JP2010235823A - Epoxy resin, epoxy resin composition and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin that gives an epoxy resin cured product excellent in flame retardancy, low moisture absorption, adhesiveness, which can be suitably used for such purposes as sealing of electric-electronic parts and materials of circuit boards, and to provide an epoxy resin composition and a cured product of the composition by using the resin. <P>SOLUTION: The epoxy resin is an imide group-containing epoxy resin, which is obtained through steps of first obtaining an amino group-containing polyhydroxy resin by reacting anilines and phenols with a crosslinking agent such as formalin and p-xylene dichloride, then further reacting the obtained resin with an acid anhydride such as phthalic anhydride to imidize the amino group to obtain an imide group-containing polyhydroxy resin, and epoxidizing the obtained resin with epichlorohydrin. The epoxy resin composition contains the imide group-containing epoxy resin and a curing agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin that provides a cured product that is excellent in flame retardancy, moisture resistance, adhesion to a metal substrate, and the like, and an epoxy resin composition using the epoxy resin and a cured product thereof And is suitably used for insulating materials in the electrical and electronic fields such as printed wiring boards and semiconductor encapsulation.

  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 demands, various new structures of epoxy resins have been studied from the epoxy resin side as the main agent. Furthermore, recently, from the viewpoint of reducing the environmental load, there has been a movement to eliminate halogen-based flame retardants, and there is a demand for epoxy resins with better flame retardancy.

  However, no conventionally known epoxy resins satisfy these requirements. 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. Further, novolak type epoxy resins are known as improved heat resistance, but there are problems with moisture resistance, adhesion, and the like. Furthermore, the conventional epoxy resin whose main skeleton is composed of only hydrocarbons has no flame retardancy.

  As a measure for improving flame retardancy without using a halogen-based flame retardant, methods for adding a phosphate ester-based flame retardant are disclosed in JP-A-9-235449, JP-A-10-182792, and the like. Has been. 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 1, 3, and 4 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 phosphorus atoms or halogen atoms. Patent Document 2 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, and heat resistance. Patent Documents 5 and 6 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.

  Patent Documents 7, 8 and 9 disclose amino group-containing phenol resins, imide group-containing phenol resins and semiconductor encapsulating materials containing the same, but nothing focuses on flame retardancy.

JP-A-11-140166 JP 2004-57992 A Japanese Patent Laid-Open No. 4-173831 JP 2000-129092 A Japanese Patent Laid-Open No. 3-90075 JP-A-3-281623 Japanese Patent Laid-Open No. 7-18060 Japanese Patent Laid-Open No. 7-10970 JP 7-33858 A

  The object of the present invention is an epoxy resin having excellent flame retardancy, moisture resistance, and excellent performance such as adhesion to a metal substrate, and useful for applications such as lamination, molding, casting, and adhesion. An object of the present invention is to provide an epoxy resin composition using them and a cured product thereof.

That is, this invention is an imide group containing epoxy resin represented by following General formula (1).
HL- (XL) _n -H (1)

Here, L is any of the groups represented by the following formula (2) and formula (3), and R ₁ is a hydrogen atom, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. 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 is represented by formula (2) and formula (3). The existing ratio (molar ratio) of the group is in the range of 1: 9 to 9: 1.
X is a bridging group represented by the following formula (a) or formula (b), and 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, n represents a number from 1 to 10, and G represents a glycidyl group.
Z is an unsaturated aliphatic group having 2 to 24 carbon atoms, an unsaturated monocyclic aliphatic group, an unsaturated condensed polycyclic aliphatic group, or a cyclic aliphatic group that is linked to each other directly or by a bridging member. Saturated non-condensed polycyclic aliphatic group, monocyclic aromatic group which may have a chain aliphatic group as a substituent, condensed polycyclic aroma which may have a chain aliphatic group as a substituent And a divalent group selected from the group consisting of a monocyclic aromatic group or a condensed polycyclic aromatic group substituent which may have an unsaturated monocyclic aliphatic group as a substituent. .

