl, n-butyl, sec-butyl, tert-butyl, n- Examples include amyl group, sec-amyl group, tert-amyl group, cyclohexyl group, phenyl group, benzyl group and the like.

X is a bridging group represented by formula (a) or formula (b), but R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. , B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring. In addition, these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. X crosslinks A, but the substitution position of X is not particularly limited.
The pine of the present invention is advantageously produced by reacting the PIN represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction.

  In addition to the reaction of reacting PIN with epichlorohydrin, a method of reacting PIN with allyl halide to form an allyl ether compound and then reacting with peroxide can be employed. The reaction for reacting the PIN with epichlorohydrin can be carried out in the same manner as a normal epoxidation reaction.

  For example, after dissolving the above PIN in excess epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 20 to 150 ° C., preferably 30 to 80 ° C. in the range of 1 to 10 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 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 hydroxyl group in PIN. 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 PINE as a part or all of an epoxy resin.
2) A composition containing the PIN as part or all of the curing agent.
3) The composition which mix | blended the said PINE and PIN as a part or all of an epoxy resin and a hardening | curing agent.

  In the case of the above compositions 2) and 3), the amount of PIN is usually in the range of 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 PIN is used as the total amount of the curing agent, the amount of PIN is usually determined in consideration of the equivalent balance between the OH group of PIN 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 PIN 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 PIN 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 the amount of PIN is less than this, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small, and if it is more than this, the moldability and the strength of the cured product are lowered.

  As the curing agent other than PIN, all those generally known as epoxy resin curing agents 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, naphthalenediol, or the like. , 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, There are polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, and the like.

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 triethylenetetramine.
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.

  Moreover, in this epoxy resin composition, you may mix | blend another kind of epoxy resin other than PINE as an epoxy resin component. 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 uses PINE of this invention as an essential component, the compounding quantity of PINE 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, transfer molding or the like. 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 4000 × 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.

Example 1
200 g (1.0 mol) of bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) manufactured by Honshu Chemical Co., Ltd.) is charged into a 1 L flask. The temperature was raised to 175 ° C. After melting, 0.1 g of p-toluenesulfonic acid was charged with stirring, and 232 g (2.0 mol) of indene was added dropwise at about 175 ° C. over about 3 hours. Further, the reaction was continued for 3 hours under total reflux. Thereafter, low-boiling components were removed under reduced pressure. Further, it was dissolved in 500 g of MIBK and washed with water at 80 ° C. five times. Subsequently, after MIBK was distilled off under reduced pressure, 413 g of a polyvalent hydroxy compound 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. Met. This compound is referred to as PIN-A.

Example 2
In a 1 L four-necked flask, phenol novolac (n = 1 component (38%) by GPC measurement (38%), n = 2 or more component (62%)) as a polyvalent hydroxy compound component, 200 g, p-toluenesulfone as an acid catalyst The acid 0.19g was prepared and it heated up at 150 degreeC. Next, with stirring at 150 ° C., 177 g of indene was added dropwise 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, 365 g of a polyvalent hydroxy compound was obtained. Its softening point is 93 ° C., melt viscosity at 150 ° C. is 0.38 Pa · s, and hydroxyl equivalent is 200 g / eq. Met. This compound is referred to as PIN-B.

Example 3
200 g of phenol aralkyl resin (Maywa Kasei Co., Ltd .; MEH-7800SS, hydroxyl group equivalent 175 g / eq., Softening point 66 ° C., melt viscosity 0.050 Pa · s at 150 ° C.) as polyvalent hydroxy compound component, acid catalyst P-toluenesulfonic acid 0.17 g was charged and heated to 150 ° C. Next, 133 g of indene was added dropwise over 3 hours while stirring at 150 ° C. to cause the reaction. Thereafter, the same treatment as in Example 1 was performed, and then 328 g of a polyvalent hydroxy compound was obtained. Its softening point is 102 ° C., melt viscosity at 150 ° C. is 1.67 Pa · s, and hydroxyl equivalent is 291 g / eq. Met. This compound is referred to as PIN-C. FIG. 1 shows the ¹ H-NMR spectrum of PIN-C, FIG. 2 shows the infrared absorption spectrum, and FIG. 3 shows the GPC chart.

Example 4
As a polyvalent hydroxy compound component, 250 g of biphenyl aralkyl resin (Maywa Kasei Co., Ltd .; MEH-7851, hydroxyl group equivalent 206 g / eq., Softening point 78 ° C., melt viscosity 0.150 Pa at 150 ° C.), acid catalyst P-toluenesulfonic acid 0.16g was prepared and heated to 150 ° C. Next, with stirring at 150 ° C., 70 g of indene was added dropwise over 2 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 312 g of a polyvalent hydroxy compound was obtained. Its softening point is 95 ° C., melt viscosity at 150 ° C. is 0.66 Pa · s, and hydroxyl equivalent is 264 g / eq. Met. This compound is referred to as PIN-D.

Example 5
250 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 a polyvalent hydroxy compound component As an acid catalyst, 0.16 g of p-toluenesulfonic acid was charged and the temperature was raised to 150 ° C. Next, with stirring at 150 ° C., 69 g of indene was dropped over 2 hours to be reacted. Thereafter, the same treatment as in Example 1 was performed, and then 311 g of a polyvalent hydroxy compound was obtained. Its softening point is 97 ° C., melt viscosity at 150 ° C. is 0.34 Pa · s, and hydroxyl equivalent is 268 g / eq. Met. This compound is referred to as PIN-E.