  Moreover, this invention is an epoxy resin composition formed by mix | blending the said epoxy resin as an essential component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Furthermore, the present invention is a cured product obtained by curing the epoxy resin composition.

Moreover, this invention is a manufacturing method of said epoxy resin characterized by making the imide group containing polyvalent hydroxy resin and epichlorohydrin represented by the following general formula (1 ') react.
HL ′-(XL ′) _n —H (1 ′)

Here, L ′ is any of the groups represented by the following formula (2 ′) and formula (3 ′), and R ′ ₁ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or 1 carbon atom. -8 represents a hydrocarbon group, 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, represented by formulas (2 ') and (3') The ratio (molar ratio) of the represented group is in the range of 1: 9 to 9: 1. X and n have the same meaning as X and n in formula (1). Z has the same meaning as Z in formula (2).

  If the epoxy resin composition of the present invention is heat-cured, it can be made into an epoxy resin cured product, and this cured product is excellent in terms of flame retardancy, low moisture absorption, adhesion, etc. It can be suitably used for applications such as sealing electronic parts and circuit board materials.

¹ H-NMR spectrum of epoxy resin A Infrared absorption spectrum of epoxy resin A GPC chart of epoxy resin A

Hereinafter, the present invention will be described in detail.
The imide group-containing epoxy resin of the present invention is represented by the general formula (1).

  In the above general formula (1), L is a group selected from the groups represented by formula (2) and formula (3), and the abundance ratio (molar ratio) is 1: 9 to 9: 1, preferably 3 : 7 to 7: 3. X is a group represented by formula (a) or formula (b), and n is a number from 1 to 10. The resin is a mixture, but the average (number average) n is preferably in the above range. In addition, when a plurality of L and X are present in the formula (1), they may be the same or different, but L is represented by the formula (2) and the formula (3) in the above-mentioned presence ratio in the resin. There are groups to be However, since the resin is a mixture, it may be present as an average.

In Formula (2), R ₁ represents a hydrogen atom, an alkoxy group having 1 to 8 carbon atoms, a 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.

  In the formula (2), Z represents an unsaturated aliphatic group having 2 to 24 carbon atoms, an unsaturated monocyclic aliphatic group, an unsaturated condensed polycyclic aliphatic group, or a cyclic aliphatic group directly or by a crosslinking member. Unsaturated non-condensed polycyclic aliphatic groups connected to each other, monocyclic aromatic groups which may have a chain aliphatic group as a substituent, and chain aliphatic groups as a substituent Good condensed polycyclic aromatic group, selected from the group consisting of an unsaturated monocyclic aliphatic group as a substituent or a condensed polycyclic aromatic group which may have an unsaturated monocyclic aliphatic group as a substituent Represents a divalent group. Since Z is a group constituting the imide ring in the formula (2), it can also be understood as a residue of dicarboxylic acids. Dicarboxylic acids include phthalic anhydride, hydrophthalic anhydride, maleic anhydride and the like.

  In the formula (3), A is a group generated by epoxidizing a phenol (which may be a polyhydric phenol or a polycyclic aromatic phenol). That is, the OG group represented by the formula (3) is a substituted benzene ring or naphthalene ring, but may further have a substituent. Furthermore, when it has a substituent, as this substituent, a C1-C8 alkyl group or a glycidyl ether group is mentioned.

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. Here, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an amyl group, and a phenyl group. Preferred examples of the crosslinking group of the formula (a) include a methylene group, an ethylidene group, an isopropylidene group, and a phenylmethylene group. Preferred examples of the crosslinking group of the formula (b) include a p-xylylene group, an m-xylylene group, and 1 , 4-bisethylidenephenylene group, 1,3-bisethylidenephenylene group, 1,4-bisisopropylidenephenylene group, 1,3-bisisopropylidenephenylene group, 4,4′-bismethylenebiphenyl group, 3,4 '-Bismethylenebiphenyl group, 3,3'-Bismethylenebiphenyl group, 4,4'-bisethylidenebiphenyl group, 3,4'-bisethylidenebiphenyl group, 3,3'-bisethylidenebiphenyl group, 4,4 '-Bisisopropylidenebiphenyl group, 3,4'-bisisopropylidenebiphenyl group, 3,3'-bisisopropylidenebiphenyl group Phenyl group, 1,4-bismethylenenaphthalene group, 1,5-bismethylenenaphthalene group, 1,6-bismethylenenaphthalene group, 2,7-bismethylenenaphthalene group, 1,4-bisethylidenenaphthalene group, 1, 5-bisethylidenenaphthalene group, 1,6-bisethylidenenaphthalene group, 2,7-bisethylidenenaphthalene group, 1,4-bisisopropylidenenaphthalene group, 1,5-bisisopropylidenenaphthalene group, 1,6-bis Examples are isopropylidenenaphthalene group and 2,7-bisisopropylidenenaphthalene group. Although X bridges L, the substitution position of X with respect to the group represented by Formula (2) and Formula (3) constituting L is not particularly limited.

  The epoxy resin of the present invention is advantageously produced by reacting the imide group-containing polyvalent hydroxy resin represented by the general formula (1 ′) with epichlorohydrin, but is not limited to this reaction. The imide group-containing polyvalent hydroxy resin represented by the general formula (1 ′) is a resin in which at least a part, preferably all of the part epoxidized with epichlorohydrin is H or OH, In the general formula (1) or the formulas (2) to (3), this corresponds to a compound in which the site of the glycidyl ether group is OH.

In general formula (1 ′), the same symbols or formulas as in general formula (1) or formulas (2) to (3) have the same meanings unless otherwise specified. In the general formula (2), only L ′ is different from the general formula (1), but the difference between L and L ′ is different in that the glycidyl ether group is an OH group. In formula (2 ′), only R ′ ₁ is different from formula (2), but the difference between R ₁ and R ′ ₁ is that when R ′ ₁ has a glycidyl ether group, it is an OH group. It is different in that. In formula (3 ′), A may differ from formula (3), and when A in formula (3) has a glycidyl ether group, it differs in that it is an OH group.

  In addition to the reaction of reacting such an imide group-containing polyvalent hydroxy resin with epichlorohydrin, the epoxy resin of the present invention reacts with an imide group-containing polyvalent hydroxy resin represented by the general formula (1 ′) and an allyl halide to form allyl. It can also be obtained by reacting with a peroxide after making an ether resin.

  Advantageously, the reaction involves reacting the imide group-containing polyvalent hydroxy resin with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction. For example, after dissolving the imide group-containing polyvalent hydroxy resin 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. The method of making it react for 1 to 10 hours in the range is mentioned. The amount of alkali metal hydroxide used is 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, based on 1 mol of hydroxyl group of the imide group-containing polyvalent hydroxy resin. It is. Moreover, epichlorohydrin is used in excess with respect to 1 mol of hydroxyl group of the imide group-containing polyvalent hydroxy resin, but usually from 1.5 to 30 mol, preferably 1 mol of hydroxyl group in the imide group-containing polyvalent hydroxy resin. Is in the range of 2-15 moles. 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 is an epoxy resin composition comprising an epoxy resin and a curing agent, and contains an epoxy resin represented by the above general formula (1) as an essential component as an epoxy resin component.

  As the curing agent when the epoxy resin represented by the general formula (1) is an essential component, any of the curing agents generally known as epoxy resin curing agents can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines. Specifically, bivalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalene diol, or tris -Trivalent or higher phenols represented by (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There is. 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 resins synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, bischloromethylnaphthalene, and the like. In addition, an imide group-containing polyvalent hydroxy resin represented by the general formula (1 ′) is also preferably exemplified.

  Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, and trimellitic anhydride.