Example 6
In a four-necked separable flask, 150 g of PIN-A obtained in Example 1, 286 g of epichlorohydrin and 43 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After being uniformly dissolved, 43.0 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours under a reduced pressure of 130 mmHg, and the refluxed water and epichlorohydrin were separated 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 169 g of an epoxy resin (PINE-A). 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.

Example 7
In a four-necked separable flask, 150 g of PIN-B obtained in Example 2, 286 g of epichlorohydrin and 43 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, 43.0 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours while maintaining the temperature at 65 ° C. under a reduced pressure of 130 mmHg. Then, the process similar to Example 6 was performed and the epoxy resin 169g was obtained (PINE-B). The epoxy equivalent of the obtained resin was 270 g / eq. The softening point was 77 ° C. and the melt viscosity at 150 ° C. was 0.16 Pa · s.

Example 8
In a four-necked separable flask, 150 g of PIN-C obtained in Example 3, 286 g of epichlorohydrin, and 43 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After being uniformly dissolved, 43.0 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours under a reduced pressure of 130 mmHg, and the refluxed water and epichlorohydrin were separated 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 170 g of an epoxy resin (PINE-C). The epoxy equivalent of the obtained resin was 350 g / eq. The softening point was 95 ° C. and the melt viscosity at 150 ° C. was 1.45 Pa · s. FIG. 4 shows the ¹ H-NMR spectrum of PINE-C, FIG. 5 shows the infrared absorption spectrum, and FIG. 6 shows the GPC chart.

Example 9
Using 150 g of PIN-D obtained in Example 4, it was reacted in the same manner as in Example 8 to obtain 173 g of epoxy resin (PINE-D). The epoxy equivalent of the obtained resin was 327 g / eq. The softening point was 85 ° C., and the melt viscosity at 150 ° C. was 0.55 Pa · s.

Example 10
Using 150 g of PIN-E obtained in Example 5, the reaction was conducted in the same manner as in Example 8 to obtain 170 g of epoxy resin (PINE-E). The epoxy equivalent of the obtained resin was 333 g / eq. The softening point was 88 ° C. and the melt viscosity at 150 ° C. was 0.28 Pa · s.

Examples 11-16 and Comparative Examples 1-2
PIN-A, PIN- obtained in Examples 1, 2, 3, 4, and 5 were used as curing agents, using o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) as an epoxy resin component. In addition to B, PIN-C, PIN-D and PIN-E, 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 measuring device. Further, 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 molding 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 17-23 and Comparative Examples 3-4
As an epoxy resin component, PINE-A, PINE-B, PINE-C, PINE-D, PINE-E or o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200 obtained in Examples 5, 6, 7, and 8) PIN-A synthesized in Example 1 and phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening point 82 ° C.) Phenol aralkyl resin (curing agent B; manufactured by Meiwa Kasei, MEH-7800SS, OH equivalent 175, softening point 67 ° C.) was used. 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.

  The 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.

¹ H-NMR spectrum of the polyvalent hydroxy compound of the present invention Infrared absorption spectrum of the polyvalent hydroxy compound of the present invention GPC chart of the polyvalent hydroxy compound of the present invention ¹ H-NMR spectrum of the epoxy resin of the present invention Infrared absorption spectrum of the epoxy resin of the present invention GPC chart of epoxy resin of the present invention

Claims (10)

The following general formula (1)

(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), p and q Represents a number of 0 to 2, but p + q is 1 or more, X is a bridging group represented by the following formula (c) or formula (d), and R ₂ , R ₃ , R ₄ and R ₅ are Independently, a hydrogen atom or a C1-C6 hydrocarbon group is shown, B shows the group which consists of a benzene ring, a biphenyl ring, or a naphthalene ring, n shows the number of 1-20.

) With a hydroxyl group equivalent of 200 to 400 g / eq. A polyvalent hydroxy compound characterized by being in the range of   The polyvalent hydroxy compound according to claim 1, wherein the melt viscosity at 150 ° C is in the range of 0.02 to 2.0 Pa · s. Formula (a), wherein 0.1 mol to 4.0 mol of indene is reacted in the presence of an acid catalyst with respect to 1 mol of a hydroxy group of a polyvalent hydroxy compound represented by the following general formula (2). The manufacturing method of the polyhydric hydroxy compound which has the structure where the substituent represented by these was substituted by the benzene ring or naphthalene ring of the polyhydric hydroxy compound.

(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, and X is a bridging group represented by formula (c) or formula (d); R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and n represents 1 to 1 20 number is shown.)   An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyvalent hydroxy compound according to claim 1 or 2 is an essential component as part or all of the curing agent.   A flame retardant epoxy resin cured product obtained by curing the epoxy resin composition according to claim 4. 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, G represents a glycidyl group, and R ₁ is represented by the following formula (a). P and q represent a number of 0 to 2, but p + q is 1 or more, X is a cross-linking group represented by the following formula (c) or formula (d), R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and n is a number from 1 to 20 Indicates.

) Represented by an epoxy equivalent of 250 to 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 0.02 to 2.0 Pa · s.   A method for producing an epoxy resin, comprising reacting the polyvalent hydroxy compound according to claim 1 with epichlorohydrin to convert the hydroxy group of the polyvalent hydroxy compound 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.   A flame-retardant epoxy resin cured product obtained by curing the epoxy resin composition according to claim 9.

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