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

  The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3 ′, 5,5′-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl-4 Epoxidized dihydric phenols such as 4,4'-dihydroxybiphenol, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Of phenol aralkyl resins synthesized from epoxidized products of trivalent or higher phenols such as phenol novolak and o-cresol novolak, epoxidized products of co-condensation resin of dicyclopentadiene and phenol, phenol and paraxylylene dichloride, etc. Epoxidized products, phenols and bischrom Examples thereof include epoxidized products of biphenyl aralkyl type phenol resins synthesized from romethyl biphenyl and the like, and epoxidized products of naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride. These epoxy resins may be used alone or in combination of two or more. More preferred epoxy resins are crystalline epoxy resins obtained from 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenol, 3,3 ′, 5,5′-tetramethyl-bisphenol F, etc. Examples thereof include solid epoxy resins at room temperature such as epoxy resins obtained from polyfunctional resins such as o-cresol novolac, phenol aralkyl resins, and epoxy resins obtained from biphenyl aralkyl resins.

  In addition, the epoxy resin composition of the present invention may be appropriately mixed with an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, phenoxy resin, etc. You may mix | blend additives, such as a filler, a pigment, a refractory agent, a thixotropic agent, a coupling agent, and a fluidity improver. Examples of the inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a sealing material is 70 wt% or more, and more preferably 80 wt% or more.

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

  Furthermore, 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.

  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, addition reaction products of organic phosphines and quinone compounds, tetraphenylphosphine Tetra-substituted phosphonium / tetra-substituted borate such as phonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / Examples include tetraphenylboron salts such as tetraphenylborate. 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.

  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.

  The cured product obtained by curing the epoxy resin composition of the present invention can be molded by a method such as casting, compression molding or transfer molding of the epoxy resin composition. 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-6911. The GPC measurement conditions were as follows: apparatus: HLC-82A (manufactured by Tosoh Corp.), column: TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent: tetrahydrofuran, flow rate 1 ml / min, temperature; 38 ° C., detector; RI; polystyrene standard solution was used for the calibration curve.

Synthesis example 1
260.0 g of aniline, 1300.0 g of phenol, and 270.0 g of a 37% formalin solution were charged and dissolved by heating to 80 ° C. while introducing nitrogen. Next, the temperature was raised to 95 ° C. with stirring and refluxed for 2 hours. After dehydration, the temperature was raised to 180 ° C. and reacted for 2 hours. Thereafter, unreacted phenol and aniline were removed at 180 ° C. under reduced pressure to obtain 596.8 g of an amino group-containing polyvalent hydroxy resin. The obtained resin had a hydroxyl equivalent of 91 g / eq. The amine equivalent is 246 g / eq. The softening point was 61 ° C. and the melt viscosity at 150 ° C. was 0.02 Pa · s.
596.8 g of the obtained amino group-containing polyvalent hydroxy resin and 334.0 g of phthalic anhydride were charged and dissolved by heating to 80 ° C. while introducing nitrogen. Then, it heated up to 150 degreeC, stirring, and was made to react for 1 hour. During this time, water produced by the reaction was removed from the system. Thereafter, unreacted phthalic anhydride was removed at 230 ° C. under reduced pressure to obtain 810.5 g of an imide group-containing polyvalent hydroxy resin. The hydroxyl equivalent of the imide group-containing polyvalent hydroxy resin is 313 g / eq. The amine equivalent was 12211 g / eq. The softening point was 105 ° C. and the melt viscosity at 150 ° C. was 0.58 Pa · s.

Synthesis example 2
372.5 g of aniline, 376.4 g of phenol, and 350.1 g of p-xylene dichloride were charged, heated to 105 ° C. while introducing nitrogen, and reacted for 1 hour with stirring. Furthermore, it heated up to 180 degreeC and was made to react for 9 hours. During this time, hydrochloric acid produced by the reaction was removed from the system. Thereafter, 560.8 g of 25% aqueous ammonia was added for neutralization, and unreacted phenol and aniline were removed at 180 ° C. under reduced pressure. This was dissolved in 700 g of methyl isobutyl ketone, washed 5 times with 500 g of pure water, and methyl isobutyl ketone was removed by distillation under reduced pressure to obtain 497.2 g of an amino group-containing polyvalent hydroxy resin. The hydroxyl group equivalent of the amino group-containing polyvalent hydroxy resin is 165 g / eq. The amine equivalent is 600 g / eq. The softening point was 61 ° C., and the melt viscosity at 150 ° C. was 0.05 Pa · s.
Next, 200.0 g of the resulting amino group-containing polyvalent hydroxy resin and 49.4 g of phthalic anhydride were charged and heated to 90 ° C. and dissolved while introducing nitrogen. Further, the temperature was raised to 150 ° C. with stirring and the reaction was carried out for 2 hours. During this time, water produced by the reaction was removed from the system. Thereafter, unreacted phthalic anhydride was distilled off at 180 ° C. under reduced pressure, and 228.7 g of an imide group-containing polyvalent hydroxy resin was obtained. The hydroxyl equivalent of the imide group-containing polyvalent hydroxy resin is 305 g / eq. The amine equivalent was 14110 g / eq. The softening point was 87 ° C., and the melt viscosity at 150 ° C. was 0.15 Pa · s.

Synthesis example 3
Charge 93.1 g of aniline, 94.1 g of phenol, 125.6 g of 4,4′-bischloromethylbiphenyl and 37.2 g of chlorobenzene, heat to 105 ° C. while introducing nitrogen, and react for 2.5 hours with stirring. I let you. Next, chlorobenzene was removed, and the temperature was further raised to 180 ° C. to react for 9 hours. During this time, hydrochloric acid produced by the reaction was removed from the system. Thereafter, 147.2 g of 25% aqueous ammonia was added for neutralization, and unreacted phenol and aniline were removed at 180 ° C. under reduced pressure. This was dissolved in 400 g of toluene, washed with 200 g of pure water five times, and toluene was removed by distillation under reduced pressure to obtain 107.2 g of an amino group-containing polyvalent hydroxy resin. The hydroxyl group equivalent of the amino group-containing polyvalent hydroxy resin is 178 g / eq. The amine equivalent was 747 g / eq. The softening point was 86 ° C., and the melt viscosity at 150 ° C. was 0.23 Pa · s.
Next, 50.0 g of the obtained amino group-containing polyvalent hydroxy resin and 9.9 g of phthalic anhydride were charged and heated to 90 ° C. and dissolved while introducing nitrogen. Further, the temperature was raised to 150 ° C. with stirring and the reaction was carried out for 2 hours. During this time, water produced by the reaction was removed from the system. Thereafter, unreacted phthalic anhydride was distilled off at 180 ° C. under reduced pressure, and then 55.5 g of an imide group-containing polyvalent hydroxy resin was obtained. The hydroxyl group equivalent of the imide group-containing polyvalent hydroxy resin is 209 g / eq. The amine equivalent was 16429 g / eq. The softening point was 109 ° C. and the melt viscosity at 150 ° C. was 1.15 Pa · s.

Example 1
150 g of the imide group-containing polyvalent hydroxy resin obtained in Synthesis Example 1 was dissolved in 266 g of epichlorohydrin and 40 g of diethylene glycol dimethyl ether. Thereafter, 28.0 g of 96% potassium hydroxide was added over 3 hours at 50 ° C. with stirring, and the reaction was continued for another hour after the addition was completed. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 167 g of an imide group-containing epoxy resin (epoxy resin A). The resulting epoxy resin had a softening point of 84 ° C., a melt viscosity of 0.45 Pa · s, and an epoxy equivalent of 481 g / eq. Met. The NMR spectrum, IR absorption spectrum and GPC chart of this epoxy resin A are shown in FIGS.

Example 2
150 g of the imide group-containing polyvalent hydroxy resin obtained in Synthesis Example 2 was dissolved in 505 g of epichlorohydrin and 76 g of diethylene glycol dimethyl ether. Thereafter, 53.1 g of 96% potassium hydroxide was added over 3 hours at 50 ° C. with stirring, and the reaction was continued for another hour after the addition was completed. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 190 g of an imide group-containing epoxy resin (epoxy resin B). The resulting epoxy resin had a softening point of 43 ° C., a melt viscosity of 0.03 Pa · s, and an epoxy equivalent of 333 g / eq. Met.

Example 3
50 g of the imide group-containing polyvalent hydroxy resin obtained in Synthesis Example 3 was dissolved in 133 g of epichlorohydrin and 20 g of diethylene glycol dimethyl ether. Thereafter, 10.0 g of 96% potassium hydroxide was added over 3 hours at 50 ° C. with stirring, and the reaction was continued for another hour after the addition was completed. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 179 g of an imide group-containing epoxy resin (epoxy resin C). The resulting epoxy resin had a softening point of 88 ° C., a melt viscosity of 0.89 Pa · s, and an epoxy equivalent of 377 g / eq. Met.

Examples 4-8 and Comparative Examples 1-2
As epoxy resin components, epoxy resins A, B and C synthesized in Examples 1 to 3, o-cresol novolac type epoxy resin (OCNE: Nippon Kayaku Co., Ltd., EOCN-1020-65; epoxy equivalent 200, hydrolyzable chlorine) 400 ppm, softening point 65 ° C.), and as a curing agent component, the imide group-containing polyvalent hydroxy resin obtained in Synthesis Example 1, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., PSM-4261; OH equivalent 103, softening Point 80 ° C.) or phenol aralkyl resin (curing agent B; manufactured by Meiwa Kasei, 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 1. 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 180 ° 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 2.
In addition, the measurement of the glass transition point and the linear expansion coefficient was calculated | required with the temperature increase rate of 10 degree-C / min using the thermomechanical measuring apparatus. 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 burning time was expressed as the total burning time in five tests in accordance with UL94V-0 standard using a test piece having a thickness of 1/16 inch. 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, Evaluated by seeking.

Claims (4)

The following general formula (1),
HL- (XL) _n -H (1)
(Where L is the following formula (2) and formula (3)

R ₁ represents a hydrogen atom, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and A represents a group having 1 to 8 carbon atoms. The group which consists of the benzene ring or naphthalene ring which an alkyl group or a glycidyloxy group may substitute is shown, and the abundance ratio (molar ratio) of the group represented by Formula (2) and Formula (3) is 1: 9-9. : 1 and G is the following formula (a) or formula (b)

R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents a benzene ring, a biphenyl ring or a naphthalene ring. N represents a number of 1 to 10, G represents a glycidyl group, Z represents an unsaturated aliphatic group having 2 to 24 carbon atoms, an unsaturated monocyclic aliphatic group, an unsaturated condensed polycyclic ring. A monocyclic fragrance optionally having a chain aliphatic group as a substituent, an unsaturated non-condensed polycyclic aliphatic group in which the cyclic aliphatic group, the cyclic aliphatic group are connected to each other directly or by a cross-linking member An aromatic group, a condensed polycyclic aromatic group which may have a chain aliphatic group as a substituent, and a monocyclic aromatic group which may have an unsaturated monocyclic aliphatic group as a substituent, or A divalent group selected from the group consisting of condensed polycyclic aromatic groups is shown. The imide group containing epoxy resin represented by this. The method for producing an epoxy resin according to claim 1, wherein the following general formula (1 ')
HL ′-(XL ′) _n —H (1 ′)
(Here, L ′ is the following formula (2 ′) and formula (3 ′):

R ′ ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and A represents an alkyl having 1 to 8 carbon atoms. A group consisting of a benzene ring or a naphthalene ring which may be substituted by a group or a hydroxyl group, wherein the abundance ratio (molar ratio) of the groups represented by formula (2) and formula (3) is 1: 9 to 9: 1 X, Z and n have the same meaning as X, Z and n in formulas (1) to (2). An epoxy resin-containing polyhydric hydroxy resin represented by (II) is reacted with epichlorohydrin.   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 1 as an essential component. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 3.

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